Battery Design Module

User’s Guide
Battery Design Module User’s Guide
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Part number: CM021501

C o n t e n t s

Chapter 1: Introduction

About the Battery Design Module 24

What Can the Battery Design Module Do? . . . . . . . . . . . . . 24
Battery Design Module Physics Interface Guide . . . . . . . . . . . 25
Common Physics Interface and Feature Settings and Nodes . . . . . . 28
Where Do I Access the Documentation and Application Libraries? . . . . 29

Overview of the User’s Guide 32

Chapter 2: Modeling with Electrochemistry

Introduction to Electrochemistry Modeling 36

What Is Electrochemistry? . . . . . . . . . . . . . . . . . . . 36
Electrochemical Applications . . . . . . . . . . . . . . . . . . 37
Fundamentals of Electrochemistry Modeling . . . . . . . . . . . . 37
Current Distribution Cases and Choosing the Right Interface to
Model an Electrochemical Cell . . . . . . . . . . . . . . . . 39
Understanding the Different Approximations for Conservation of
Charge in Electrolytes . . . . . . . . . . . . . . . . . . . 40
Modeling Electrochemical Reactions . . . . . . . . . . . . . . . 44
Double Layer Capacitance . . . . . . . . . . . . . . . . . . . 51
Porous Electrodes . . . . . . . . . . . . . . . . . . . . . . 52
Boundary Conditions for Running and Controlling Electrochemical
Cells . . . . . . . . . . . . . . . . . . . . . . . . . . 53
Aspects to Consider When Modeling Batteries or Fuel Cells . . . . . . 54
Modeling Cyclic Voltammetry . . . . . . . . . . . . . . . . . . 56
Common Simplifications When Modeling Electrochemical Cells . . . . . 57
Before You Start Building Your Model . . . . . . . . . . . . . . . 59
Meshing Advice . . . . . . . . . . . . . . . . . . . . . . . 60
Solving Electrochemical Models . . . . . . . . . . . . . . . . . 61
Postprocessing Your Solution . . . . . . . . . . . . . . . . . . 65

CONTENTS |3
 Connecting to Electrical Circuits 68
About Connecting Electrical Circuits to Physics Interfaces . . . . . . . 68
Connecting Electrical Circuits Using Predefined Couplings . . . . . . . 69
Connecting Electrical Circuits by User-Defined Couplings . . . . . . . 69
Solving . . . . . . . . . . . . . . . . . . . . . . . . . . . 70
Postprocessing. . . . . . . . . . . . . . . . . . . . . . . . 71
References . . . . . . . . . . . . . . . . . . . . . . . . . 71

SPICE Import and Export 72

SPICE Import . . . . . . . . . . . . . . . . . . . . . . . . 72
SPICE Export . . . . . . . . . . . . . . . . . . . . . . . . 73
Reference . . . . . . . . . . . . . . . . . . . . . . . . . 74

Chapter 3: AC/DC Interfaces

The Electrostatics Interface 76

Domain, Boundary, Edge, Point, and Pair Nodes for the
Electrostatics Interface . . . . . . . . . . . . . . . . . . . 78
Charge Conservation . . . . . . . . . . . . . . . . . . . . . 80
Conduction Loss (Time-Harmonic) . . . . . . . . . . . . . . . . 81
Initial Values . . . . . . . . . . . . . . . . . . . . . . . . 82
Space Charge Density . . . . . . . . . . . . . . . . . . . . . 83
Zero Charge . . . . . . . . . . . . . . . . . . . . . . . . 83
Ground . . . . . . . . . . . . . . . . . . . . . . . . . . 83
Electric Potential . . . . . . . . . . . . . . . . . . . . . . . 84
Surface Charge Density . . . . . . . . . . . . . . . . . . . . 84
External Surface Charge Accumulation . . . . . . . . . . . . . . 85
Electric Displacement Field . . . . . . . . . . . . . . . . . . . 85
Periodic Condition . . . . . . . . . . . . . . . . . . . . . . 86
Thin Low Permittivity Gap . . . . . . . . . . . . . . . . . . . 87
Line Charge . . . . . . . . . . . . . . . . . . . . . . . . . 87
Line Charge (on Axis) . . . . . . . . . . . . . . . . . . . . . 88
Line Charge (Out-of-Plane) . . . . . . . . . . . . . . . . . . . 88
Point Charge . . . . . . . . . . . . . . . . . . . . . . . . 89
Point Charge (on Axis) . . . . . . . . . . . . . . . . . . . . 89
Change Cross Section . . . . . . . . . . . . . . . . . . . . . 90

4 | CONTENTS
Change Thickness (Out-of-Plane). . . . . . . . . . . . . . . . . 90
Charge Conservation, Piezoelectric . . . . . . . . . . . . . . . . 91

The Electric Currents Interface 92

Domain, Boundary, Edge, Point, and Pair Nodes for the Electric
Currents Interface . . . . . . . . . . . . . . . . . . . . . 94
Current Conservation . . . . . . . . . . . . . . . . . . . . . 96
Initial Values . . . . . . . . . . . . . . . . . . . . . . . . 98
External Current Density . . . . . . . . . . . . . . . . . . . 98
Current Source . . . . . . . . . . . . . . . . . . . . . . . 99
Electric Insulation . . . . . . . . . . . . . . . . . . . . . . 99
Boundary Current Source . . . . . . . . . . . . . . . . . . . 99
Normal Current Density . . . . . . . . . . . . . . . . . . . 100
Distributed Impedance. . . . . . . . . . . . . . . . . . . . 100
Contact Impedance . . . . . . . . . . . . . . . . . . . . . 101
Sector Symmetry . . . . . . . . . . . . . . . . . . . . . . 102
Line Current Source . . . . . . . . . . . . . . . . . . . . 103
Line Current Source (on Axis). . . . . . . . . . . . . . . . . 104
Point Current Source . . . . . . . . . . . . . . . . . . . . 104
Point Current Source (on Axis) . . . . . . . . . . . . . . . . 105
Piezoresistive Material . . . . . . . . . . . . . . . . . . . . 105

The Electrical Circuit Interface 107

Ground Node . . . . . . . . . . . . . . . . . . . . . . . 108
Voltmeter . . . . . . . . . . . . . . . . . . . . . . . . 109
Ampère Meter. . . . . . . . . . . . . . . . . . . . . . . 109
Resistor . . . . . . . . . . . . . . . . . . . . . . . . . 109
Capacitor. . . . . . . . . . . . . . . . . . . . . . . . . 110
Inductor . . . . . . . . . . . . . . . . . . . . . . . . . 110
Voltage Source . . . . . . . . . . . . . . . . . . . . . . 110
Current Source . . . . . . . . . . . . . . . . . . . . . . 111
Voltage-Controlled Voltage Source . . . . . . . . . . . . . . . 112
Voltage-Controlled Current Source. . . . . . . . . . . . . . . 113
Current-Controlled Voltage Source. . . . . . . . . . . . . . . 113
Current-Controlled Current Source . . . . . . . . . . . . . . 113
Switch . . . . . . . . . . . . . . . . . . . . . . . . . . 114
Subcircuit Definition . . . . . . . . . . . . . . . . . . . . 115
Subcircuit Instance . . . . . . . . . . . . . . . . . . . . . 115

CONTENTS |5
 NPN BJT and PNP BJT. . . . . . . . . . . . . . . . . . . . 116
n-Channel MOSFET and p-Channel MOSFET . . . . . . . . . . . 116
Mutual Inductance . . . . . . . . . . . . . . . . . . . . . 117
Transformer . . . . . . . . . . . . . . . . . . . . . . . 117
Battery Open Circuit Voltage . . . . . . . . . . . . . . . . . 118
Resistor-Capacitor Couple . . . . . . . . . . . . . . . . . . 118
Diode . . . . . . . . . . . . . . . . . . . . . . . . . . 119
External I vs. U . . . . . . . . . . . . . . . . . . . . . . 119
External U vs. I . . . . . . . . . . . . . . . . . . . . . . 120
External I-Terminal . . . . . . . . . . . . . . . . . . . . . 121
SPICE Circuit Import . . . . . . . . . . . . . . . . . . . . 122
SPICE Circuit Export . . . . . . . . . . . . . . . . . . . . 122

Theory for the Electrostatics Interface 123

Charge Relaxation Theory . . . . . . . . . . . . . . . . . . 123
Electrostatics Equations . . . . . . . . . . . . . . . . . . . 125
The Electrostatics Interface in Time Dependent or Frequency
Domain Studies . . . . . . . . . . . . . . . . . . . . . 126

Theory for the Electric Currents Interface 127

Electric Currents Equations in Steady State . . . . . . . . . . . . 127

Theory for the Electrical Circuit Interface 129

Electric Circuit Modeling and the Semiconductor Device Models. . . . 129
Bipolar Transistors . . . . . . . . . . . . . . . . . . . . . 130
MOSFET Transistors . . . . . . . . . . . . . . . . . . . . 133
Diode . . . . . . . . . . . . . . . . . . . . . . . . . . 136
Reference for the Electrical Circuit Interface . . . . . . . . . . . 138

Chapter 4: Electrochemistry Interfaces

The Primary and Secondary Current Distribution Interfaces 140

The Primary Current Distribution and Secondary Current Distribution
Interfaces . . . . . . . . . . . . . . . . . . . . . . . 140
Electrolyte . . . . . . . . . . . . . . . . . . . . . . . . 143
Initial Values . . . . . . . . . . . . . . . . . . . . . . . 144

6 | CONTENTS
Porous Electrode. . . . . . . . . . . . . . . . . . . . . . 144
Periodic Condition . . . . . . . . . . . . . . . . . . . . . 146
Thin Electrolyte Layer . . . . . . . . . . . . . . . . . . . . 146
Edge Electrode. . . . . . . . . . . . . . . . . . . . . . . 146
Electrode Line Current Source . . . . . . . . . . . . . . . . 147
Electrolyte Line Current Source . . . . . . . . . . . . . . . . 147
Electrode Symmetry Axis Current Source . . . . . . . . . . . . 148
Electrolyte Symmetry Axis Current Source . . . . . . . . . . . . 148
Electrode Point Current Source . . . . . . . . . . . . . . . . 148
Electrolyte Point Current Source. . . . . . . . . . . . . . . . 149
Electrode Current . . . . . . . . . . . . . . . . . . . . . 149

The Tertiary Current Distribution, Nernst-Planck Interface 150

The Tertiary Current Distribution, Nernst-Planck Interface . . . . . 150
Electrolyte . . . . . . . . . . . . . . . . . . . . . . . . 155
Porous Electrode. . . . . . . . . . . . . . . . . . . . . . 156
Separator. . . . . . . . . . . . . . . . . . . . . . . . . 157
Reactions. . . . . . . . . . . . . . . . . . . . . . . . . 157
Initial Values . . . . . . . . . . . . . . . . . . . . . . . 157
Ion Exchange Membrane . . . . . . . . . . . . . . . . . . . 158
Ion Exchange Membrane Boundary . . . . . . . . . . . . . . . 158
Thin Electrolyte Layer . . . . . . . . . . . . . . . . . . . . 159

Shared Physics Features in the Current Distribution Interfaces

160
Domain, Boundary, Pair, Edge, and Point Nodes for the
Electrochemistry Interfaces . . . . . . . . . . . . . . . . 160
Electrode. . . . . . . . . . . . . . . . . . . . . . . . . 162
Highly Conductive Porous Electrode . . . . . . . . . . . . . . 162
Electrode Current Source . . . . . . . . . . . . . . . . . . 162
Electrolyte Current Source . . . . . . . . . . . . . . . . . . 163
Porous Electrode Reaction . . . . . . . . . . . . . . . . . . 163
Porous Matrix Double Layer Capacitance . . . . . . . . . . . . 164
Insulation . . . . . . . . . . . . . . . . . . . . . . . . . 164
Symmetry . . . . . . . . . . . . . . . . . . . . . . . . 164
Electrode Surface. . . . . . . . . . . . . . . . . . . . . . 165
Electrode Reaction . . . . . . . . . . . . . . . . . . . . . 168
Double Layer Capacitance . . . . . . . . . . . . . . . . . . 174

CONTENTS |7
 Internal Electrode Surface . . . . . . . . . . . . . . . . . . 174
Electrolyte Potential . . . . . . . . . . . . . . . . . . . . 175
Electrolyte Current . . . . . . . . . . . . . . . . . . . . . 175
Electrolyte Current Density. . . . . . . . . . . . . . . . . . 176
Thin Electrode Layer . . . . . . . . . . . . . . . . . . . . 176
Electrode-Electrolyte Boundary Interface. . . . . . . . . . . . . 177
Electric Ground . . . . . . . . . . . . . . . . . . . . . . 177
Electric Potential . . . . . . . . . . . . . . . . . . . . . . 178
Electrode Current Density . . . . . . . . . . . . . . . . . . 178
Electrode Current . . . . . . . . . . . . . . . . . . . . . 178
Electrode Power . . . . . . . . . . . . . . . . . . . . . . 179
Harmonic Perturbation . . . . . . . . . . . . . . . . . . . 179
Electrode Potential . . . . . . . . . . . . . . . . . . . . . 180
External Short . . . . . . . . . . . . . . . . . . . . . . . 180
Initial Values for Dissolving-Depositing Species . . . . . . . . . . 181
Non-Faradaic Reactions . . . . . . . . . . . . . . . . . . . 181
Reference Electrode . . . . . . . . . . . . . . . . . . . . 181
Electric Reference Potential . . . . . . . . . . . . . . . . . . 181
Charge-Discharge Cycling . . . . . . . . . . . . . . . . . . 182
Circuit Terminal . . . . . . . . . . . . . . . . . . . . . . 183

The Electrode, Shell Interface 184

Boundary, Edge, Point, and Pair Nodes for the Electrode, Shell
Interface. . . . . . . . . . . . . . . . . . . . . . . . 185
Electrode . . . . . . . . . . . . . . . . . . . . . . . . . 186
Initial Values . . . . . . . . . . . . . . . . . . . . . . . 187
External Current Density . . . . . . . . . . . . . . . . . . 187
Current Source . . . . . . . . . . . . . . . . . . . . . . 187
Normal Current Density . . . . . . . . . . . . . . . . . . . 188
Electric Insulation . . . . . . . . . . . . . . . . . . . . . 188
Boundary Current Source . . . . . . . . . . . . . . . . . . 188
Ground . . . . . . . . . . . . . . . . . . . . . . . . . 188
Electric Potential . . . . . . . . . . . . . . . . . . . . . . 189

The Electroanalysis Model Wizard Entry 190

Theory for the Current Distribution Interfaces 191

The Nernst-Planck Equations . . . . . . . . . . . . . . . . . 191

8 | CONTENTS
Domain Equations for Primary and Secondary Current Distributions . . 192
Electrochemical Reactions and the Difference Between a Primary and
a Secondary Current Distribution . . . . . . . . . . . . . . 193
Domain Equations for Tertiary Current Distributions Using the
Nernst-Planck Equations and Electroneutrality . . . . . . . . . 196
Mass Fluxes and Sources Due to Electrochemical Reactions . . . . . 197
Deposition-Dissolution Rates, Growth Velocities, and Thicknesses on
an Electrode Surface . . . . . . . . . . . . . . . . . . . 198
Stoichiometric Coefficients for Double Layer Capacitive Charging . . . 199
Film Resistance . . . . . . . . . . . . . . . . . . . . . . 199
Equilibrium Potentials and the Nernst Equation . . . . . . . . . . 200
Electrode Kinetics Expressions . . . . . . . . . . . . . . . . 201
Theory for Specific Current Distribution Feature Nodes . . . . . . . 206
References . . . . . . . . . . . . . . . . . . . . . . . . 213

Theory for Electrochemical Heat Sources 214

Joule Heating Due to Charge Transport . . . . . . . . . . . . . 215
Heating Due to Electrochemical Reactions . . . . . . . . . . . . 215
Heating Due to Heat of Mixing . . . . . . . . . . . . . . . . 216
Heat of Mixing in Intercalating Electrodes . . . . . . . . . . . . 217

Theory for the Electrode, Shell Interface 219

Governing Equations . . . . . . . . . . . . . . . . . . . . 219
Coupling to Other Physics Interfaces . . . . . . . . . . . . . . 219

Theory for Electroanalysis 221

Electroanalytical Methods . . . . . . . . . . . . . . . . . . 221
Supporting Electrolyte . . . . . . . . . . . . . . . . . . . . 221
Domain Equations for the Electroanalysis Case . . . . . . . . . . 222
Electrode Boundary Conditions in the Electroanalysis Model . . . . . 224
The Electroanalytical Butler-Volmer Equation . . . . . . . . . . . 226
Counter Electrodes and Overall Charge Balance . . . . . . . . . . 227

Electrode Potentials and Reference Electrodes 228

Reference Electrodes . . . . . . . . . . . . . . . . . . . . 228
Boundary Conditions Using Reference Electrode Potentials. . . . . . 229
Nodes for Handling Electrode Potentials and Reference Electrodes. . . 229

CONTENTS |9
 Chapter 5: Battery Interfaces

The Lithium-Ion Battery Interface 232

About the Domain, Boundary, Edge, Point, and Pair Nodes for the
Lithium-Ion Battery Interface . . . . . . . . . . . . . . . . 236
Initial Values . . . . . . . . . . . . . . . . . . . . . . . 236
Electrode Reaction . . . . . . . . . . . . . . . . . . . . . 237

The Battery with Binary Electrolyte Interface 238

Domain, Boundary, Edge, Point, and Pair Nodes for the Battery
with Binary Electrolyte Interface. . . . . . . . . . . . . . . 242
Initial Values . . . . . . . . . . . . . . . . . . . . . . . 242
Porous Matrix Adsorption/Desorption Reaction . . . . . . . . . . 242

The Lead-Acid Battery Interface 244

Domain, Boundary, Edge, Point, and Pair Nodes for the Lead-Acid
Battery Interface. . . . . . . . . . . . . . . . . . . . . 246
Reservoir. . . . . . . . . . . . . . . . . . . . . . . . . 247
Initial Values . . . . . . . . . . . . . . . . . . . . . . . 247
Negative Porous Electrode . . . . . . . . . . . . . . . . . . 248
Positive Porous Electrode . . . . . . . . . . . . . . . . . . 248
Separator. . . . . . . . . . . . . . . . . . . . . . . . . 249

The Single Particle Battery Interface 250

Model Tree Nodes for the Single Particle Battery Interface . . . . . . 254
Electrolyte and Separator . . . . . . . . . . . . . . . . . . 254
Positive Electrode . . . . . . . . . . . . . . . . . . . . . 255
Negative Electrode . . . . . . . . . . . . . . . . . . . . . 255
Lithium Insertion Reaction . . . . . . . . . . . . . . . . . . 255

The Lumped Battery Interface 257

Model Tree Nodes for the Lumped Battery Interface . . . . . . . . 259
Cell Equilibrium Potential. . . . . . . . . . . . . . . . . . . 260
Voltage Losses . . . . . . . . . . . . . . . . . . . . . . . 260
Capacity Loss . . . . . . . . . . . . . . . . . . . . . . . 261
Short Circuit . . . . . . . . . . . . . . . . . . . . . . . 262

10 | C O N T E N T S
 The Battery Equivalent Circuit Model Wizard Entry 263

Shared Nodes for Battery Interfaces 264

Electrolyte . . . . . . . . . . . . . . . . . . . . . . . . 265
Separator. . . . . . . . . . . . . . . . . . . . . . . . . 266
Porous Electrode. . . . . . . . . . . . . . . . . . . . . . 266
Particle Intercalation . . . . . . . . . . . . . . . . . . . . 268
Porous Electrode Reaction . . . . . . . . . . . . . . . . . . 271
Reaction Source . . . . . . . . . . . . . . . . . . . . . . 272
Additional Porous Electrode Material . . . . . . . . . . . . . . 273
Concentration . . . . . . . . . . . . . . . . . . . . . . . 273
No Flux . . . . . . . . . . . . . . . . . . . . . . . . . 273
Flux . . . . . . . . . . . . . . . . . . . . . . . . . . . 274
Initial Cell Charge Distribution . . . . . . . . . . . . . . . . 274
Negative Electrode Selection . . . . . . . . . . . . . . . . . 275
Positive Electrode Selection . . . . . . . . . . . . . . . . . . 276

Theory for the Lithium-Ion Battery Interface 277

References . . . . . . . . . . . . . . . . . . . . . . . . 287

Theory for the Battery with Binary Electrolyte Interface 288

Theory for the Lead-Acid Battery Interface 296

The Electrode Reactions Equations . . . . . . . . . . . . . . . 296
Electrode Kinetics and Active Available Surface Areas . . . . . . . . 297
Electrode Charge Transport Equations . . . . . . . . . . . . . 297
Electrolyte Transport Equations . . . . . . . . . . . . . . . . 298

Theory for the Single Particle Battery Interface 302

Theory for the Lumped Battery Interface 309

Chapter 6: Chemical Species Transport Interfaces

The Transport of Diluted Species Interface 318

The Transport of Diluted Species in Porous Media Interface . . . . . 322

CONTENTS | 11
 Domain, Boundary, and Pair Nodes for the Transport of Diluted
Species Interface. . . . . . . . . . . . . . . . . . . . . 323
Transport Properties . . . . . . . . . . . . . . . . . . . . 325
Turbulent Mixing . . . . . . . . . . . . . . . . . . . . . . 327
Initial Values . . . . . . . . . . . . . . . . . . . . . . . 328
Mass-Based Concentrations . . . . . . . . . . . . . . . . . . 328
Reactions. . . . . . . . . . . . . . . . . . . . . . . . . 328
No Flux . . . . . . . . . . . . . . . . . . . . . . . . . 330
Inflow . . . . . . . . . . . . . . . . . . . . . . . . . . 331
Outflow . . . . . . . . . . . . . . . . . . . . . . . . . 331
Concentration . . . . . . . . . . . . . . . . . . . . . . . 332
Flux . . . . . . . . . . . . . . . . . . . . . . . . . . . 332
Symmetry . . . . . . . . . . . . . . . . . . . . . . . . 333
Flux Discontinuity . . . . . . . . . . . . . . . . . . . . . 334
Partition Condition . . . . . . . . . . . . . . . . . . . . . 334
Periodic Condition . . . . . . . . . . . . . . . . . . . . . 335
Line Mass Source . . . . . . . . . . . . . . . . . . . . . . 336
Point Mass Source . . . . . . . . . . . . . . . . . . . . . 336
Open Boundary . . . . . . . . . . . . . . . . . . . . . . 337
Thin Diffusion Barrier . . . . . . . . . . . . . . . . . . . . 337
Thin Impermeable Barrier . . . . . . . . . . . . . . . . . . 338
Equilibrium Reaction . . . . . . . . . . . . . . . . . . . . 338
Surface Reactions . . . . . . . . . . . . . . . . . . . . . 339
Surface Equilibrium Reaction . . . . . . . . . . . . . . . . . 340
Fast Irreversible Surface Reaction . . . . . . . . . . . . . . . 340
Porous Electrode Coupling . . . . . . . . . . . . . . . . . . 340
Reaction Coefficients . . . . . . . . . . . . . . . . . . . . 341
Electrode Surface Coupling . . . . . . . . . . . . . . . . . . 341
Porous Medium . . . . . . . . . . . . . . . . . . . . . . 342
Fluid . . . . . . . . . . . . . . . . . . . . . . . . . . 342
Porous Matrix . . . . . . . . . . . . . . . . . . . . . . . 344
Dispersion . . . . . . . . . . . . . . . . . . . . . . . . 345
Unsaturated Porous Medium . . . . . . . . . . . . . . . . . 345
Liquid . . . . . . . . . . . . . . . . . . . . . . . . . . 346
Gas . . . . . . . . . . . . . . . . . . . . . . . . . . . 348
Adsorption . . . . . . . . . . . . . . . . . . . . . . . . 349
Volatilization . . . . . . . . . . . . . . . . . . . . . . . 351
Species Source. . . . . . . . . . . . . . . . . . . . . . . 351

12 | C O N T E N T S
Hygroscopic Swelling . . . . . . . . . . . . . . . . . . . . 352
Fracture . . . . . . . . . . . . . . . . . . . . . . . . . 353

The Transport of Diluted Species in Fractures Interface 354

Boundary, Edge, Point, and Pair Nodes for the Transport of Diluted
Species in Fractures Interface . . . . . . . . . . . . . . . . 356
Adsorption . . . . . . . . . . . . . . . . . . . . . . . . 357
Concentration . . . . . . . . . . . . . . . . . . . . . . . 358
Flux . . . . . . . . . . . . . . . . . . . . . . . . . . . 359
Fracture . . . . . . . . . . . . . . . . . . . . . . . . . 359
Inflow . . . . . . . . . . . . . . . . . . . . . . . . . . 360
No Flux . . . . . . . . . . . . . . . . . . . . . . . . . 361
Outflow . . . . . . . . . . . . . . . . . . . . . . . . . 361
Reactions. . . . . . . . . . . . . . . . . . . . . . . . . 361
Species Source. . . . . . . . . . . . . . . . . . . . . . . 362

The Transport of Concentrated Species Interface 363

Domain, Boundary, and Pair Nodes for the Transport of
Concentrated Species Interface . . . . . . . . . . . . . . . 369
Transport Properties . . . . . . . . . . . . . . . . . . . . 370
Porous Media Transport Properties. . . . . . . . . . . . . . . 374
Electrode Surface Coupling . . . . . . . . . . . . . . . . . . 377
Turbulent Mixing . . . . . . . . . . . . . . . . . . . . . . 378
Reaction . . . . . . . . . . . . . . . . . . . . . . . . . 379
Reaction Sources . . . . . . . . . . . . . . . . . . . . . . 380
Initial Values . . . . . . . . . . . . . . . . . . . . . . . 381
Mass Fraction . . . . . . . . . . . . . . . . . . . . . . . 382
Flux . . . . . . . . . . . . . . . . . . . . . . . . . . . 383
Inflow . . . . . . . . . . . . . . . . . . . . . . . . . . 384
No Flux . . . . . . . . . . . . . . . . . . . . . . . . . 385
Outflow . . . . . . . . . . . . . . . . . . . . . . . . . 385
Symmetry . . . . . . . . . . . . . . . . . . . . . . . . 385
Flux Discontinuity . . . . . . . . . . . . . . . . . . . . . 386
Open Boundary . . . . . . . . . . . . . . . . . . . . . . 386
Equilibrium Reaction . . . . . . . . . . . . . . . . . . . . 387
Surface Equilibrium Reaction . . . . . . . . . . . . . . . . . 388

CONTENTS | 13
 The Chemistry Interface 389
Feature Nodes Available for the Chemistry Interface . . . . . . . . 393
Reaction . . . . . . . . . . . . . . . . . . . . . . . . . 393
Species . . . . . . . . . . . . . . . . . . . . . . . . . 398
Electrode Reaction . . . . . . . . . . . . . . . . . . . . . 400
Electrode Reaction Group . . . . . . . . . . . . . . . . . . 403
Reversible Reaction Group . . . . . . . . . . . . . . . . . . 403
Equilibrium Reaction Group. . . . . . . . . . . . . . . . . . 405
Species Group . . . . . . . . . . . . . . . . . . . . . . . 406
Reaction Thermodynamics . . . . . . . . . . . . . . . . . . 406
Species Activity . . . . . . . . . . . . . . . . . . . . . . 407
Species Thermodynamics. . . . . . . . . . . . . . . . . . . 407

The Nernst-Planck-Poisson Equations Interface 408

The Electrophoretic Transport Interface 410

Common Settings for the Species Nodes in the Electrophoretic
Transport Interface . . . . . . . . . . . . . . . . . . . 413
Diffusion and Migration Settings . . . . . . . . . . . . . . . . 415
Domain, Boundary, and Pair Nodes for the Electrophoretic Transport
Interface. . . . . . . . . . . . . . . . . . . . . . . . 416
Solvent . . . . . . . . . . . . . . . . . . . . . . . . . 417
Porous Matrix Properties . . . . . . . . . . . . . . . . . . 417
Fully Dissociated Species . . . . . . . . . . . . . . . . . . . 417
Uncharged Species . . . . . . . . . . . . . . . . . . . . . 417
Weak Acid . . . . . . . . . . . . . . . . . . . . . . . . 418
Weak Base . . . . . . . . . . . . . . . . . . . . . . . . 418
Ampholyte . . . . . . . . . . . . . . . . . . . . . . . . 418
Protein . . . . . . . . . . . . . . . . . . . . . . . . . 419
Current Source . . . . . . . . . . . . . . . . . . . . . . 419
Initial Potential. . . . . . . . . . . . . . . . . . . . . . . 419
Current . . . . . . . . . . . . . . . . . . . . . . . . . 419
Current Density . . . . . . . . . . . . . . . . . . . . . . 419
Insulation . . . . . . . . . . . . . . . . . . . . . . . . . 420
Potential . . . . . . . . . . . . . . . . . . . . . . . . . 420
Species Source. . . . . . . . . . . . . . . . . . . . . . . 420
Initial Concentration . . . . . . . . . . . . . . . . . . . . 421
Concentration . . . . . . . . . . . . . . . . . . . . . . . 421

14 | C O N T E N T S
No Flux . . . . . . . . . . . . . . . . . . . . . . . . . 421
Flux . . . . . . . . . . . . . . . . . . . . . . . . . . . 421
Inflow . . . . . . . . . . . . . . . . . . . . . . . . . . 422
Outflow . . . . . . . . . . . . . . . . . . . . . . . . . 422

The Surface Reactions Interface 423

Boundary, Edge, Point, and Pair Nodes for the Surface Reactions
Interface. . . . . . . . . . . . . . . . . . . . . . . . 424
Surface Properties . . . . . . . . . . . . . . . . . . . . . 425
Initial Values . . . . . . . . . . . . . . . . . . . . . . . 426
Reactions. . . . . . . . . . . . . . . . . . . . . . . . . 426
Surface Concentration . . . . . . . . . . . . . . . . . . . . 427

The Reacting Flow Interfaces 428

The Reacting Laminar Flow Interface . . . . . . . . . . . . . . 428
The Reacting Flow Coupling Feature . . . . . . . . . . . . . . 429
Physics Interface Features . . . . . . . . . . . . . . . . . . 431

The Reacting Flow in Porous Media Interfaces 433

The Reacting Flow in Porous Media, Transport of Diluted Species
Interface. . . . . . . . . . . . . . . . . . . . . . . . 433
The Reacting Flow in Porous Media, Transport of Concentrated
Species Interface. . . . . . . . . . . . . . . . . . . . . 434
The Reacting Flow, Diluted Species Coupling Feature . . . . . . . . 434
The Reacting Flow Coupling Feature . . . . . . . . . . . . . . 435
Physics Interface Features . . . . . . . . . . . . . . . . . . 435

Theory for the Transport of Diluted Species Interface 436

Mass Balance Equation . . . . . . . . . . . . . . . . . . . . 437
Equilibrium Reaction Theory . . . . . . . . . . . . . . . . . 438
Convective Term Formulation. . . . . . . . . . . . . . . . . 440
Solving a Diffusion Equation Only . . . . . . . . . . . . . . . 441
Mass Sources for Species Transport . . . . . . . . . . . . . . 441
Adding Transport Through Migration . . . . . . . . . . . . . . 443
Supporting Electrolytes . . . . . . . . . . . . . . . . . . . 444
Crosswind Diffusion . . . . . . . . . . . . . . . . . . . . 445
Danckwerts Inflow Boundary Condition . . . . . . . . . . . . . 446
Mass Balance Equation for Transport of Diluted Species in Porous

CONTENTS | 15
 Media . . . . . . . . . . . . . . . . . . . . . . . . . 447
Convection in Porous Media . . . . . . . . . . . . . . . . . 448
Diffusion in Porous Media . . . . . . . . . . . . . . . . . . 450
Dispersion . . . . . . . . . . . . . . . . . . . . . . . . 451
Adsorption . . . . . . . . . . . . . . . . . . . . . . . . 453
Reactions. . . . . . . . . . . . . . . . . . . . . . . . . 455
Mass Transport in Fractures . . . . . . . . . . . . . . . . . 456
References . . . . . . . . . . . . . . . . . . . . . . . . 457

Theory for the Transport of Concentrated Species Interface 459

Multicomponent Mass Transport . . . . . . . . . . . . . . . . 459
Multicomponent Gas Diffusion: Maxwell–Stefan Description . . . . . 460
Multicomponent Diffusivities . . . . . . . . . . . . . . . . . 462
Multicomponent Diffusion: Mixture-Averaged Approximation . . . . . 464
Multispecies Diffusion: Fick’s Law Approximation . . . . . . . . . 466
Multicomponent Thermal Diffusion . . . . . . . . . . . . . . . 467
Regularization of Reaction Rate Expression . . . . . . . . . . . . 467
References for the Transport of Concentrated Species Interface . . . . 468

Theory for the Electrophoretic Transport Interface 469

Theory for the Surface Reactions Interface 475

Governing Equations for the Surface Concentrations . . . . . . . . 475
Governing Equations for the Bulk Concentrations . . . . . . . . . 476
ODE Formulations for Surface Concentrations . . . . . . . . . . 478
Surface Reaction Equations on Deforming Geometries . . . . . . . 479
Reference for the Surface Reactions Interface . . . . . . . . . . . 480

Theory for the Coupling of Mass Transport to

Electrochemical Reactions 481
Molar Sources and Sinks . . . . . . . . . . . . . . . . . . . 481
Mass Sources and Sinks . . . . . . . . . . . . . . . . . . . 482

Theory for the Reacting Flow Interface 483

Pseudo Time Stepping for Mass Transport . . . . . . . . . . . . 483
The Stefan Velocity . . . . . . . . . . . . . . . . . . . . . 483
The Chemical Reaction Rate . . . . . . . . . . . . . . . . . 485

16 | C O N T E N T S
Chapter 7: Fluid Flow Interfaces

The Laminar Flow and Creeping Flow Interfaces 488

The Creeping Flow Interface . . . . . . . . . . . . . . . . . 488
The Laminar Flow Interface . . . . . . . . . . . . . . . . . . 489
Domain, Boundary, Pair, and Point Nodes for Single-Phase Flow . . . . . 494
Fluid Properties . . . . . . . . . . . . . . . . . . . . . . 495
Volume Force . . . . . . . . . . . . . . . . . . . . . . . 496
Initial Values . . . . . . . . . . . . . . . . . . . . . . . 497
Wall . . . . . . . . . . . . . . . . . . . . . . . . . . 497
Inlet . . . . . . . . . . . . . . . . . . . . . . . . . . . 499
Outlet . . . . . . . . . . . . . . . . . . . . . . . . . . 503
Symmetry . . . . . . . . . . . . . . . . . . . . . . . . 505
Open Boundary . . . . . . . . . . . . . . . . . . . . . . 506
Boundary Stress . . . . . . . . . . . . . . . . . . . . . . 506
Periodic Flow Condition . . . . . . . . . . . . . . . . . . . 508
Flow Continuity . . . . . . . . . . . . . . . . . . . . . . 509
Pressure Point Constraint . . . . . . . . . . . . . . . . . . 509
Point Mass Source . . . . . . . . . . . . . . . . . . . . . 510
Line Mass Source . . . . . . . . . . . . . . . . . . . . . . 510
Gravity . . . . . . . . . . . . . . . . . . . . . . . . . 511

The Darcy’s Law Interface 513

Domain, Boundary, Edge, Point, and Pair Nodes for the Darcy’s
Law Interface . . . . . . . . . . . . . . . . . . . . . . 515
Fluid and Matrix Properties . . . . . . . . . . . . . . . . . . 517
Mass Source . . . . . . . . . . . . . . . . . . . . . . . 520
Initial Values . . . . . . . . . . . . . . . . . . . . . . . 520
Storage Model . . . . . . . . . . . . . . . . . . . . . . . 521
Richards’ Equation Model . . . . . . . . . . . . . . . . . . 522
Poroelastic Storage . . . . . . . . . . . . . . . . . . . . . 522
Gravity . . . . . . . . . . . . . . . . . . . . . . . . . 523
Porous Electrode Coupling . . . . . . . . . . . . . . . . . . 523
Electrode Surface Coupling . . . . . . . . . . . . . . . . . . 524
Pressure . . . . . . . . . . . . . . . . . . . . . . . . . 524
Mass Flux. . . . . . . . . . . . . . . . . . . . . . . . . 525
Line Mass Source . . . . . . . . . . . . . . . . . . . . . . 525

CONTENTS | 17
 Point Mass Source . . . . . . . . . . . . . . . . . . . . . 526
Inlet . . . . . . . . . . . . . . . . . . . . . . . . . . . 526
Symmetry . . . . . . . . . . . . . . . . . . . . . . . . 528
No Flow . . . . . . . . . . . . . . . . . . . . . . . . . 528
Flux Discontinuity . . . . . . . . . . . . . . . . . . . . . 528
Outlet . . . . . . . . . . . . . . . . . . . . . . . . . . 529
Precipitation . . . . . . . . . . . . . . . . . . . . . . . 529
Cross Section . . . . . . . . . . . . . . . . . . . . . . . 529
Thickness. . . . . . . . . . . . . . . . . . . . . . . . . 530
Interior Wall . . . . . . . . . . . . . . . . . . . . . . . 530
Thin Barrier. . . . . . . . . . . . . . . . . . . . . . . . 530
Pressure Head . . . . . . . . . . . . . . . . . . . . . . . 531
Hydraulic Head . . . . . . . . . . . . . . . . . . . . . . 531
Atmosphere/Gauge . . . . . . . . . . . . . . . . . . . . . 532
Pervious Layer . . . . . . . . . . . . . . . . . . . . . . . 532
Well . . . . . . . . . . . . . . . . . . . . . . . . . . 534
Fracture Flow . . . . . . . . . . . . . . . . . . . . . . . 534

The Free and Porous Media Flow Interface 535

Domain, Boundary, Point, and Pair Nodes for the Free and Porous
Media Flow Interface . . . . . . . . . . . . . . . . . . . 536
Fluid Properties . . . . . . . . . . . . . . . . . . . . . . 537
Fluid and Matrix Properties . . . . . . . . . . . . . . . . . . 538
Mass Source . . . . . . . . . . . . . . . . . . . . . . . 539
Volume Force . . . . . . . . . . . . . . . . . . . . . . . 539
Porous Electrode Coupling . . . . . . . . . . . . . . . . . . 540
Initial Values . . . . . . . . . . . . . . . . . . . . . . . 540
Electrode-Electrolyte Interface Coupling . . . . . . . . . . . . . 540
Wall . . . . . . . . . . . . . . . . . . . . . . . . . . 541

The Brinkman Equations Interface 543

Domain, Boundary, Point, and Pair Nodes for the Brinkman
Equations Interface . . . . . . . . . . . . . . . . . . . . 545
Fluid and Matrix Properties . . . . . . . . . . . . . . . . . . 546
Mass Source . . . . . . . . . . . . . . . . . . . . . . . 548
Volume Force . . . . . . . . . . . . . . . . . . . . . . . 548
Initial Values . . . . . . . . . . . . . . . . . . . . . . . 549
Fluid Properties . . . . . . . . . . . . . . . . . . . . . . 549

18 | C O N T E N T S
Theory for the Laminar Flow and Creeping Flow Interfaces 551
General Single-Phase Flow Theory . . . . . . . . . . . . . . . 552
Compressible Flow . . . . . . . . . . . . . . . . . . . . . 554
Weakly Compressible Flow . . . . . . . . . . . . . . . . . . 554
The Mach Number Limit . . . . . . . . . . . . . . . . . . . 554
Incompressible Flow . . . . . . . . . . . . . . . . . . . . 555
The Reynolds Number. . . . . . . . . . . . . . . . . . . . 556
Theory for the Wall Boundary Condition . . . . . . . . . . . . 556
Prescribing Inlet and Outlet Conditions . . . . . . . . . . . . . 560
Mass Flow . . . . . . . . . . . . . . . . . . . . . . . . 561
Fully Developed Flow (Inlet) . . . . . . . . . . . . . . . . . 563
Fully Developed Flow (Outlet). . . . . . . . . . . . . . . . . 564
No Viscous Stress . . . . . . . . . . . . . . . . . . . . . 565
Normal Stress Boundary Condition . . . . . . . . . . . . . . . 566
Pressure Boundary Condition . . . . . . . . . . . . . . . . . 567
Mass Sources for Fluid Flow . . . . . . . . . . . . . . . . . 569
Numerical Stability — Stabilization Techniques for Fluid Flow . . . . . 571
Solvers for Laminar Flow . . . . . . . . . . . . . . . . . . . 573
Pseudo Time Stepping for Laminar Flow Models . . . . . . . . . . 575
Discontinuous Galerkin Formulation . . . . . . . . . . . . . . 577
Particle Tracing in Fluid Flow . . . . . . . . . . . . . . . . . 577
References for the Single-Phase Flow, Laminar Flow Interfaces . . . . 578

Theory for the Darcy’s Law Interface 581

About Darcy’s Law . . . . . . . . . . . . . . . . . . . . . 581
Darcy’s Law — Equation Formulation . . . . . . . . . . . . . . 582
Storage Model . . . . . . . . . . . . . . . . . . . . . . . 583
Average Linear Velocity . . . . . . . . . . . . . . . . . . . 584
References for the Darcy’s Law Interface. . . . . . . . . . . . . 584

Theory for the Free and Porous Media Flow Interface 586
Reference for the Free and Porous Media Flow Interface. . . . . . . 586

Theory for the Brinkman Equations Interface 587

About the Brinkman Equations . . . . . . . . . . . . . . . . 587
Brinkman Equations Theory. . . . . . . . . . . . . . . . . . 587
References for the Brinkman Equations Interface. . . . . . . . . . 589

CONTENTS | 19
 Theory for the Coupling of Fluid Flow to Electrochemical
Reactions 590
Momentum Sources and Sinks . . . . . . . . . . . . . . . . . . 590

Chapter 8: Heat Transfer Interfaces

Coupling of Heat Transfer to Electrochemical Reactions 592

Joule Heating Due to Charge Transport . . . . . . . . . . . . . 593
Heating Due to Electrochemical Reactions . . . . . . . . . . . . 593

Chapter 9: Thermodynamics

Using Thermodynamic Properties 598

Workflow for Thermodynamics Property Calculations . . . . . . . 598
Thermodynamics . . . . . . . . . . . . . . . . . . . . . . 600
Thermodynamic System . . . . . . . . . . . . . . . . . . . 601
External Thermodynamic Packages . . . . . . . . . . . . . . . 609
External Thermodynamic System . . . . . . . . . . . . . . . . 610
Predefined System . . . . . . . . . . . . . . . . . . . . . 613
Exporting and Importing Thermodynamic Systems . . . . . . . . . 616
Species Property . . . . . . . . . . . . . . . . . . . . . . 616
Mixture Property. . . . . . . . . . . . . . . . . . . . . . 622
Equilibrium Calculation . . . . . . . . . . . . . . . . . . . 623
Generate Chemistry . . . . . . . . . . . . . . . . . . . . 627
Generate Material . . . . . . . . . . . . . . . . . . . . . 629
Coupling with the Reaction Engineering and the Chemistry Interfaces . . 633
Evaluating a Property Function in a Physics Interface . . . . . . . . 637
User-Defined Species . . . . . . . . . . . . . . . . . . . . 638
References . . . . . . . . . . . . . . . . . . . . . . . . 644

Thermodynamic Models and Theory 645

Introduction . . . . . . . . . . . . . . . . . . . . . . . 645
Thermodynamic Models . . . . . . . . . . . . . . . . . . . 645
Selecting the Right Thermodynamic Model . . . . . . . . . . . . 660
Species Property References . . . . . . . . . . . . . . . . . 662

20 | C O N T E N T S
 Thermodynamic Properties Definitions . . . . . . . . . . . . . 663
Standard Enthalpy of Formation and Absolute Entropy Terms . . . . . 667
Reference State . . . . . . . . . . . . . . . . . . . . . . 668
Transport Properties . . . . . . . . . . . . . . . . . . . . 668
Surface Tension . . . . . . . . . . . . . . . . . . . . . . 693
References . . . . . . . . . . . . . . . . . . . . . . . . 694

Chapter 10: Multiphysics Coupling Nodes

Electrochemical Heating . . . . . . . . . . . . . . . . . . . 702
Potential Coupling . . . . . . . . . . . . . . . . . . . . . 702
Space Charge Density Coupling . . . . . . . . . . . . . . . . 702

Chapter 11: Glossary

Glossary of Terms 706

CONTENTS | 21
22 | C O N T E N T S
 1

Introduction

This guide describes the Battery Design Module, an optional add-on package for
COMSOL Multiphysics® designed to assist you in building detailed models of the
configuration of the electrodes and electrolyte in electrochemical cells.

This chapter introduces you to the capabilities of the module. A summary of the
physics interfaces and where you can find documentation and model examples is
also included. The last section is a brief overview with links to each chapter in this
guide.

• About the Battery Design Module

• Overview of the User’s Guide

23
 About the Battery Design Module
In this section:

• What Can the Battery Design Module Do?

• Battery Design Module Physics Interface Guide
• Common Physics Interface and Feature Settings and Nodes
• Where Do I Access the Documentation and Application Libraries?

What Can the Battery Design Module Do?

The Battery Design Module extends the COMSOL Multiphysics environment with
customized physics interfaces for modeling of batteries. These physics interfaces
provide tools for building detailed models of the configuration of the electrodes and
electrolyte in electrochemical cells. They include descriptions of the electrochemical
reactions and the transport properties that influence the performance of batteries and
other electrochemical cells. With this module, you have the perfect tools to investigate
the influence of using different materials, geometric configurations, and operating
conditions on the performance of a cell.

The physics interfaces include chemical species transport, current balances, heat
transfer, and fluid flow in electrochemical cells. You can use the module to investigate
the performance of batteries at different operating conditions for different electrode
configurations, structures and dimensions, for separators, current collectors and
current feeders, and for the choice of materials and chemistry.

The module adds the electrochemistry interfaces, which contains the Primary Current
Distribution, Secondary Current Distribution, and Tertiary Current Distribution,
Nernst-Planck interfaces. These are available for solid non-porous electrodes and for
porous electrodes. General tertiary current distribution models can also be set up using
the Chemical Species Transport interfaces. In addition to these generic physics
interfaces, the Electrochemistry branch contains these dedicated physics interfaces:
Battery with Binary Electrolyte, Lead-Acid Battery, and Lithium-Ion Battery.

The tailored physics interfaces mentioned above are also complemented with extended
functionality in other physics interfaces for chemical species transport, heat transfer,
and fluid flow.

24 | CHAPTER 1: INTRODUCTION
The physics interfaces for chemical species transport of neutral species are extended by
adding functionality that directly couples to electrochemical reactions defined in the
physics interfaces for electrochemical cells.

Heat Transfer Interfaces includes heat sources that describe ohmic losses in the
electrodes and electrolyte and heat sources due to electrochemical reactions in
electrochemical cells.

The fluid flow capabilities are extended for laminar flow, where the chemical species
transport and the energy balances influence the properties of the flow.

A selection of suitable materials are also available in the Battery Material

Library. For more detailed information about materials, see Materials in
the COMSOL Multiphysics Reference Manual.

Finally, the Battery Design Module includes various model examples, such as:

• Lithium-ion (Li-ion) batteries

• Lead-Acid batteries
• Nickel-metal hydride (NiMH) batteries
• Vanadium redox flow batteries
• Soluble lead-acid flow batteries

See Where Do I Access the Documentation and Application Libraries? to locate and
use these examples and tutorials as a starting point to your own investigations.

Battery Design Module Physics Interface Guide

The table lists the physics interfaces available with this module in addition to the core
physics included with COMSOL Multiphysics.

In the COMSOL Multiphysics Reference Manual:

• Studies and Solvers

• The Physics Interfaces
• For a list of all the core physics interfaces included with a COMSOL
Multiphysics license, see Physics Interface Guide.

ABOUT THE BATTERY DESIGN MODULE | 25

 PHYSICS INTERFACE ICON TAG SPACE AVAILABLE STUDY TYPE
DIMENSION

Chemical Species Transport

Surface Reactions sr all dimensions stationary (3D, 2D, and 2D

axisymmetric models only);
time dependent
Transport of Diluted tds all dimensions stationary; time dependent
Species
Transport of Diluted tds all dimensions stationary; time dependent
Species in Porous Media
Transport of Diluted dsf 3D, 2D, 2D stationary; time dependent
Species in Fractures axisymmetric
Electrophoretic Transport el all dimensions stationary; stationary with
initialization; time
dependent; time dependent
with initialization
Chemistry chem all dimensions stationary; time dependent

Transport of tcs all dimensions stationary; time dependent

Concentrated Species
Nernst-Planck-Poisson tds+es all dimensions stationary; time dependent;
Equations stationary source sweep;
small-signal analysis,
frequency domain
Reacting Flow

Laminar Flow — 3D, 2D, 2D stationary; time dependent

axisymmetric
Laminar Flow, Diluted — 3D, 2D, 2D stationary; time dependent
Species axisymmetric

Reacting Flow in Porous Media

Transport of Diluted rfds 3D, 2D, 2D stationary; time dependent

Species axisymmetric
Transport of rfcs 3D, 2D, 2D stationary; time dependent
Concentrated Species axisymmetric

26 | CHAPTER 1: INTRODUCTION
PHYSICS INTERFACE ICON TAG SPACE AVAILABLE STUDY TYPE
DIMENSION

Electrochemistry

Primary Current cd all dimensions stationary; stationary with

Distribution initialization; time
dependent; time dependent
with initialization; AC
Secondary Current
impedance, initial values;
Distribution
AC impedance, stationary;
AC impedance, time
dependent
Tertiary Current tcd all dimensions stationary; stationary with
Distribution, initialization; time
Nernst-Planck dependent; time dependent
(Electroneutrality, with initialization; AC
Water-Based with impedance, initial values;
Electroneutrality, AC impedance, stationary;
Supporting Electrolyte) AC impedance, time
dependent
Electroanalysis tcd all dimensions stationary; time dependent;
AC impedance, initial
values; AC impedance,
stationary; AC impedance,
time dependent; cyclic
voltammetry
Electrode, Shell els 3D, 2D, 2D stationary; time dependent
axisymmetric
Battery Interfaces

Lithium-Ion Battery liion all dimensions stationary; time dependent;

(Binary 1:1 Liquid AC impedance, initial
Electrolyte, values; AC impedance,
stationary; AC impedance,
Single-Ion Conductor)
time dependent
Battery with Binary batbe all dimensions stationary; time dependent;
Electrolyte AC impedance, initial
values; AC impedance,
stationary; AC impedance,
time dependent

ABOUT THE BATTERY DESIGN MODULE | 27

 PHYSICS INTERFACE ICON TAG SPACE AVAILABLE STUDY TYPE
DIMENSION

Lead Acid Battery leadbat all dimensions stationary; time dependent;

AC impedance, initial
values; AC impedance,
stationary; AC impedance,
time dependent
Single Particle Battery spb all dimensions time dependent; time
dependent with
initialization
Lumped Battery lb all dimensions time dependent; AC
impedance, initial values;
Battery Equivalent ec Not space stationary; time dependent;
Circuit dependent frequency domain
Fluid Flow

Porous Media and Subsurface Flow

Brinkman Equations br 3D, 2D, 2D stationary; time dependent

axisymmetric
Darcy’s Law dl all dimensions stationary; time dependent

Free and Porous Media fp 3D, 2D, 2D stationary; time dependent

Flow axisymmetric
Heat Transfer

Heat Transfer in Porous ht all dimensions stationary; time dependent

Media

Common Physics Interface and Feature Settings and Nodes

There are several common settings and sections available for the physics interfaces and
feature nodes. Some of these sections also have similar settings or are implemented in
the same way no matter the physics interface or feature being used. There are also some
physics feature nodes that display in COMSOL Multiphysics.

28 | CHAPTER 1: INTRODUCTION
In each module’s documentation, only unique or extra information is included;
standard information and procedures are centralized in the COMSOL Multiphysics
Reference Manual.

In the COMSOL Multiphysics Reference Manual see Table 2-4 for

links to common sections and Table 2-5 to common feature nodes.
You can also search for information: press F1 to open the Help
window or Ctrl+F1 to open the Documentation window.

Where Do I Access the Documentation and Application Libraries?

A number of internet resources have more information about COMSOL, including
licensing and technical information. The electronic documentation, topic-based (or
context-based) help, and the application libraries are all accessed through the
COMSOL Desktop.

If you are reading the documentation as a PDF file on your computer,

the blue links do not work to open an application or content
referenced in a different guide. However, if you are using the Help
system in COMSOL Multiphysics, these links work to open other
modules, application examples, and documentation sets.

THE DOCUMENTATION AND ONLINE HELP

The COMSOL Multiphysics Reference Manual describes the core physics interfaces
and functionality included with the COMSOL Multiphysics license. This book also has
instructions about how to use COMSOL Multiphysics and how to access the
electronic Documentation and Help content.

Opening Topic-Based Help

The Help window is useful as it is connected to the features in the COMSOL Desktop.
To learn more about a node in the Model Builder, or a window on the Desktop, click
to highlight a node or window, then press F1 to open the Help window, which then
displays information about that feature (or click a node in the Model Builder followed
by the Help button ( ). This is called topic-based (or context) help.

ABOUT THE BATTERY DESIGN MODULE | 29

 Opening the Documentation Window

THE APPLICATION LIBRARIES WINDOW

Each model or application includes documentation with the theoretical background
and step-by-step instructions to create a model or application. The models and
applications are available in COMSOL Multiphysics as MPH files that you can open
for further investigation. You can use the step-by-step instructions and the actual
models as templates for your own modeling. In most models, SI units are used to
describe the relevant properties, parameters, and dimensions, but other unit systems
are available.

Once the Application Libraries window is opened, you can search by name or browse
under a module folder name. Click to view a summary of the model or application and
its properties, including options to open it or its associated PDF document.

Opening the Application Libraries Window

To open the Application Libraries window ( ):

CONTACTING COMSOL BY EMAIL

For general product information, contact COMSOL at info@[Link].

COMSOL ACCESS AND TECHNICAL SUPPORT

To receive technical support from COMSOL for the COMSOL products, please
contact your local COMSOL representative or send your questions to
support@[Link]. An automatic notification and a case number are sent to you by
email. You can also access technical support, software updates, license information, and
other resources by registering for a COMSOL Access account.

COMSOL ONLINE RESOURCES

COMSOL website [Link]

Contact COMSOL [Link]/contact
COMSOL Access [Link]/access
Support Center [Link]/support
Product Download [Link]/product-download
Product Updates [Link]/support/updates
COMSOL Blog [Link]/blogs
Discussion Forum [Link]/community
Events [Link]/events

30 | CHAPTER 1: INTRODUCTION
COMSOL Application Gallery [Link]/models
COMSOL Video Gallery [Link]/video
Support Knowledge Base [Link]/support/knowledgebase

ABOUT THE BATTERY DESIGN MODULE | 31

 Overview of the User’s Guide
The Battery Design Module User’s Guide gets you started with modeling using
COMSOL Multiphysics. The information in this guide is specific to this module.
Instructions how to use COMSOL in general are included with the COMSOL
Multiphysics Reference Manual.

As detailed in the section Where Do I Access the Documentation and

Application Libraries? this information can also be searched from the
COMSOL Multiphysics software Help menu.

TABLE OF CONTENTS, GLOSSARY, AND INDEX

To help you navigate through this guide, see the Contents, Glossary of Terms, and
Index.

MODELING WITH ELECTROCHEMISTRY

The Modeling with Electrochemistry chapter discusses a variety of topics, including
Fundamentals of Electrochemistry Modeling, Modeling Electrochemical Reactions,
Modeling Cyclic Voltammetry, and Postprocessing Your Solution.

THE ELECTROCHEMISTRY INTERFACES

The Electrochemistry Interfaces chapter describes the Primary Current Distribution,
Secondary Current Distribution, Tertiary Current Distribution, Nernst-Planck,
Electrode, Shell, Current Distribution on Edges, BEM, and Electroanalysis interfaces.
The chapter also includes the underlying theory.

THE BATTERY INTERFACES

The Battery Interfaces chapter describes the Battery with Binary Electrolyte,
Lead-Acid Battery, and the Lithium-Ion Battery interfaces and the underlying theory
for these interfaces.

THE CHEMICAL SPECIES TRANSPORT INTERFACES

The Chemical Species Transport Interfaces chapter describes the Transport of Diluted
Species, Transport of Concentrated Species, the Transport of Diluted Species in
Porous Media, and the Surface Reaction interfaces. The rest of the chapter describes
these interfaces in detail as well as the underlying theory.

32 | CHAPTER 1: INTRODUCTION
Theory for the Transport of Diluted Species Interface section describes the Reacting
Flow in Porous Media (rfcs) and Reacting Flow in Porous Media (rfds) interfaces
including its underlying theory.

THE FLUID FLOW INTERFACES

The Fluid Flow Interfaces chapter describes the Darcy’s Law and Free and Porous
Media Flow interfaces, both included under the Porous Media and Subsurface Flow
branch. The Laminar Flow interface is also available and is described in the COMSOL
Multiphysics Reference Manual.

THE HEAT TRANSFER INTERFACES

The Heat Transfer Interfaces chapter describes how to couple electrochemical heat
sources to heat transfer.

THE MULTIPHYSICS COUPLING NODES

The Multiphysics Coupling Nodes chapter describes the coupling nodes available
under the Multiphysics node for coupling various electrochemical interfaces using
flow, potential, and temperature couplings, for example.

OVERVIEW OF THE USER’S GUIDE | 33

34 | CHAPTER 1: INTRODUCTION
 2

Modeling with Electrochemistry

In this chapter:
• Introduction to Electrochemistry Modeling
• Connecting to Electrical Circuits
• SPICE Import and Export

35
 Introduction to Electrochemistry
Modeling
In this section:

• What Is Electrochemistry?
• Electrochemical Applications
• Fundamentals of Electrochemistry Modeling
• Current Distribution Cases and Choosing the Right Interface to Model an
Electrochemical Cell
• Understanding the Different Approximations for Conservation of Charge in
Electrolytes
• Modeling Electrochemical Reactions
• Double Layer Capacitance
• Porous Electrodes
• Boundary Conditions for Running and Controlling Electrochemical Cells
• Aspects to Consider When Modeling Batteries or Fuel Cells
• Modeling Cyclic Voltammetry
• Common Simplifications When Modeling Electrochemical Cells
• Before You Start Building Your Model
• Meshing Advice
• Solving Electrochemical Models
• Postprocessing Your Solution

What Is Electrochemistry?
An electrochemical process is one that either converts electrical energy to chemical
energy or converts chemical energy to electrical energy.

In electrochemical reactions, chemicals react by gaining or losing electrons. Chemicals

can exchange these electrons with an electrical conductor or circuit. The chemical
potential — or thermodynamic driving force — for a chemical reaction is thus
converted into an electrical potential or voltage, which can be exploited to do useful
work when electrical current is drawn.

36 | CHAPTER 2: MODELING WITH ELECTROCHEMISTRY

Electrochemical Applications
Electrochemical systems may be classified in different ways.

One approach is to contrast those electrochemical systems involving desirable reactions

from those involving undesirable reactions. Synthetic electrolysis is an example of a
desirable reaction because the chemical process is promoted to generate a desired
product. Or, in designing a battery, for example, we might want to set up conditions
to promote an electrochemical reaction in order to extract useful energy.

Corrosion is an example of undesirable electrochemistry because in this case

spontaneous electrochemical reactions destroy structural materials and so harm the
integrity of a system: we aim to minimize the rate of these reactions.

Electrochemical systems can also be classified into systems that output energy or
systems that consume energy. Batteries and fuel cells are energy extraction devices —
an electrochemical reaction is used to convert the energy in chemical system into a
voltage. Such cells are also called galvanic cells. By contrast, in electrolysis, the system
consumes energy to promote an electrochemical reaction for synthesis. Similar
electrochemical systems needing energy input include manufacturing processes such as
electroplating. Electrochemical reactions may also be driven for electroanalysis, to
quantify or otherwise explore the chemical constituents or reactivity of a system.

The different electrochemical modules in COMSOL Multiphysics are designed to

offer tailored physics interfaces provision for each of these electrochemical situations.
The underlying physical description provided by the general physics interfaces
described below is common to all the modules — the differences between the modules
lies in the particular expected system inputs and outputs and the intended behavior of
the system.

Fundamentals of Electrochemistry Modeling

Electrochemical systems consist of electrically conducting media. These may be
classified as electrodes or electrolyte. An electrode carries current by transport of
electrons; normally the electrode is a conventional electrical conductor such as a metal.
The electrolyte carries current by transport of charged chemical species (ions).
Electrolytes are often salt solutions in water but may include salt solutions in other
liquid solvents, as well as solids, such as concrete, which can conduct by transport of
oxide ions. The electrical conductivity of an electrode is normally several orders of
magnitude larger than the electrical conductivity of an electrolyte.

INTRODUCTION TO ELECTROCHEMISTRY MODELING | 37

 THE ELECTRODE-ELECTROLYTE INTERFACE
At the electrode-electrolyte interface, conventional electrical current in the electrode
is converted into ionic current in the electrolyte. According to the overall conservation
of charge, these currents must balance here. The conversion between the two types of
current may arise due to electrochemical reaction (electrolysis) or capacitive charging.

Electrolysis occurs when a chemical species in the electrolyte exchanges one or more
electrons with the electrode. Capacitive charging occurs when the potential of an
electrode is changing, so that ions in the electrolyte are either attracted or repelled
from the surface, drawing a current.

Batteries and fuel cells can also involve porous electrodes, in which an electrode
material has a micro- or nanostructure that is permeable to electrolyte. The advantage
of such a material is the great increase in the area of the electrode-electrolyte interface.

Note that all current must move in circuits. An isolated electrode-electrolyte interface
cannot draw a net current, but a system with two such interfaces can. An
electrochemical system with two or more electrodes in contact with electrolyte is called
an electrochemical cell.

In an electrochemical cell with two electrodes, these electrodes are identified as an

anode, at which the electrochemical reaction transfers electrons from electrolyte to
electrode, and a cathode, at which electrons are transferred from the electrode to the
electrolyte. Note that it is the direction of the current that will determine if an
electrode reaction is anodic or cathodic. For a battery, for instance, the location of the
anode and cathode will change depending on whether the battery is charged or
discharged. (The general habit in the battery community to always denounce the
positive electrode as the “cathode” is hence strictly only correct during battery
discharge.)

Conventional electric current is the flow of positive charge, which is then from anode
to cathode through the electrolyte. A closed circuit, conserving overall system charge,
is formed by the flow of electric current in the electrode domains (and any electrical
circuitry) from cathode to anode, and by the transport of ions through the electrolyte
domains from anode to cathode.

OUTPUTS OF INTEREST FROM A MODEL

The experimentally measurable features of an electrochemical system are the external
(lumped) current and voltage acting between the two electrodes. It is, in general,
impossible to measure local current densities or potentials at different points on the

38 | CHAPTER 2: MODELING WITH ELECTROCHEMISTRY

surface of a conducting electrode, or at arbitrary points within an electrochemical
system.

The advantage of physical modeling is the ability to investigate the full

space-dependent behavior of the system under a wide range of circumstances to
identify the reasons for the observed current-voltage relationship, and so to identify
the appropriate physical conditions to optimize current and voltage as required.

The overall current-voltage curve of an electrochemical cell is also known as a

polarization curve or, in an analytical context, a voltammogram. These curves are not
unique but rather depend on the means by which the current or voltage is altered, since
these lumped parameters are related to multiple physical effects with different length
and time scales. Hysteresis in practical polarization curves is not uncommon.

Polarization curves are frequently nonlinear. The combination of nonlinearity and

hysteresis means that electrochemical cells do not necessarily resemble “ideal”
electrical components (such as a circuit of resistors and capacitors) in the sense of
giving a predictable and linear current-voltage response.

• Potential Variables
• Current Variables and Calculating the Total Cell Current

Current Distribution Cases and Choosing the Right Interface to

Model an Electrochemical Cell
COMSOL Multiphysics has many built-in physics interfaces aimed at specific
applications. In many generic cases, however, the modeler has to make some basic
assumptions about his system before starting to build his model.

Under the assumption of a linear relation of current density to electric field, Ohm’s law
is obeyed for the electrolyte current. This is the assumption of primary current
distribution, where one also assumes infinitely fast electrodes kinetics, resulting in
negligible potential drops over the electrode-electrolyte interfaces. If the electrode
reaction kinetics proceed at a finite rate, then the system has a secondary current
distribution. In the cases of more advanced nonlinear charge conservation equations
being required and concentration-dependent electrode polarization, the system is
described as obeying tertiary current distribution.

In some applications, especially within the field of electroanalysis, the potential

gradients in the electrolyte are so small that the spatial distribution of current in the

INTRODUCTION TO ELECTROCHEMISTRY MODELING | 39

 electrolyte is not solved for. Such models are instead centered around the interplay of
electrode kinetics and transport (by diffusion) of the reacting species in the vicinity of
the electrode.

A rule-of-thumb flowchart for selecting a proper current distribution interface for a

model is shown below. The recommendations here are indicative and the modeler may
sometimes want to deviate from the suggested route; in particular, simpler descriptions
are recommended at an earlier stage of model development. In the following sections
we explain some of the theory behind this flowchart with regards to the description of
the electrolyte charge transport and electrode reactions.

Understanding the Different Approximations for Conservation of

Charge in Electrolytes
Deciding how to model the charge transport in the electrolyte is usually the starting
point when setting up an electrochemical model since this will determine what physics

40 | CHAPTER 2: MODELING WITH ELECTROCHEMISTRY

interface you will use when starting to build your model. Different theoretical
descriptions of the electrolyte current density are included in COMSOL Multiphysics.
They are applicable in different circumstances as discussed in this section.

The electric displacement field in a medium is related to the local charge density
according to Gauss’s law, one of Maxwell’s equations:

∇ ⋅ D = ρv

In electrolytes, we can normally assume that the electrical permittivity is constant and
equal to a bulk value:

D = ε 0 ε s E = – ε 0 ε s ∇V

Hence

2 ρv
∇ V + ---------- = 0
ε0 εs

In an electrolyte with ionic charge carriers, the charge density can be written as:

ρv = F  zi ci
i

Hence

F
ε0 εs 
2
∇ V + ---------- zi ci = 0
i

This is the Poisson equation relating the electrolyte potential to the distribution of
charge carriers within the electrolyte. In its derivation we assumed that the only charge
carriers are ions, and that the solvated ions and electric field do not alter the
permittivity of the medium.

The mass transport of the charge carriers in aqueous systems is normally given by the
Nernst-Planck equations. These equations neglect ion-ion interactions, and so they
are only exact for infinitely dilute solutions:

N i = – D i ∇c i – z i u m, i Fc i ∇φ l + c i u

Note that concentrated electrolyte systems, such as those in many batteries, use an
extended concentrated species flux definition, based on the Maxwell-Stefan set of

INTRODUCTION TO ELECTROCHEMISTRY MODELING | 41

 equations. This will result in a different set of equations to solve for, but the general
principles and conclusion in this section will be the same.

Substituting the Nernst-Einstein relation for the electrical mobility of an ion we get:

ziF
N i = – D i  ∇c i + -------- c i ∇φ l + c i u
RT

The above expressions for the n species i, together with the Poisson equation, give a
set of n+1 equations in n+1 unknowns. These are the Nernst-Planck-Poisson
equations. They can be defined in COMSOL Multiphysics by coupling Transport of
Diluted Species with Electrostatics, or by using the Tertiary Current Distribution,
Nernst-Planck interface with Charge conservation model: Poisson, but they are highly
nonlinear and difficult to converge. Most often, further approximations can simplify
the problem without compromising accuracy.

• Theory for the Transport of Diluted Species Interface

• Theory of Electrostatics in the COMSOL Multiphysics Reference
Manual

An important dimensional quantity occurring in the Poisson equation is:

RT ε 0 ε s
xD = ------------------
-
2
F I

This is the length across which electric fields are screened. It is called the Debye length.
This is a very short length in electrolyte solutions: for a typical ionic strength, it is of
the order of 1 nm. Electroneutrality holds at distances much larger than 1 nm from a
charged surface:

 zi ci = 0

The constraint of electroneutrality can be used as a condition determine the electric

potential in the Nernst-Planck equations, in place of the full Poisson equation. The

42 | CHAPTER 2: MODELING WITH ELECTROCHEMISTRY

Nernst-Planck equations with electroneutrality are used to describe current flow in the
Tertiary Current Distribution, Nernst-Planck interface.

The Tertiary Current Distribution, Nernst-Planck Interface

The current flow itself is given by:

il = F  zi Ni
From substitution of the Nernst-Planck expressions for Ni, the laws of conservation of
mass and charge combine to automatically satisfy conservation of current.

We can simplify the system further by considering the arising expression for il in more
detail:

2
F
  zi  zi ci
2
il = – F D i z i ∇c i – -------- ∇φ l Di ci + u
RT

Clearly, the right-most term is zero: that is, convection of an electroneutral solution
does not cause current flow. The leftmost term (diffusion current) also vanishes due to
electroneutrality if the gradients of the charge carrying species are zero.

Even if this is not the case, however, this term is often much smaller than the central
term (migration current), so long as the concentrations of the current-carrying ions do
not vary markedly through the solution. Under conditions where the composition of
the electrolyte can be considered nearly constant and current-carrying ions are not
significantly depleted, the diffusion current can be assumed to contribute negligibly.

Hence, it follows that:

i l = – σ l ∇φ l

This expression for current density is used in the Secondary Current Distribution
interface, and also the Primary Current Distribution interface. The difference between
these interfaces lies in the treatment of the electrode-electrolyte interfaces (see Kinetics
of Electrochemical Reactions below). From the above, the conductivity of the
electrolyte σl is given as:

2
F
 zi
2
σ l = -------- Di ci
RT

INTRODUCTION TO ELECTROCHEMISTRY MODELING | 43

 So long as this quantity does not vary markedly through the solution, the
approximation of zero diffusion current is good. If the diffusivities and concentrations
can be taken as constant, we can approximate that:

2
2F ID mean
σ l ≈ -----------------------------
RT

The advantage of the ohmic expression for current density is that it is a linear relation
of current density to electrolyte potential. It is only weakly nonlinear if σl is allowed to
depend on a concentration solved for in a species transport interface. By comparison,
the Nernst-Planck equations with electroneutrality can be highly nonlinear.

The approximations used to derive the secondary current distribution expression place
tighter constraints on the allowed system configurations, however. The ionic strength
of the solution must remain near-constant for the constant conductivity approximation
to be valid. Usually this is only the case for relatively high conductivity solutions.

When the conductivity is large with respect to the current drawn, the electric field
becomes negligible in solution. For negligible electric fields, a diffusion-only
approximation may be used, where E = 0. This converts the Nernst-Planck equations
into Fick’s laws, with a term for convective transport where necessary. Fick’s laws with
convection and electrochemical boundary conditions are solved for in the
Electroanalysis interface.

Even if you think a problem will involve the full Nernst-Planck equations,
it is best to set the model up in Secondary Current Distribution first, in order
to identify any other possible complications in the system while using a
simpler electrochemical model.

Theory for the Current Distribution Interfaces

Modeling Electrochemical Reactions

Electrochemical reactions are defined by using Electrode Reaction or Porous Electrode
Reaction nodes. An electrode reaction is defined by its thermodynamics, kinetics, and
stoichiometry. The latter describes the mass fluxes, sources and sinks arising due to a
certain current density of the reaction.

44 | CHAPTER 2: MODELING WITH ELECTROCHEMISTRY

THERMODYNAMICS OF ELECTROCHEMICAL REACTIONS
An electrolytic reaction involves the exchange of electrons with the electrode. Such a
reaction is written as reduction, even if the reaction occurs predominantly in the
oxidative direction. For example:

+ -
Ag (aq)+e ↔ Ag(s)

This reaction is called a “half-cell” reaction, since it will occur at a specific

electrode-electrolyte interface. It cannot occur in isolation, but only when coupled to
another half-cell reaction within a two-electrode electrochemical cell. Each reaction
has a characteristic Gibbs energy change that determines whether or not it is
thermodynamically favorable. A negative Gibbs energy change means that the reaction
proceeds spontaneously — it is thermodynamically “downhill”.

The Gibbs energy change is related to the equilibrium potential difference from the
electrode to the electrolyte according to:

ΔG m
E eq, m = – -------------
nm F

where Eeq,m is the potential difference on some external reference scale for which the
reaction is at equilibrium (ΔG = 0). This is called the equilibrium potential or
reduction potential (or in corrosion, corrosion potential) of the electrochemical
reaction, and its absolute value depends on the choice of reference electrode.

Equilibrium potentials should always be quoted versus a specific

reference. If a different reference scale is used in different parts of your
model, the thermodynamics of the system may not behave as expected.

From the standard thermodynamic relation

ΔG = – RT ln K

it follows

RT
E – E eq = -------- ln K
nF

This is the Nernst equation which is a universal thermodynamic expression. It is always

true of systems at thermodynamic equilibrium; it does not necessarily apply to systems
not at equilibrium.

INTRODUCTION TO ELECTROCHEMISTRY MODELING | 45

 Assuming that the species are ideal and that activity effects can be treated as constant,
then for the conversion between unimolecular reduced and oxidized species:

[Ox] = [Red] exp   -------- ( φ s – φ l – E f )

nF
  RT 

Hence at equilibrium, the concentrations of reactants and products at the

electrolyte-electrode surface are related by an expression which depends on the
potential difference between the two phases, and two reaction parameters: n, the
number of electrons transferred per molecule reduced; and Ef, the formal reduction
potential of the reaction measured on the same potential scale as the
electrode-electrolyte potential difference.

The quantity

η m = φ s – φ l – E eq, m

is known as the overpotential and is particular to a specific reaction occurring at the

interface.

η m depends on both the electric potential in the electrode φ s and the

electrolyte potential φ l . Where there is substantial resistance to current
flow through a solution, the corresponding potential difference in φ l
called ohmic drop, alters the position of the electrochemical equilibrium.
Additional applied potential in the electrical circuit may then be needed
to drive an equivalent overpotential.

KINETICS OF ELECTROCHEMICAL REACTIONS

The Nernst equation tells us the position of equilibrium of a reaction. However, it tells
us nothing about how fast the system may get there. If there is a kinetic limitation —
that is, if the reaction proceeds slowly — the equilibrium condition may never be
observed. As a familiar example, diamond is thermodynamically unstable with respect
to reacting to form graphite at room temperature and pressure. However, this reaction
is kinetically limited by a vast activation energy for the reorientation of atoms, such that
it is never in practice observed, and diamond is technically described as metastable.

We encounter the same issue in many electrochemical contexts. Reactions are

prevented from proceeding to their equilibrium by kinetic limitations. Indeed,
overcoming the natural kinetic sluggishness of the surface reactions of small, nonpolar
molecules such as hydrogen and oxygen is key to much fuel cell research.

46 | CHAPTER 2: MODELING WITH ELECTROCHEMISTRY

There are two important expressions describing the current density due to an
electrochemical reaction as a function of the overpotential and the concentrations of
reactant and product. It should be noted that the validity of these expressions is not
general and can never replace experimental kinetic data if such is available.

The first is the Tafel law which describes an irreversible anodic or cathodic process:

log  ---- = Aη
i
 i 0

The constant A is the Tafel slope and has units 1/V. It is usually close to a half-integer
multiple of F/RT and is less than or equal to nF/RT. Note that a reference exchange
current density i0 must be specified for the reaction. This is by definition the current
density drawn at zero overpotential.

The Tafel law assumes that a reaction is irreversible. If the reverse reaction
might occur in practice, Tafel kinetics will not be correct.

The second expression is the Butler-Volmer equation which describes a reversible

process, so that either anodic or cathodic current may flow depending on the sign and
magnitude of the overpotential:

α a Fη – α c Fη
i = i 0  exp  --------------- – exp  ----------------- 
RT RT

The Butler-Volmer equation is the most general description of electrode kinetics. It is

highly adaptable because:

• i0 is an empirical quantity.
• It agrees with the Nernst equation when i = 0, so for a very fast reaction ( i 0 → ∞ )
then the Butler-Volmer equation gives the same potential difference as the Nernst
equation. This is equally true under high resistance conditions.
• It agrees with the Tafel equation when either the anodic or cathodic term
dominates. For highly irreversible reactions (very low i0), appreciable current is only
drawn for large overpotential, so this is typically the case.

For a discussion on the Butler-Volmer expression and concentration changes of the

participating species, see the Defining Concentration Dependent Butler-Volmer
Kinetics section below.

INTRODUCTION TO ELECTROCHEMISTRY MODELING | 47

 For a reversible reaction at very low overpotential (η of order RT/F ~ 25 mV), the
exponentials in the Butler-Volmer equation can be linearized:

( α a + α c )F
i loc = i 0  ---------------------------- η
 RT 

Using a linearized Butler-Volmer reaction can be advantageous when

investigating convergence issues of a model.

The linearized Butler-Volmer equation is not correct for applied

overpotentials larger than (RT/F). This is about 25 mV at room
temperature. It is not suitable outside this range and therefore its use is
confined to electrochemical processes occurring exclusively at low current
density, such as electroplating or electrochemical impedance spectroscopy.

Electrode Kinetics Expressions

FLUXES AND SOURCES/SINKS DUE TO ELECTRODE REACTIONS

Electrode reactions will result in a molecular flux of reacting species to or from the
electrode surface. If you are including mass transport in your model it is common to
couple the flux of a reacting species on a boundary to the electrode reaction current
density (by the Faraday’s law of electrolysis).

The coupling of chemical flux to electric current density is automated in some of the
Electrochemistry interfaces by defining the reaction stoichiometry in the Electrode
Reaction and Porous Electrode Reaction nodes. In the Chemical species transport
interfaces the coupling however needs to be set up manually by the Electrode Surface
Couplingnodes. When modeling porous electrodes, the corresponding coupling node
to create a source/sink in a domain is the Porous Electrode Coupling node.

The mathematical treatment can be summed up by the expression:

ν jm i m
N j = – ----------------
nm F

48 | CHAPTER 2: MODELING WITH ELECTROCHEMISTRY

This means that the flux Nj of chemical species j into the surface is proportional to the
current density im due to reaction m drawn at an electrode-electrolyte interface. The
constant of proportionality is the stoichiometric number for the species divided by n m,
the number of electrons transferred in reaction m, in a reductive direction and F the
Faraday constant (96485 C/mol, the absolute charge on a mole of electrons).

As such, knowledge of the stoichiometry of an electrochemical reaction allows the local

flux of a chemical species to be coupled to the current density contributed by that
reaction. Note that multiple reactions may take place simultaneously at an electrode,
and their contributions to the current density are simply summed.

The stoichiometric coefficients of the chemical species in an

electrochemical reaction are conventionally written with the forward
reaction in the direction of reduction, even if in practice within the system
the reaction predominantly proceeds in the other direction.

COMSOL Multiphysics uses the standard convention that anodic

(oxidative) current is positive. Cathodic (reductive) current is negative.

DEFINING CONCENTRATION DEPENDENT BUTLER-VOLMER KINETICS

If the concentrations at an electrode surface change, this will have an impact on the
local kinetics. The Butler-Volmer kinetics expression is derived by considering the rate
of a redox reaction

-
Ox + ne ↔ Red (2-1)

as the sum of the forward and backward rates according to:

i loc α a FE α c FE
r = -------- = k fwd c R exp  --------------- – k rwd c O exp  – --------------- (2-2)
nF  RT   RT 

where kfwd and krwd are reaction rate constants and cO and cR are the activities of the
oxidized and reduced species of the redox couple, respectively. The potential E is here
defined as

E = φs – φl (2-3)

and the transfer coefficients are equal the sum of electrons in the charge transfer
reaction according to

INTRODUCTION TO ELECTROCHEMISTRY MODELING | 49

 αa + αc = n (2-4)

By defining an equilibrium potential at which the forward reaction and backward

reaction rates are equal, Equation 2-1 can be shown to be equivalent to the commonly
used Butler-Volmer equation:

α a Fη α c Fη
i loc = i 0  exp  --------------- – exp  – --------------  (2-5)
  RT   RT  

In this formulation the exchange current density, i0, is defined as:

α ⁄ n αa ⁄ n
i 0 = i 0, 0 c Rc cO (2-6)

where i0,0 is the exchange current density at standard conditions.

The overpotential is here defined as

η = E – E eq (2-7)

where Eeq is the equilibrium potential is defined by the Nernst equation as

RT c R
E eq = E eq, 0 – -------- ln ------ (2-8)
nF c O

and Eeq,0 is the equilibrium potential at standard conditions.

Note that in Equation 2-5 both i0 and Eeq are concentration dependent. This has some
numerical drawbacks when modeling electrochemical cells including mass transport,
since for low concentrations of the participating species (that is, when c O → 0 or
cR
c R → 0 ), the factor ln ------ may become undefined during the solution process. An
c
expression of the form of O Equation 2-2 is more desirable since this expressions contains
a simple linear dependence on the species activities.

A common solution to this issue is to rewrite the Butler-Volmer expression by defining

the overpotential with respect to a fixed reference state for the activities cR, ref and cO,
ref (typically corresponding to the inlet or initial concentrations), resulting in

cR α a Fη ref cO α c Fη ref
i loc = i 0, ref  ------------- exp  -------------------- – -------------- exp  – -------------------  (2-9)
 c R, ref  RT  c O, ref  RT  

where

50 | CHAPTER 2: MODELING WITH ELECTROCHEMISTRY

 α ⁄n α ⁄n
i 0, ref = i 0, 0 c Rc, ref c Oa, ref (2-10)

and

η ref = E – E eq,ref (2-11)

with

RT c R, ref
E eq,ref = E eq, 0 – -------- ln -------------- (2-12)
nF c O, ref

Note that Equation 2-9 now contains a linear dependence on the activities cO and cR.

Double Layer Capacitance

The Tafel and Butler-Volmer expressions can be used to calculate the magnitude of the
current due to electrolysis: this is called faradaic current. However, the
electrode-electrolyte interface may also draw capacitive current due to the attraction
or repulsion of ions creating an oppositely charged layer of ions to form in solution
close to the electrode.

The layer of charge on the electrode and layer of opposite charge in the adjacent
electrolyte is called the double layer and can be thought of as behaving like a parallel
plate capacitor, since the absolute amount of charge it separates varies with the charge
density on the electrode, and hence with its voltage. The physics of double layer
structure and formation are highly complex and are not yet well understood. One of
the simplest empirical methods to account for the observed influence of capacitance
on polarization curves is to introduce a constant ideal capacitance across the
electrode-electrolyte interface.

This effect can be added to via the Double Layer Capacitance condition. The capacitor
stores a surface charge density Q = C d ( φ s – φ l ) , and contributes a dynamic charging
current density (non-faradaic current) equal to iNF = dQ/dt. The total current
recorded in a real experiment equals:

i tot = i Far + i NF

Sometimes in electroanalysis a blank scan with no electrolysis is run to subtract

non-faradaic current. If double layer capacitance is ignored in your model, you should

INTRODUCTION TO ELECTROCHEMISTRY MODELING | 51

 make sure that you are comparing it to experimental data recorded under the same
conditions.

The ability of COMSOL Multiphysics to model electrostatics and

transport of charged species make it tempting to incorporate the double
layer explicitly to add more detail to a model. These coupled equations are
always extremely nonlinear and convergence is not trivial except in the
simplest cases. Although the diffuse double layer can be modeled in
isolation (see example), this is not recommended in conjunction with a
fuller electrochemical model.

Double Layer Capacitance

Porous Electrodes
A porous electrode is one in which the three-dimensional structure of the electrode is
permeable to electrolyte. The electrode-electrolyte interface then extends over a much
larger surface area. This specific surface area (“SSA”, area per unit volume, units 1/m)
is a key property of a porous electrode. Additionally, such an electrode can conduct
electrical current independently through its electrode and electrolyte domains.

Most electrochemical interfaces in COMSOL Multiphysics include Porous Electrode

domain nodes that can be used to model the above situation. In a Porous Electrode,
current density is carried in both the electrode and in the pores which are assumed to
contain electrolyte. For gas diffusion electrodes where the solid is conducting but the
pore phase is not, the Electrode condition should be used.

It is common to combine an electrochemical interface with other physics, in order to

model the mass transport, heat transfer and flow properties of a porous medium. For

52 | CHAPTER 2: MODELING WITH ELECTROCHEMISTRY

instance, Secondary Current Distribution might be coupled to Transport of Diluted
Species in Porous Media, Heat Transfer in Porous Media and Darcy’s Law.

Homogenized transport parameters such as diffusion coefficients are

commonly obtained for a bulk solution of the material. In porous media
these must be corrected for tortuosity and porosity. Carefully consider
such effects when defining your material properties.

Porous Electrode Theory

Boundary Conditions for Running and Controlling Electrochemical

Cells
An electrochemical cell is typically operated by controlling either the cell voltage
(potentiostatic control) or the cell current (galvanostatic control). In a lab experiment
this is accomplished by using a potentiostat.

In a model, potentiostatic control is defined by using fixed potential boundary

conditions. This can be done by setting the Electric Potential with respect to ground to
control the cell potential, or the Electrode Potential with respect to a reference potential
somewhere in the system. Galvanostatic control can be accomplished using Total
Current or Average Current Density boundary conditions. For both cases, one electrode
in the cell needs to be grounded.

Mathematically, a Total Current or Average Current Density condition implies setting the
potential of a boundary to be equal to an additional extra global potential degree of
freedom (floating potential) to comply with the specified current condition. For this
reason, solving for galvanic control is numerically slightly more complex.

Note that explicitly prescribing the current density distribution on an electrode

boundary is hard to accomplish in a real world experiment. In higher dimensions than
1D, Electrode Current Density and Electrolyte Current Density boundary conditions
should be used with care.

SHORT-CIRCUITING A CELL AND GALVANIC CORROSION

The simplest way to model a short-circuited cell is to set both electrodes to the same
(electronic) potential, using a fixed potential boundary condition. The charge balance

INTRODUCTION TO ELECTROCHEMISTRY MODELING | 53

 equation of the electrolyte will make sure the total current over all electrode surfaces
sums up to zero.

Note that many galvanic corrosion situations are practically equivalent to a short circuit
of two electrodes consisting of different metals. In such models, the two metals are set
to the same potential. Usually this potential is chosen to be zero (ground).

• Electrode Potential
• Reference Electrode

Aspects to Consider When Modeling Batteries or Fuel Cells

Batteries and fuel cells are electrochemical energy extraction devices that work by using
a conducting domain to separate two regions, where the two halves of an overall
favorable chemical reaction proceed. By preventing the mixing of reactants and instead
forcing the reaction to proceed by mediation of electrical current between the
separated reactants, energy can be extracted as a voltage.

In a battery, there is a finite supply of reactant and the system is closed. In a fuel cell,
by contrast, there is a continuous feed of reactant to the system. A battery can be
simpler since it involves a single closed system, but a fuel cell may have other
advantages such as decreasing overall weight since it separates the site of energy storage
from that of energy extraction.

A battery does not have a steady state condition since its feedstock of reactants
progressively depletes until it is consumed. Once consumed, the battery is discharged
and it will no longer provide a voltage as its source of electrochemical energy has run
out. In a rechargeable battery, the process is reversible and the application of a voltage
can return the battery to saturation with feedstock under charging.

The electrochemistry in a battery model usually does not have a steady

state, and so it is not appropriate to use a Stationary study with a battery
interface.

Fuel cells do have steady states, although transient effects may also be important in fuel
cell research. In a fuel cell, it is typically important to identify what features of the
system may be rate-limiting for the steady-state current: the transport of reactants to

54 | CHAPTER 2: MODELING WITH ELECTROCHEMISTRY

the electrodes, the electrode kinetics themselves and the transport of current through
the electrolyte may all cause bottlenecks.

The maximum achievable voltage in a battery or fuel cell is the difference between the
half-cell potentials. The discharge mode is the direction in which the overall reaction
is thermodynamically downhill (negative ΔG).

There can be variation in the literature between whether the charge or

discharge mode is assumed when an electrode in a battery is referred to as
the “anode” or “cathode”. Each electrode can operate in both roles,
depending on whether the battery is charging or discharging.

Typically a battery model can be set up using Secondary Current Distribution to describe
charge transport since the long charge and discharge times ensure that conductivities
remain relatively uniform through the cell. If coupling to species transport is required,
Transport of Diluted Species can be added with an Electrode Reaction Coupling condition.

PREDEFINED BATTERY INTERFACES

Certain common battery types have predefined physics interfaces. Common for all
these interfaces is that by the use of concentrated electrolyte theory for the charge and
mass transport in the electrolyte, a more accurate electrolyte transport model is
achieved, compared to the Nernst-Planck equations described earlier in this chapter.

Lithium-Ion Battery is used for solving problems in batteries where the anode (in
discharge mode) is lithium metal intercalated into a material such as graphite, and the
cathode (in discharge mode) is lithium ions intercalated into a transition metal oxide.
The electrical current through the electrolyte is carried by lithium ions, typically in an
organic solution. Because both the anode and cathode materials are typically porous to
maximize the active surface area, the Porous Electrode domain node is standard do
define each electrode.

The Battery with Binary Electrolyte interface can be used for a range of general battery
types involving porous electrodes and current transfer through an ionic conductor. An
example is the nickel-metal hydride battery — an early type of rechargeable battery in
which the discharge anode is a metal hydride, the discharge cathode is a hydrated nickel
oxide, and the current is transferred by high concentration potassium hydroxide in
aqueous solution.

The Lead-Acid Battery interface is designed for batteries in which the discharge process
is the conproportionation of Pb(0) and Pb(IV) through a sulfuric acid medium.

INTRODUCTION TO ELECTROCHEMISTRY MODELING | 55

 FUEL CELL MODELING
Fuel cell modeling is complex since it is a closely coupled multiphysics problem
involving charge, mass and momentum conservation. These physics are normally set
up by coupling Secondary Current Distribution for the charge transfer, Transport of
Concentrated Species for gas phase mass transport, and Free and Porous Media Flow for
momentum transport (fluid flow) in the porous gas diffusion layers and the free flow
gas channels. The latter is a combination of Laminar Flow for free flow and Brinkman
Equations for porous flow.

In a fuel cell, any one of electrochemical reactivity, mass transport of reactants to either
electrode, and electrical resistance can cause a “bottleneck”, limiting the current drawn
for a given voltage. An accurate study of the polarization curve of a fuel cell must
therefore incorporate all of the physical effects to identify the voltages at which the fuel
cell behavior varies from transport-limited to being limited by the kinetics of the
electrolysis reaction.

When setting up a fuel cell study, it is a good idea to include physics

interfaces one at a time. In particular, make sure that Fluid Flow physics
interfaces are correctly set up before proceeding to incorporate species
transport. See also Solving Electrochemical Models below.

• The Transport of Concentrated Species Interface

• The Free and Porous Media Flow Interface
• The Primary and Secondary Current Distribution Interfaces

Modeling Cyclic Voltammetry

In a cyclic voltammetry experiment, a potentiostat is used to sweep the voltage at the
working electrode linearly from a start potential to a vertex potential, and back again.
Typically, the potential window is chosen to span the formal potential of a redox couple
of interest, allowing both the kinetics and transport properties of the chemical species
to be investigated. The target species reacts under kinetic control to the point of
depletion where the current becomes transport-controlled.

The built-in Cyclic Voltammetry study step in the Electroanalysis interface can be used
to automatically set up the voltage sweep in a time-dependent study.

56 | CHAPTER 2: MODELING WITH ELECTROCHEMISTRY

Common Simplifications When Modeling Electrochemical Cells

SHOULD I MODEL IN 3D OR CAN I MODEL IN 1D?

Many electrochemical systems use repetitive unit cells of high aspect ratio. In these
cases, the lumped effect of edge phenomena in the system will be small. For example,
in fuel cells or batteries it is often possible to use one-dimensional geometries with little
loss of detail. Consider also any mirror or rotational symmetries. Reducing the
geometry dimension where possible, either exactly or approximately, will reduce the
meshing and solving time significantly.

Starting with a 1D model helps to understand the influence of different

reactions and phenomena in an electrochemical system, and gives a good
first estimate of current-voltage behavior.

NEGLECTING THE CHARGE TRANSFER AND POTENTIAL GRADIENTS IN

ELECTRODES
The voltage over the surface of an electrode is typically constant — or very nearly
constant — since it is a good conductor. This implies that it is either the intrinsic
resistance of the electrolyte or the rate of the electrochemical reaction at the
electrode-electrolyte interface that controls the amount of current drawn in an
electrochemical cell. On the assumption of a constant surface voltage, the electrode
domain itself need not be modeled, and the coupling of charge and mass transport at
its surface treated by an Electrode Surface node.

Electrode Surface

However, when modeling porous and gas diffusion electrodes the metal phase
potential is need typically to be included since the conductivity of the metal phase
potential can be much lower in this type of electrodes. This is done in the Porous
Electrode nodes.

HALF-CELL MODELS
Often, an investigator is only interested in the chemistry taking place at one electrode
in a cell. A model of one electrode is called a “half-cell model”.

INTRODUCTION TO ELECTROCHEMISTRY MODELING | 57

 This would correspond to an experimental situation where the electrode of interest —
be it anode or cathode — is classified as the working electrode, and the other electrode
is called the counter electrode.

One usually ignores the kinetics of the counter electrode in a model; commonly it is
represented by a constant potential boundary condition. Such a model is only valid if
the counter electrode can draw arbitrarily large amounts of current compared to the
working electrode, so that it never limits the current flow in the electrochemical cell.

REPLACING THIN LAYERS WITH BOUNDARY CONDITIONS

When considering a layer that is very thin compared to other dimensions in the
geometry, it is usually correct to treat that layer using a physical condition, rather than
meshing it.

One important example is the catalyst layer in a fuel cell. Since this layer is only
nanometers in size, transport across it is very fast compared to other parts of the
system. Hence, it is not necessary to resolve a distribution of concentrations or
potentials through the layer.

Another example is the passivation layer on an oxidized electrode surface, for which
the “Thin Film Resistance” setting can be used. Because the layer is much thinner than
its surroundings, the electric field through it is almost constant. Therefore, an ohmic
expression can be substituted to create a boundary condition with a potential drop.
This is much more efficient than meshing a geometrically narrow layer.

Film Resistance

INFINITE ELEMENTS FOR STEADY-STATE ELECTROANALYSIS

For microelectrodes, the diffusion profile may approach a steady state whose size is
much larger than that of the working electrode of interest. In such an example, it is
preferable to circumscribe the simulation space to a region not more than about
twenty-five times the electrode size - assuming that the surrounding electrolyte is
uniform. Applying a bulk boundary condition such as a fixed concentration at this
finite distance causes inaccuracy in the solution, however.

It is better to use a layer of Infinite Elements around the finite simulation space to
project the simulation space to infinity, eliminating any error from artificially limiting
the simulation space. This is a typical approximation when the electrolyte domain is a

58 | CHAPTER 2: MODELING WITH ELECTROCHEMISTRY

few orders of magnitude larger than the electrode: for example, a microelectrode in a
cm-scale reaction vessel.

Infinite Elements, Perfectly Matched Layers, and Absorbing Layers in the

COMSOL Multiphysics Reference Manual

Before You Start Building Your Model

INTRODUCING COMPLEXITY ONE STEP AT A TIME

The true art of modeling is knowing what phenomena to include and what phenomena
to neglect. Building complexity in a model by adding one additional piece of physics
or geometric feature at a time is usually the fastest way to reach the modeling goal.
Here are some general tips:

• Start thinking about your cell in the lowest possible dimension. Starting with a 1D
model helps to understand the influence of different reactions in an electrochemical
system, and gives a good first estimate of current-voltage behavior. Go from 1D to
2D, then from 2D to 3D.
• Every electrode reaction adds numerical nonlinearities to your model. If you have
multiple electrode reactions, add them one at a time.
• Start with a simple description of the electrolyte current, such as Secondary Current
Distribution. Analyze the results to ensure that the electrochemical model is
consistent. Switch only to more complex electrolyte models, or add extra physics
such as mass transfer, heat transfer or flow, only if deemed necessary and when
satisfied with the results from a simpler case.
• If you are including flow in your model, solve for the flow field first before coupling
flow and electrochemistry together.

MODELING CHECKLIST
• Identify which domains are electrode and electrolyte. How will their conductivity
be assessed?
• What is happening on the electrode-electrolyte interfaces? Do both the anode and
the cathode need to be modeled? Do either need to be modeled as domains, or can
they be treated as boundaries?
• What electrochemical reactions take place at the electrode surfaces to cause charge
transfer? Can you parameterize their thermodynamics? Do you know the

INTRODUCTION TO ELECTROCHEMISTRY MODELING | 59

 equilibrium potentials? Can you parameterize their kinetics — and are the kinetics
ever going to be important? If not, ignore them.
• What is the system reference potential used to quote equilibrium potentials? Where
is the system ground?
• Are charge carriers in the electrolyte plentiful with respect to the drawn current
density, or is charge depletion important? Be aware of nonlinear effects that may
make convergence more difficult.
• If you are performing a time-dependent study, do your initial conditions have a
consistent current-voltage relationship?
• What other physics interfaces need to be coupled? How does charge transfer
influence these physics interfaces?

Meshing Advice
The default triangular (2D) or tetrahedral (3D) mesh is normally suitable for solving
the equations describing conservation of charge and mass for an general
electrochemical problem.

Electrochemical models involving mass transport generally benefit from a finer mesh
at the electrode surfaces, and at singularities such as the boundary between an
electrode surface and an insulating surface. This may be accomplished by adding
additional Size mesh nodes for these boundaries only. Also, consider refining the
“element growth rate”, and/or using boundary layer meshing in 3D.

Sometimes, a regular Mapped mesh can be more appropriate in a rectangular (2D)

domain; such domains are common in cutaway schematic studies of batteries and fuel
cells. Similarly the Swept mesh is often appropriate for very thin layers in a 3D model.

For fluid domains, the default physics-controlled mesh should be used, with boundary
layers as required.

For some problems with a stationary flow velocity field and time-dependent
convection of electrochemically reacting species, it may improve convergence to set up
a refined mesh without boundary layers for the species transport study step.

Meshing in the COMSOL Multiphysics Reference Manual

60 | CHAPTER 2: MODELING WITH ELECTROCHEMISTRY

Solving Electrochemical Models
Due to the highly nonlinear nature of electrode kinetics, some electrochemical models
can be difficult to solve. This section includes some general tips and tricks to facilitate
model solving, trouble shooting, and to improve solution accuracy.

GENERAL CURRENT DISTRIBUTION PROBLEMS

Start with the following suggestions if you encounter difficulty solving a problem.

• Make sure that the potential levels are “boot-strapped” somewhere in the model,
preferably by grounding one electrode. If there is no potential level defined
anywhere in the model, your model may have infinitely many solutions, and the
model will not converge.
• Consider using a Stationary with Initialization or a Time Dependent with Initialization
study. Both these studies will use a Current Distribution Initialization study step as a
first step to solve for the potentials only. If you run into problems solving for the
second step in this study you may have to change the “Current distribution type”
setting to Secondary on the Current Distribution Initialization study step node, and
also review the Initial Values as described in the next bullet.
• Review the Initial Values, especially the potentials. Suitable initial potential values can
usually be derived making a “potential walk” through the geometry, starting at the
grounded boundary. Compute electric and electrolyte potentials in other domains
by assuming equilibrium potential differences between electrode and electrolyte for
the main electrode reactions.
• Switch to Linearized Butler-Volmer kinetics (or a Primary current distribution) while
troubleshooting. This can be useful to help achieve a solution for a model that does
not solve with nonlinear kinetics, thereby indicating suitable initial values for the
nonlinear problem.
• If your model contains porous electrodes, try refining the mesh resolution in these
domains, especially toward the electrolyte boundaries.

• Electrochemistry Interfaces
• Specifying Initial Values and Meshing Techniques in the COMSOL
Multiphysics Reference Manual

INTRODUCTION TO ELECTROCHEMISTRY MODELING | 61

 ELECTROCHEMISTRY COUPLED TO MASS TRANSPORT
If the model involves electrochemistry coupled to mass transport, here are a few things
to try to help improve model convergence.

• Review the Initial Values for the concentration values. Zero initial concentration
values can be unsuitable for tertiary current distribution problems and battery
simulations, since they could imply that no charge carriers or no reacting material is
present.
• If steep concentration gradients are expected close to electrode surfaces, use
boundary layer meshing or finer mesh Size settings at these boundaries.
• When setting up user-defined kinetics expressions, avoid evaluating negative
concentrations by using expressions such as max(c, eps^2), where eps is the
machine epsilon (a very small but finite number).
• Try to solve for low currents and low overpotentials first, then increase the cell load
(for stationary problems this can be done using an auxiliary sweep with
continuation).
• If a problem involving mass transport is hard to solve for high currents, but solves
for low currents, it might be due to mass transport limitations. In this case, review
the transport parameter values and check that the current magnitudes are
reasonable. If the current densities are unreasonably high, review the electrode
reaction settings.
• For time-dependent problems that run into convergence problems after a certain
time, review the solution at the last time-step. If the solution of a reactant reaches
zero or a maximum value (for insertion electrodes in batteries) when the
convergence issues occur, the current load of the model is too high in relation to
your initial concentrations or mass transport properties.

• Electrochemistry Interfaces
In the COMSOL Multiphysics Reference Manual:

• 2D and 3D Boundary Layer Meshes

• Stationary and Parametric Sweep

SETTING UP A STUDY SEQUENCE FOR MULTIPHYSICS PROBLEMS

For multiphysics problems, try to adjust the study sequence.

• Solve certain physics interfaces in a sequence. This can in many cases reduce
computational time and improve convergence. Analyzing the results when solving a

62 | CHAPTER 2: MODELING WITH ELECTROCHEMISTRY

 physics interface separately can also help when troubleshooting a nonconverging
model.
• A good strategy is often to solve for the potentials only (that is, disable mass
transport and flow interfaces), using a stationary study step, before solving the full
model in the study sequence. In this way the stationary solution is used as initial
values for the following steps. This can be manually by modifying the settings of the
study node, or in an automated way by using the Stationary with Initialization or Time
Dependent with Initialization study sequences, as described above.
• In many models the flow profile is only slightly (or not at all) affected by changes in
current density. Therefore it can be a good strategy to solve separately for the flow
early in the study sequence, and then solve for the other physics interfaces in the
subsequent steps. (If the flow is not affected at all by the current distribution,
solving for the flow can be disabled entirely in consecutive steps.)

• Electrochemistry Interfaces
In the COMSOL Multiphysics Reference Manual:

• Studies and Solvers

• Analyzing Model Convergence and Accuracy
• Achieving Convergence When Solving Nonlinear Equations

TIME-DEPENDENT PROBLEMS WITH LOAD STEPS

For time-dependent problems, try the following to address accuracy and convergence
issues with regards to sudden current or potential load steps.

• Use smoothed current or potential load functions in order to avoid instantaneous

or discrete load steps.
• Add a double layer capacitance to the model, which can improve the numerical
stability.
• Reduce the Maximum step taken by the solver if you want to prevent the solver from
“missing” short square load steps, or change the Steps taken by solver setting from
Free to Strict, or Intermediate, to control the time steps using the Times text field.

INTRODUCTION TO ELECTROCHEMISTRY MODELING | 63

 Using the Events interface can also be an option in certain cases if the load cycle
itself varies dynamically.

• Double Layer Capacitance

In the COMSOL Multiphysics Reference Manual:

• Step and Time Dependent

• Building a COMSOL Multiphysics Model and The Events Interface

SOLVER SETTINGS
Try adjusting the solver settings.

• In rare cases, try to increase the Maximum number of iterations.

• If you know the order of magnitude of the dependent variables beforehand, setting
the scaling method to Manual for these can improve convergence and the accuracy
of the results. This may be of special importance when solving for concentrations
that are initially very small but where the final order of magnitude is know a priori.
This could be the case for the active species in a battery model, for example.

In the COMSOL Multiphysics Reference Manual:

• Studies and Solvers

• Analyzing Model Convergence and Accuracy
• Achieving Convergence When Solving Nonlinear Equations

Electrochemistry Studies and Study Steps and Cyclic Voltammetry in the

COMSOL Multiphysics Reference Manual

In multicomponent systems it is rarely straightforward to predict the rest

potential and direction of current flow. The Current Initialization step in
COMSOL Multiphysics does this for you but is only correct if
concentrations and formal potentials for all electrode reactions are
specified precisely and with respect to a common reference scale.

64 | CHAPTER 2: MODELING WITH ELECTROCHEMISTRY

 Electrochemistry Studies and Study Steps in the COMSOL Multiphysics
Reference Manual

Studies and Solvers and Building a COMSOL Multiphysics Model in the

COMSOL Multiphysics Reference Manual

Postprocessing Your Solution

POTENTIAL VARIABLES
Several different potential variables are available for postprocessing and during
computation. The most common ones are described in Table 2-1.
TABLE 2-1: COMMON POTENTIAL VARIABLES

VARIABLE DESCRIPTION DEFINED AT

phil Electrolyte phase potential Electrolyte and Porous

Electrode domains
phis Electrode phase potential Electrode and Porous
Electrode domains
[Link] Electrode phase potential Electrode Reaction boundaries
to Electrolyte domains
xxx.Eeq_yy Equilibrium potential Electrode Reaction boundaries
and Porous Electrode Reaction
domains
xxx.eta_yy Overpotential Electrode Reaction boundaries

The unit is V for all the above variables.

xxx denotes the tag of the physics interface. For instance, cd for the Secondary Current Distribution inter-
face.
yy denotes the tag of the (Porous) Electrode Reaction node, for instance, er1 for an Electrode Reaction
node.

CURRENT VARIABLES AND CALCULATING THE TOTAL CELL CURRENT

The current density may vary between locations on an electrode surface. This effect is
very important to understand through modeling because it cannot be directly
measured. Experimental measurement can only return the total current drawn at an
electrode, although the variation in current density can be inferred by other means.

INTRODUCTION TO ELECTROCHEMISTRY MODELING | 65

 To calculate the total current in COMSOL Multiphysics, it is necessary to integrate the
total drawn current density along the boundary or over the domain of the electrode.
Some common current density variables are shown in Table 2-2.
TABLE 2-2: COMMON CURRENT DENSITY VARIABLES.

VARIABLE UNIT DESCRIPTION DEFINED AT

2
[Link] A/m Electrolyte current density in Boundaries to Electrolyte and
normal direction Porous Electrode domains
[Link] A/m2 Electrode current density in Boundaries to Electrolyte and
normal direction Porous Electrode domains
xxx.iloc_yy A/m2 Local current density of Electrode Reaction boundaries
electrode reaction
[Link] A/m2 Total interface current density Electrode Reaction boundaries
(local sum of all xxx.iloc_yy)
xxx.iv_yy A/m3 Volumetric current density of a Porous Electrode domains
Porous Electrode Reaction
[Link] A/m3 Total volumetric current Porous Electrode domains
densities (local sum of all
xxx.iv_yy)
[Link] A/m2 Electrolyte current density Electrolyte domains
magnitude (L2 norm)
[Link] A/m2 Electrode current density Electrode domains
magnitude (L2 norm)

xxx denotes the tag of the physics interface. For instance cd for the Secondary Current Distribution inter-
face.
yy denotes the tag of the (Porous) Electrode Reaction node, For instance er1 for an Electrode Reaction
node.

In 1D or 1D axisymmetric, the electrode is implicitly uniform so you can just multiply

by the area of the electrode. In 2D or 2D axisymmetric, compute the appropriate line
integral. In 3D, compute the surface integral.

You can also define your own total current variable by using an Integration nonlocal
coupling across the electroactive boundaries. This variable can also be used during the

66 | CHAPTER 2: MODELING WITH ELECTROCHEMISTRY

computation. In 1D axisymmetric and 2D axisymmetric components, make sure to
select the Compute integral in revolved geometry check box.

In the COMSOL Multiphysics Reference Manual:

• Nonlocal Couplings and Coupling Operators and Integration

Avoid evaluating the [Link]/[Link] variables on boundaries. These

are generally less accurate than the [Link]/[Link] variables.

INTRODUCTION TO ELECTROCHEMISTRY MODELING | 67

 Connecting to Electrical Circuits
In this section:

• About Connecting Electrical Circuits to Physics Interfaces

• Connecting Electrical Circuits Using Predefined Couplings
• Connecting Electrical Circuits by User-Defined Couplings
• Solving
• Postprocessing

About Connecting Electrical Circuits to Physics Interfaces

This section describes the various ways electrical circuits can be connected to other
physics interfaces in COMSOL Multiphysics. If you are not familiar with circuit
modeling, it is recommended that you review the Theory for the Electrical Circuit
Interface.

In general electrical circuits connect to other physics interfaces via one or more of three
special circuit features:

• External I vs. U
• External U vs. I
• External I-Terminal

These features either accept a voltage measurement from the connecting noncircuit
physics interface and return a current from a Battery or Current Distribution Interface
(or the Electrical Circuit interface), or the other way around.

The “External” features are considered “ideal” current or voltage sources

by the Electrical Circuit interface. Hence, you cannot connect them
directly in parallel (voltage sources) or in series (current sources) with
other ideal sources. This results in the error message The DAE is
structurally inconsistent. A workaround is to provide a suitable parallel
or series resistor, which can be tuned to minimize its influence on the
results.

68 | CHAPTER 2: MODELING WITH ELECTROCHEMISTRY

Connecting Electrical Circuits Using Predefined Couplings
In addition to these circuit features, interfaces in the AC/DC Module, RF Module,
MEMS Module, Plasma Module, and Semiconductor Module (the modules that
include the Electrical Circuit interface) also contain features that provide couplings to
the Electrical Circuit interface by accepting a voltage or a current from one of the
specific circuit features (External I vs. U, External U vs. I, and External I-Terminal).

This coupling is typically activated when:

• A choice is made in the Settings window for the noncircuit physics interface feature,
which then announces (that is, includes) the coupling to the Battery or Current
Distribution (or Electrical Circuit) interface. Its voltage is then included to make it
visible to the connecting circuit feature.
• A voltage that has been announced (that is, included) is selected in a feature node’s
Settings window.

These circuit connections are supported in Circuit Terminals.

Connecting Electrical Circuits by User-Defined Couplings

A more general way to connect a physics interface to the Electrical Circuit interface is
to:

• Apply the voltage or current from the connecting “External” circuit feature as an
excitation in the noncircuit physics interface.
• Define your own voltage or current measurement in the noncircuit physics interface
using variables, coupling operators and so forth.
• In the Settings window for the Electrical Circuit interface feature, selecting the
User-defined option and entering the name of the variable or expression using
coupling operators defined in the previous step.

DETERMINING A CURRENT OR VOLTAGE VARIABLE NAME

To determine a current or voltage variable name, look at the Dependent Variables node
under the Study node. To do this:

1 In the Model Builder, right-click the Study node and select Show Default Solver.

CONNECTING TO ELECTRICAL CIRCUITS | 69

 2 Expand the Solver>Dependent Variables node and click the state node, in this
example, Current through device R1 ([Link]). The variable name is shown in
the Settings window for State.

Typically, voltage variables are named cir.Xn_v and current variables

cir.Xn_i, where n is the “External” device number — 1, 2, and so on.

Solving

Some modeling errors lead to the error message The DAE is structurally
inconsistent being displayed when solving. This error typically occurs
from having an open current loop, from connecting voltage sources in
parallel, or connecting current sources in series.

In this respect, the predefined coupling features are also treated as (ideal)
voltage or current sources. The remedy is to close current loops and to
connect resistors in series with voltage sources or in parallel with current
sources.

70 | CHAPTER 2: MODELING WITH ELECTROCHEMISTRY

Postprocessing
The Electrical Circuits interface, unlike most of the other physics interfaces, solves for
a relatively large number of global dependent variables (such as voltages and currents),
instead of solving for a few space-varying fields (such as temperature or displacement).
For this reason, the Electrical Circuit interface does not provide default plots when
computing a study.

The physics interface defines a number of variables that can be used in postprocessing.
All variables defined by the Electrical Circuit interface are of a global scope, and can
be evaluated in a Global Evaluation node (under Derived Values). In addition, the time
evolution or dependency on a parameter can be plotted in a Global plot (under a 1D
Plot Group node).

The physics interface defines a Node voltage variable for each electrical node in the
circuit, with name cir.v_name, where cir is the physics interface Label and <name>
is the node Name. For each two-pin component, the physics interface also defines
variables containing the voltage across it and the current flowing through it.

In the COMSOL Multiphysics Reference Manual:

• Derived Values, Evaluation Groups, and Tables and Global Evaluation

• Plot Groups and Plots and Global

References
1. V. Kaajakari, Practical MEMS, Small Gear Publishing, Las Vegas, 2009.

2. S.D. Senturia, Microsystem Design, Springer Science and Business Media, New
York, 2001.

3. A.F. Bower, Applied Mechanics of Solids, CRC Press, Boca Raton, FL, 2010
([Link]

CONNECTING TO ELECTRICAL CIRCUITS | 71

 SPICE Import and Export
The following text is a generic description of the SPICE Import and Export
functionality available with various add-on products from COMSOL.

SPICE Import
The circuit definition in COMSOL Multiphysics adheres to the SPICE format
developed at the University of California, Berkeley (Ref. 1). SPICE netlists can be
imported and the corresponding circuit nodes are generated in the COMSOL
Multiphysics model. Most circuit simulators can export to this format or some version
of it.

The Electrical Circuit interface supports the following device models:

TABLE 2-3: SUPPORTED SPICE DEVICE MODELS

STATEMENT DEVICE MODEL

R Resistor
C Capacitor
L Inductor
V Voltage Source
I Current Source
E Voltage-Controlled Voltage Source
F Current-Controlled Voltage Source
G Voltage-Controlled Current Source
H Current-Controlled Voltage Source
D Diode
Q NPN BJT and PNP BJT
M n-Channel MOSFET and p-Channel MOSFET
X Subcircuit Instance

Statements corresponding to multiple devices are resolved by parsing the associated

.model statement. The physics interface also supports the .subckt statement, which
is represented in COMSOL by a Subcircuit Definition node, and the .include
statement. SPICE commands are interpreted case-insensitively. The statement defining
each device is also interpreted as the Device name.

72 | CHAPTER 2: MODELING WITH ELECTROCHEMISTRY

According to SPICE specification, the first line in the netlist file is assumed to be the
title of the netlist and it is ignored by the parser.

SPICE Export
The SPICE Export functionality creates a SPICE netlist file containing a description of
the circuit represented by the physics interface. This functionality can be accessed from
the physics interface context menu (right-click the physics interface node and select
Export SPICE Netlist). After specifying a filename, the circuit is exported and messages
from the export process display in the Messages window. During the export process, a
series of operations are performed:

• In order to avoid conflicts, each component must be identified by a unique Device

name. If one or more components have the same device name, the export operation
fails and an error message is displayed. All characters in a Device name that are not
letters, digits or underscores are replaced by underscores.
• According to the SPICE specification, each circuit must have a node with name 0,
which is assumed to be the only ground node. When exporting a circuit, any node
with name 0 that is not connected to a Ground component is exported with a
different node name. All nodes that are connected to a Ground components are
exported as a merged node with name 0. The Messages window shows a log message
if these operations are performed, showing the name of the renamed or merged
nodes.
• All characters in node names that are not letters, digits or underscores are replaced
by underscores.
• Some components (most notably, the External components used to couple to other
physics interfaces) cannot be exported to a SPICE netlist. These components are
ignored during the export process, and a message is shown in the Messages window.
Note that this can change the exported circuit, since some components are then
missing.
• Subcircuit definitions are added as .subckt statements in the netlist.
Semiconductor devices (such as MOSFETs, BJTs, and diodes) are exported as a
SPICE device with a corresponding .model statement.

The title of the exported netlist file is the model’s filename, and the time, date, and
version of COMSOL Multiphysics is added as a comment in the netlist file.

SPICE IMPORT AND EXPORT | 73

 Reference
1. [Link]

74 | CHAPTER 2: MODELING WITH ELECTROCHEMISTRY

 3

AC/DC Interfaces

This chapter describes the physics interfaces found under the AC/DC branch .

In this chapter:

• The Electrostatics Interface

• The Electric Currents Interface
• The Electrical Circuit Interface
• Theory for the Electrostatics Interface
• Theory for the Electric Currents Interface
• Theory for the Electrical Circuit Interface

See the COMSOL Multiphysics Reference Manual for details about The Magnetic
Fields Interface and the Theory of Magnetic Fields.

75
 The Electrostatics Interface
The Electrostatics (es) interface ( ), found under the AC/DC>Electric Fields and
Currents branch when adding a physics interface, is used to compute the electric field,
electric displacement field, and potential distributions in dielectrics under conditions
where the electric charge distribution is explicitly prescribed. The formulation is
stationary except for use together with other physics interfaces. Eigenfrequency,
frequency-domain, small-signal analysis, and time-domain modeling are supported in
all space dimensions.

The physics interface solves Gauss’ law for the electric field using the scalar electric
potential as the dependent variable.

Charge Conservation is the main node, which adds the equation for the electric
potential and has a Settings window for defining the constitutive relation for the
electric displacement field and its associated properties such as the relative permittivity.

When this physics interface is added, these default nodes are also added to the Model
Builder — Charge Conservation, Zero Charge (the default boundary condition), and
Initial Values. Then, from the Physics toolbar, add other nodes that implement, for
example, boundary conditions and space charges. You can also right-click Electrostatics
to select physics features from the context menu.

Physics-Controlled Mesh
The physics-controlled mesh is controlled from the Mesh node’s Settings window (if the
Sequence type is Physics-controlled mesh). There, in the table in the Physics-Controlled
Mesh section, find the physics interface in the Contributor column and select or clear
the check box in the Use column on the same table row for enabling (the default) or
disabling contributions from the physics interface to the physics-controlled mesh.

Information from the physics, such as the presence of an infinite elements domain or
periodic condition, will be used to automatically set up an appropriate meshing
sequence.

In the COMSOL Multiphysics Reference Manual see the

Physics-Controlled Mesh section for more information about how to
define the physics-controlled mesh.

76 | CHAPTER 3: AC/DC INTERFACES

SETTINGS
The Label is the default physics interface name.

The Name is used primarily as a scope prefix for variables defined by the physics
interface. Refer to such physics interface variables in expressions using the pattern
<name>.<variable_name>. In order to distinguish between variables belonging to
different physics interfaces, the name string must be unique. Only letters, numbers, and
underscores (_) are permitted in the Name field. The first character must be a letter.

The default Name (for the first physics interface in the model) is es.

CROSS-SECTION AREA (1D COMPONENTS)

For 1D components, enter a default value for the Cross-section area A (SI unit: m2).
The default value of 1 is typically not representative for a thin domain. Instead it
describes a unit thickness that makes the 1D equation identical to the equation used
for 3D components. See also Change Cross Section.

THICKNESS (2D COMPONENTS)

For 2D components, enter a default value for the Out-of-plane thickness d (SI unit: m).
The default value of 1 is typically not representative for a thin dielectric medium, for
example. Instead it describes a unit thickness that makes the 2D equation identical to
the equation used for 3D components. See also Change Thickness (Out-of-Plane).

DEPENDENT VARIABLES
The dependent variable is the Electric potential V. You can change its name, which
changes both the field name and the variable name. If the new name coincides with the
name of another electric potential field in the model, the physics interfaces shares
degrees of freedom. The new name must not coincide with the name of a field of
another type or with a component name belonging to some other field.

DISCRETIZATION
Select the shape order for the Electric potential dependent variable — Linear, Quadratic
(the default), Cubic, Quartic, or Quintic. For more information about the Discretization

THE ELECTROSTATICS INTERFACE | 77

 section, see Settings for the Discretization Sections in the COMSOL Multiphysics
Reference Manual.

In the COMSOL Multiphysics Reference Manual, see Table 2-4 for links
to common sections and Table 2-5 to common feature nodes. You can
also search for information: press F1 to open the Help window or Ctrl+F1
to open the Documentation window.

Electric Sensor: Application Library path COMSOL_Multiphysics/

Electromagnetics/electric_sensor

Domain, Boundary, Edge, Point, and Pair Nodes for the

Electrostatics Interface
The Electrostatics interface has these domain, boundary, edge, point, and pair nodes
available.

ABOUT THE BOUNDARY CONDITIONS

The relevant physics interface condition at interfaces between different media is

n2 ⋅ ( D1 – D2 ) = ρs

In the absence of surface charges, this condition is fulfilled by the natural boundary
condition

n ⋅ [ ( ε 0 ∇V – P ) 1 – ( ε 0 ∇V – P ) 2 ] = – n ⋅ ( D 1 – D 2 ) = 0

AVAILABLE NODES
These nodes, listed in alphabetical order, are available from the Physics ribbon toolbar
(Windows users), Physics context menu (Mac or Linux users), or right-click to access
the context menu (all users). Also see Table 3-1 for a list of interior and exterior
boundary conditions, including edge, point, and pair availability.

In general, to add a node, go to the Physics toolbar no matter what

operating system you are using. Subnodes are available by clicking the
parent node and selecting it from the Attributes menu.

78 | CHAPTER 3: AC/DC INTERFACES

• Change Cross Section • Line Charge (on Axis)
• Change Thickness (Out-of-Plane) • Line Charge (Out-of-Plane)
• Charge Conservation • Periodic Condition
1,2
• Charge Conservation, Piezoelectric • Point Charge
• Conduction Loss (Time-Harmonic) • Point Charge (on Axis)
• Electric Displacement Field • Space Charge Density
• Electric Potential • Surface Charge Density
• External Surface Charge Accumulation • Thin Low Permittivity Gap
• Zero Charge (the default boundary
condition)
1
This feature is available with the Piezoelectricity multiphysics interface.
2
Rrequires the Acoustics Module, MEMS Module, or the Structural Mechanics
Module.

THE ELECTROSTATICS INTERFACE | 79

 Table 3-1 lists the interior and exterior boundary conditions available with this physics
interface. It also includes edge, point, and pair availability.
TABLE 3-1: INTERIOR AND EXTERIOR BOUNDARY CONDITIONS (INCLUDING EDGE, POINT, AND PAIR
AVAILABILITY) FOR THE ELECTROSTATICS INTERFACE

NODE INTERIOR EXTERIOR ALSO AVAILABLE FOR

Change Cross Section x x pairs

Change Thickness (Out-of-Plane) x x pairs
Electric Displacement Field x x pairs
Electric Potential x x edges, points, and pairs
External Surface Charge x pairs
Accumulation
Ground x x edges, points, and pairs
Periodic Condition x not applicable
Surface Charge Density x x pairs
Thin Low Permittivity Gap x not applicable
Zero Charge (the default) x x pairs

For axisymmetric components, COMSOL Multiphysics takes the axial

symmetry boundaries (at r = 0) into account and automatically adds an
Axial Symmetry node to the model that is valid on the axial symmetry
boundaries only. There are also Line Charge (on Axis) and Point Charge (on
Axis) available.

In the COMSOL Multiphysics Reference Manual, see Table 2-4 for links
to common sections and Table 2-5 to common feature nodes. You can
also search for information: press F1 to open the Help window or Ctrl+F1
to open the Documentation window.

Charge Conservation
The Charge Conservation node adds the equations for charge conservation according to
Gauss’ law for the electric displacement field. It provides an interface for defining the
constitutive relation and its associated properties such as the relative permittivity.

80 | CHAPTER 3: AC/DC INTERFACES

MATERIAL TYPE
The Material type setting decides how materials behave and how material properties are
interpreted when the mesh is deformed. Select Solid for materials whose properties
change as functions of material strain, material orientation, and other variables
evaluated in a material reference configuration (material frame). Select Nonsolid for
materials whose properties are defined only as functions of the current local state at
each point in the spatial frame, and for which no unique material reference
configuration can be defined. Select From material to pick up the corresponding setting
from the domain material on each domain.

CONSTITUTIVE RELATION D-E

Select a Dielectric model to describe the macroscopic properties of the medium
(relating the electric displacement D with the electric field E) and the applicable
material properties, such as the relative permittivity. Select:

• Relative permittivity (the default) to use the constitutive relation D = ε0εrE. Then
the default is to take the Relative permittivity εr (dimensionless) values From material.
For User defined, select Isotropic, Diagonal, Symmetric, or Full and enter values or
expressions in the field or matrix. The default is 1.
• Polarization to use the constitutive relation D = ε0E + P. Then enter the components
based on space dimension for the Polarization vector P (SI unit: C/m2). The
defaults are 0 C/m2.
• Remanent electric displacement to use constitutive relation D = ε0εrE + Dr, where Dr
is the remanent displacement (the displacement when no electric field is present).
Then the default is to take the Relative permittivity εr (dimensionless) values From
material. For User defined, select Isotropic, Diagonal, Symmetric, or Full and enter
values or expressions in the field or matrix. Then enter the components based on
space dimension for the Remanent electric displacement Dr (SI unit: C/m2). The
defaults are 0 C/m2.

Conduction Loss (Time-Harmonic)

This feature requires the Acoustics Module, MEMS Module, or the

Structural Mechanics Module. See the individual documentation for
information.

THE ELECTROSTATICS INTERFACE | 81

 The Conduction Loss (Time-Harmonic) subnode allows you to model possible conductive
losses in a dielectric material. The effect is only active in a Eigenfrequency or Frequency
response study.

CONDUCTION CURRENT
By default, the Electrical conductivity σ for the media is defined From material. You can
also select User defined or Linearized resistivity.

• For User defined select Isotropic, Diagonal, Symmetric, or Full depending on the
characteristics of the electrical conductivity, and then enter values or expressions for
the Electrical conductivity σ in the field or matrix.
• For Linearized resistivity the default Reference temperature Tref, and Resistivity
temperature coefficient α, and Reference resistivity ρ0 are taken From material, which
means that the values are taken from the domain (or boundary) material. T is the
current temperature, which can be a value that is specified as a model input or the
temperature from a heat transfer interface. The definition of the temperature field
appears in the Model Inputs section.

LOCATION IN USER INTERFACE

Context Menus
Electrostatics>Charge Conservation>Conduction Loss (Time-Harmonic)

Ribbon
Physics tab with Charge Conservation node selected in the model tree:

Attributes>Conduction Loss (Time-Harmonic)

Initial Values
The Initial Values node adds an initial value for the electric potential V that can serve
as an initial condition for a transient simulation or as an initial guess for a nonlinear
solver.

INITIAL VALUES
Enter a value or expression for the initial value of the Electric potential V (SI unit: V).
The default value is 0 V.

82 | CHAPTER 3: AC/DC INTERFACES

Space Charge Density
The Space Charge Density node adds a space charge density ρ, which appears on the
right-hand side of the equation that the physics interface defines.

SPACE CHARGE DENSITY

Enter a value or expression for the Space charge density ρv (SI unit: C/m3). The default
is 0 C/m3.

Zero Charge
The Zero Charge node adds the condition that there is zero charge on the boundary so
that n ⋅ D = 0. This boundary condition is also applicable at symmetry boundaries
where the potential is known to be symmetric with respect to the boundary. This is the
default boundary condition at exterior boundaries. At interior boundaries, it means
that no displacement field can penetrate the boundary and that the electric potential is
discontinuous across the boundary.

Ground
The Ground node implements ground (zero potential) as the boundary condition
V = 0.

Ground means that there is a zero potential on the boundary. This boundary condition
is also applicable at symmetry boundaries where the potential is known to be
antisymmetric with respect to the boundary.

For some physics interfaces, also select additional Ground nodes from the Edges (3D
components) or Points (2D and 3D components) submenus. For 2D axisymmetric
components, it can be applied on the Symmetry axis.

BOUNDARY, EDGE, OR POINT SELECTION

Beware that constraining the potential on edges or points in 3D or on

points in 2D usually yields a current outflow that is mesh dependent.

CONSTRAINT SETTINGS
To display this section, click the Show More Options button ( ) and select Advanced
Physics Options in the Show More Options dialog box.

THE ELECTROSTATICS INTERFACE | 83

 Electric Potential
The Electric Potential node provides an electric potential V0 as the boundary condition
V = V0.

Because the electric potential is being solved for in the physics interface, the value of
the potential is typically defined at some part of the geometry. For some physics
interfaces, also select additional Electric Potential nodes from the Edges (3D
components) or Points (2D and 3D components) submenus. For 2D axisymmetric
components, it can be applied on the symmetry axis.

BOUNDARY, EDGE, OR POINT SELECTION

Beware that constraining the potential on edges or points in 3D or on

points in 2D usually yields a current outflow that is mesh dependent.

ELECTRIC POTENTIAL
Enter the value or expression for the Electric potential V0 (SI unit: V). The default is
0 V.

CONSTRAINT SETTINGS
To display this section, click the Show More Options button ( ) and select Advanced
Physics Options in the Show More Options dialog box.

Surface Charge Density

The Surface Charge Density node provides the following surface-charge boundary
condition for exterior boundaries (left) and interior boundaries (right):

–n ⋅ D = ρs , n ⋅ ( D1 – D2 ) = ρs

Specify the surface charge density ρs at an outer boundary or at an interior boundary

between two nonconducting media.

Add a contribution as a Harmonic Perturbation by right-clicking the parent node or

click Harmonic Perturbation on the Physics toolbar. For more information, see
Harmonic Perturbation — Exclusive and Contributing Nodes.

SURFACE CHARGE DENSITY

Enter the value or expression for the Surface charge density ρs (SI unit: C/m2).

84 | CHAPTER 3: AC/DC INTERFACES

External Surface Charge Accumulation
The External Surface Charge Accumulation node implements the boundary condition

–n ⋅ D = ρs

where ρs is the solution of the following distributed ODE on the boundary:

dρ s
= n ⋅ Ji + n ⋅ Je
dt

where n·Ji is the normal component of the total ion current density on the wall and
n·Je is the normal component of the total electron current density on the wall, which
are feature inputs.

MATERIAL TYPE
The Material type setting decides how materials behave and how material properties are
interpreted when the mesh is deformed. Select Solid for materials whose properties
change as functions of material strain, material orientation, and other variables
evaluated in a material reference configuration (material frame). Select Nonsolid for
materials whose properties are defined only as functions of the current local state at
each point in the spatial frame, and for which no unique material reference
configuration can be defined. Select From material to pick up the corresponding setting
from the domain material on each domain.

EXTERNAL SURFACE CHARGE ACCUMULATION

Enter values or expressions for the Normal ion current density n·Ji (SI unit: A/m2)
and the Normal electron current density n·Je (SI unit: A/m2).

Electric Displacement Field

The Electric Displacement Field node adds the following electric-displacement
boundary condition:

n ⋅ D = n ⋅ D0

It specifies the normal component of the electric displacement field at a boundary.

ELECTRIC DISPLACEMENT FIELD

Enter the coordinates of the Boundary electric displacement field D0 (SI unit: C/m2).

THE ELECTROSTATICS INTERFACE | 85

 Periodic Condition
The Periodic Condition node defines periodicity or antiperiodicity between two
boundaries. If required, activate periodic conditions on more than two boundaries, in
which case the Periodic Condition tries to identify two separate surfaces that can each
consist of several connected boundaries. For more complex geometries, it might be
necessary to use the Destination Selection subnode. With this subnode the boundaries
which constitute the source and destination surfaces can be manually specified. The
Destination Selection subnode is available from the context menu (right-click the parent
node) as well as from the Physics toolbar, Attributes menu.

When this feature is used in conjunction with a feature on connected

boundaries, wherever the sector symmetry boundaries connect with the
periodic boundaries, the same periodic condition feature cannot be used
on both sides. At least two periodic condition features are required for the
model to compute correctly.

BOUNDARY SELECTION
When using nonconforming meshes on the source and destination of a periodic
boundary pair, for numerical stability, a finer mesh should be applied on the
destination side. Use conforming meshes if possible.

PERIODIC CONDITION
Select a Type of periodicity — Continuity (the default), Antiperiodicity, or Floquet
periodicity. Select:

• Continuity to make the electric potential periodic (equal on the source and
destination).
• Antiperiodicity to make it antiperiodic.
• Floquet periodicity (only available with products supporting piezoelectric modeling).
Specify the components of the k-vector for Floquet periodicity kF (SI unit: rad/m).

CONSTRAINT SETTINGS
To display this section, click the Show More Options button ( ) and select Advanced
Physics Options in the Show More Options dialog box.

For information about the Orientation of Source section, see Orientation of Source
and Destination.

86 | CHAPTER 3: AC/DC INTERFACES

Thin Low Permittivity Gap
Use the Thin Low Permittivity Gap node

ε0 εr
n ⋅ D 1 = ---------- ( V 1 – V 2 )
d
ε0 εr
n ⋅ D 2 = ---------- ( V 2 – V 1 )
d

to model a thin gap of a material with a small permittivity compared to the adjacent
domains. The layer has the thickness d and the relative permittivity εr. The indices 1
and 2 refer to the two sides of the boundary.

THIN LOW PERMITTIVITY GAP

The default is to take the Relative permittivity εr (dimensionless) values From material.
For User defined, enter a different value or expression. Enter a Thickness d (SI unit: m).
The default is 5 mm.

Line Charge
For 3D components, use the Line Charge node to specify line charges along the edges
of a geometry. Add a contribution as a Harmonic Perturbation by right-clicking the
parent node or clicking Harmonic Perturbation on the Physics toolbar. For more
information see Harmonic Perturbation — Exclusive and Contributing Nodes.

EDGE SELECTION

Beware that constraining the potential on edges usually yields a current

outflow that is mesh dependent.

LINE CHARGE
Enter a value or expression to apply a Line charge QL (SI unit: C/m). This source
represents electric charge per unit length and the default is 0 C/m.

Line Charge (on Axis) and Line Charge (Out-of-Plane)

THE ELECTROSTATICS INTERFACE | 87

 Line Charge (on Axis)
For 2D axisymmetric components, use the Line Charge (on Axis) node to specify line
charges along the symmetry axis.

Add a contribution as a Harmonic Perturbation by right-clicking the parent node or

click Harmonic Perturbation on the Physics toolbar. For more information see
Harmonic Perturbation — Exclusive and Contributing Nodes.

LINE CHARGE (ON AXIS)

Enter a value or expression to apply a Line charge QL (SI unit: C/m). This source
represents electric charge per unit length and the default is 0 C/m.

Line Charge and Line Charge (Out-of-Plane)

Line Charge (Out-of-Plane)

For 2D and 2D axisymmetric components, points are selected and this is the same as
a line out-of-plane.

Add a contribution as a Harmonic Perturbation by right-clicking the parent node or

clicking Harmonic Perturbation on the Physics toolbar. For more information see
Harmonic Perturbation — Exclusive and Contributing Nodes.

Use the Line Charge (Out-of-Plane) node to specify line charges along the points of a
geometry for 2D and 2D axisymmetric components.

POINT SELECTION

Beware that constraining the potential on points usually yields a current

outflow that is mesh dependent.

88 | CHAPTER 3: AC/DC INTERFACES

LINE CHARGE (OUT-OF-PLANE)
Enter a value or expression to apply a Line charge QL (SI unit: C/m). This source
represents electric charge per unit length and the default is 0 C/m.

Line Charge and Line Charge (on Axis)

Point Charge
The Point Charge node adds a point source to 3D components. The point charge
represents an electric displacement field flowing out of the point.

Add a contribution as a Harmonic Perturbation by right-clicking the parent node or

clicking Harmonic Perturbation on the Physics toolbar. For more information see
Harmonic Perturbation — Exclusive and Contributing Nodes.

POINT SELECTION

Beware that constraining the potential on points usually yields a current

outflow that is mesh dependent.

POINT CHARGE
Enter a value or expression to apply a Point charge QP (SI unit: C) to points. This
source represents an electric displacement field flowing out of the point. The default is
0 C.

Point Charge (on Axis) and Line Charge (Out-of-Plane)

Point Charge (on Axis)

The Point Charge (on Axis) node adds a point source to 2D axisymmetric components.
The point charge represents an electric displacement field flowing out of the point.

Add a contribution as a Harmonic Perturbation by right-clicking the parent node or

clicking Harmonic Perturbation on the Physics toolbar. For more information see
Harmonic Perturbation — Exclusive and Contributing Nodes.

THE ELECTROSTATICS INTERFACE | 89

 POINT SELECTION

Beware that constraining the potential on points usually yields a current

outflow that is mesh dependent.

POINT CHARGE (ON AXIS)

Enter a value or expression to apply a Point charge QP (SI unit: C) to points on an axis.
This source represents an electric displacement field flowing out of the point. The
default is 0 C.

Point Charge and Line Charge (Out-of-Plane)

Change Cross Section

This node is available with 1D components. This setting overrides the global
Cross-Section Area setting made in any physics interface that uses this feature. For 2D
components, see Change Thickness (Out-of-Plane).

Use the Change Cross Section node to set the cross-section area for specific geometric
entities.

CHANGE CROSS SECTION

Enter a value or expression for the Cross-section area A. The default value of 1 unit
length is typically not representative for a thin domain. Instead it describes a unit
thickness that makes the 1D equation identical to the equation used for 3D
components.

Change Thickness (Out-of-Plane)

This node is available for 2D components. This setting overrides the global Thickness
setting made in any physics interface that uses this node. For 1D components, see
Change Cross Section.

Use the Change Thickness (Out-of-Plane) node to set the out-of-plane thickness for
specific geometric entities.

90 | CHAPTER 3: AC/DC INTERFACES

CHANGE THICKNESS (OUT-OF-PLANE)
Enter a value or expression for the Out-of-plane thickness d (SI unit: m). The default
value is, in most cases, 1 unit length, which is typically not representative for a thin
domain. Instead it describes a unit thickness that makes the 2D equation identical to
the equation used for 3D components.

Charge Conservation, Piezoelectric

This feature is available with the Piezoelectricity interface, which requires

the Acoustics Module, MEMS Module, or the Structural Mechanics
Module. See the individual documentation for information.

The Charge Conservation, Piezoelectric node is normally used together with a

Piezoelectric Effect multiphysics coupling node and a corresponding Piezoelectric
Material node in the Solid Mechanics interface. The node is added by default to the
Electrostatics interface when adding a Piezoelectricity interface. It is also available from
the context menu (right-click the Electrostatics interface parent node) or from the
Physics toolbar.

When the Charge Conservation, Piezoelectric node is added to the

electrostatics interface in the absence of an active Piezoelectric Effect
multiphysics coupling node, the material behaves similarly to a Charge
Conservation node, with electric properties corresponding to the relative
permittivity entered (see below). The piezoelectric effect is not included
in the corresponding equation system.

ELECTRIC DISPLACEMENT
If the node is used together with an active Piezoelectric Effect multiphysics coupling
node, then these settings are locked. Note that if they are unlocked, then the material
behaves like a dielectric and not a piezoelectric. In this case, the default is to take the
Relative permittivity εrS (dimensionless) values From material. For User defined, select
Isotropic, Diagonal, Symmetric, or Full and enter values or expressions in the field or
matrix.

THE ELECTROSTATICS INTERFACE | 91

 The Electric Currents Interface
The Electric Currents (ec) interface ( ), under the AC/DC>Electric Fields and Currents
branch when adding a physics interface, is used to compute electric field, current, and
potential distributions in conducting media under conditions where inductive effects
are negligible; that is, when the skin depth is much larger than the studied device.

Depending on the licensed products, stationary, frequency-domain, small-signal

analysis, and time-domain modeling are supported in all space dimensions. In the time
and frequency domains, capacitive effects are also accounted for.

The physics interface solves a current conservation equation based on Ohm’s law using
the scalar electric potential as the dependent variable.

Current Conservation is the main node, which adds the equation for the electric
potential and provides a Settings window for defining the electrical conductivity as well
as the constitutive relation for the electric displacement field and its associated material
properties, such as the relative permittivity.

When this physics interface is added, these default nodes are also added to the Model
Builder — Current Conservation, Electric Insulation (the default boundary condition),
and Initial Values. Then, from the Physics toolbar, add other nodes that implement, for
example, boundary conditions and current sources. You can also right-click Electric
Currents to select physics features from the context menu.

Physics-Controlled Mesh
The physics-controlled mesh is controlled from the Mesh node’s Settings window (if the
Sequence type is Physics-controlled mesh). There, in the table in the Physics-Controlled
Mesh section, find the physics interface in the Contributor column and select or clear
the check box in the Use column on the same table row for enabling (the default) or
disabling contributions from the physics interface to the physics-controlled mesh.

Information from the physics, such as the presence of an infinite elements domain or
periodic condition, will be used to automatically set up an appropriate meshing
sequence.

In the COMSOL Multiphysics Reference Manual see the

Physics-Controlled Mesh section for more information about how to
define the physics-controlled mesh.

92 | CHAPTER 3: AC/DC INTERFACES

SETTINGS
The Label is the default physics interface name.

The Name is used primarily as a scope prefix for variables defined by the physics
interface. Refer to such physics interface variables in expressions using the pattern
<name>.<variable_name>. In order to distinguish between variables belonging to
different physics interfaces, the name string must be unique. Only letters, numbers, and
underscores (_) are permitted in the Name field. The first character must be a letter.

The default Name (for the first physics interface in the model) is ec.

CROSS-SECTION AREA (1D)

Enter a default value for the Cross-section area A (SI unit: m2). The default value of 1
is typically not representative for a thin domain. Instead it describes a unit thickness
that makes the 1D equation identical to the equation used for 3D components. See
also (described for the Electrostatics interface).

THICKNESS (2D)
Enter a default value for the Out-of-plane thickness d (SI unit: m) (see ). The default
value of 1 m is typically not representative for a thin dielectric medium, for example.
Instead it describes a unit thickness that makes the 2D equation identical to the
equation used for 3D components. See also (described for the Electrostatics
interface).

DEPENDENT VARIABLES
The dependent variable is the Electric potential V. You can change its name, which
changes both the field name and the variable name. If the new name coincides with the
name of another electric potential field in the model, the physics interfaces share
degrees of freedom. The new name must not coincide with the name of a field of
another type or with a component name belonging to some other field.

DISCRETIZATION
Select the shape order for the Electric potential dependent variable — Linear, Quadratic
(the default), Cubic, Quartic, or Quintic. For more information about the Discretization
section, see Settings for the Discretization Sections in the COMSOL Multiphysics
Reference Manual.

• Domain, Boundary, Edge, Point, and Pair Nodes for the Electric
Currents Interface

THE ELECTRIC CURRENTS INTERFACE | 93

 Pacemaker Electrode: Application Library path COMSOL_Multiphysics/
Electromagnetics/pacemaker_electrode

Domain, Boundary, Edge, Point, and Pair Nodes for the Electric
Currents Interface
The Electric Currents interface has these domain, boundary, edge, point, and pair
nodes available from the Physics ribbon toolbar (Windows users) or Physics context
menu (Mac or Linux users). You can also right-click to access the context menu (all
users).

In general, to add a node, go to the Physics toolbar, no matter what

operating system you are using. Subnodes are available by clicking the
parent node and selecting it from the Attributes menu.

ABOUT THE BOUNDARY CONDITIONS

The exterior and interior boundary conditions listed in Table 3-1 are available. The
relevant physics interface condition at interfaces between different media and interior
boundaries is continuity; that is,

n2 ⋅ ( J1 – J2 ) = 0

which is the natural boundary condition.

94 | CHAPTER 3: AC/DC INTERFACES

AVAILABLE NODES
These nodes are available for this physics interface, listed in alphabetical order. Also see
Table 3-1 for a list of interior and exterior boundary conditions, including edge, point,
and pair availability.

• Boundary Current Source • Initial Values

• Contact Impedance • Line Current Source
• Current Conservation • Line Current Source (on Axis)
• Current Source • Normal Current Density
• Distributed Impedance • Piezoresistive Material1
• Electric Insulation • Point Current Source
• Sector Symmetry

1This feature is available with the Piezoresistivity, Domain Currents interface, which

requires the MEMS Module.

These nodes are described for the Electrostatics interface:

• Change Cross Section • Ground

• Change Thickness (Out-of-Plane) • Periodic Condition
• Electric Potential

In the COMSOL Multiphysics Reference Manual, see Table 2-4 for links
to common sections and Table 2-5 for common feature nodes. You can
also search for information: press F1 to open the Help window or Ctrl+F1
to open the Documentation window.

For axisymmetric components, COMSOL Multiphysics takes the axial

symmetry boundaries (at r = 0) into account and automatically adds an
Axial Symmetry node to the model that is valid on the axial symmetry
boundaries only.

THE ELECTRIC CURRENTS INTERFACE | 95

 Table 3-1 lists the interior and exterior boundary conditions available with this physics
interface. It also includes edge, point, and pair availability.
TABLE 3-2: INTERIOR AND EXTERIOR BOUNDARY CONDITIONS (INCLUDING EDGE, POINT, AND PAIR
AVAILABILITY) FOR THE ELECTRIC CURRENTS INTERFACE

NODE INTERIOR EXTERIOR ALSO AVAILABLE FOR

Boundary Current Source x pairs

Contact Impedance x pairs
Distributed Impedance x x not applicable
Electric Insulation x x pairs
Electric Potential x x edges, points, and pairs
Ground x x edges, points, and pairs
Normal Current Density x not applicable
Periodic Condition x not applicable

Current Conservation
The Current Conservation node adds the continuity equation for the electrical potential
and provides an interface for defining the electric conductivity as well as the
constitutive relation and the relative permittivity for the displacement current.

MATERIAL TYPE
The Material type setting decides how materials behave and how material properties are
interpreted when the mesh is deformed. Select Solid for materials whose properties
change as functions of material strain, material orientation, and other variables
evaluated in a material reference configuration (material frame). Select Non-solid for
materials whose properties are defined only as functions of the current local state at
each point in the spatial frame, and for which no unique material reference
configuration can be defined. Select From material to pick up the corresponding setting
from the domain material on each domain.

CONSTITUTIVE RELATION JC-E

By default, the Electrical conductivity σ (SI unit: S/m) for the media is defined From
material. Or select User defined or Linearized resistivity.

User Defined
For User defined select Isotropic, Diagonal, Symmetric, or Full depending on the
characteristics of the electrical conductivity, and then enter values or expressions for the
electrical conductivity σ in the field or matrix. The default is 0 S/m. If type of

96 | CHAPTER 3: AC/DC INTERFACES

temperature dependence is used other than a linear temperature relation, enter any
expression for the conductivity as a function of temperature.

Linearized Resistivity
Select Linearized resistivity for a temperature-dependent conductivity (this occurs in,
for example, Joule heating, and is also called resistive heating). The equation
describing the conductivity:

1
σ = ---------------------------------------------------
ρ 0 ( 1 + α ( T – T ref ) )

where ρ0 is the resistivity at the reference temperature Tref, and α is the temperature
coefficient of resistance, which describes how the resistivity varies with temperature.

The default Reference resistivity ρ0 (SI unit: Ω⋅m), Reference temperature Tref
(SI unit: K), and Resistivity temperature coefficient α (SI unit: 1/K) are taken From
material, which means that the values are taken from the domain (or boundary)
material. T is the current temperature, which can be a value that is specified as a model
input or the temperature from a heat transfer interface. The definition of the
temperature field is in the Model Inputs section.

To specify other values for any of these properties, select User defined from the list and
then enter a value or expression for each. The default values are:

• 1 Ω⋅m for the Reference resistivity

• 273.15 K for the Reference temperature, and
• 0 1/K for the Resistivity temperature coefficient

CONSTITUTIVE RELATION D-E

Select a Dielectric model to describe the macroscopic properties of the medium
(relating the electric displacement D with the electric field E) and the applicable
material properties, such as the relative permittivity. For a description of the
constitutive relations Relative permittivity, Polarization, and Remanent electric
displacement, see Electric Field as described for the node for the Electrostatics interface.
The constitutive relations specific to Electric Currents are:

• Dielectric losses: uses the constitutive relation D = ε0(ε' + ε")E. Specify that the
Relative permittivity (real part) ε' (dimensionless) and the Relative permittivity
(imaginary part) ε" (dimensionless) must be taken From material or be User defined.
For User defined, select Isotropic, Diagonal, Symmetric, or Full and enter values or
expressions in the field or matrix. The default is 1.

THE ELECTRIC CURRENTS INTERFACE | 97

 • Loss tangent, loss angle: uses the constitutive relation D = ε0ε'(1+jtanδ)E. Specify the
Relative permittivity (real part) ε' (dimensionless) and Loss angle δ (SI unit: rad).
• Loss tangent, dissipation factor: uses the constitutive relation D = ε0ε'(1+jtanδ)E.
Specify the Relative permittivity (real part) ε' (dimensionless) and the Dissipation
factor tanδ (dimensionless).

Initial Values
The Initial Values node adds an initial value for the electric potential that can serve as
an initial condition for a transient simulation or as an initial guess for a nonlinear solver.
If more than one set of initial values is required, from the Physics toolbar, add other
nodes that implement, for example, boundary conditions and current sources. Add
more Initial Values nodes from the Physics toolbar.

INITIAL VALUES
Enter a value or expression for the initial value of the Electric potential V (SI unit: V).
The default value is 0 V.

External Current Density

The External Current Density node adds an externally generated current density Je,
which appears in Ohm’s law

J = σE + J e

and in the equation that the physics interface defines.

The external current density does not contribute to the losses (due to Joule heating),
since there is no electric field associated with it. To include the contribution to the
losses from the external current density, select the Add contribution of the external
current density to the losses check box. Then select an option from the External losses
list — From domain conductivity (the default) or User defined. If From domain
conductivity is selected, the heat source is computed using the conductivity specified in
the material model feature (such as Current Conservation) that is applied in the domain.
For User defined, enter a value for Qe (SI unit: W/m3) to specify a user-defined heat
source.

Add a contribution as a Harmonic Perturbation by right-clicking the parent node or

clicking Harmonic Perturbation on the Physics toolbar. For more information see
Harmonic Perturbation — Exclusive and Contributing Nodes.

98 | CHAPTER 3: AC/DC INTERFACES

EXTERNAL CURRENT DENSITY
Based on space dimension, enter the coordinates (x, y, and z for 3D components, for
example) of the External current density Je (SI unit: A/m2). The defaults are 0 A/m2.

Current Source
The Current Source node adds a distributed current source Qj in the equation that the
physics interface defines. Use this node with caution as it can violate the current
conservation law that is inherent in Maxwell-Ampère’s law.

Add a contribution as a Harmonic Perturbation by right-clicking the parent node or

clicking Harmonic Perturbation on the Physics toolbar. For more information see
Harmonic Perturbation — Exclusive and Contributing Nodes.

CURRENT SOURCE
Enter a value or expression for the Current source Qj (SI unit: A/m3). The default is
0 A/m3.

Electric Insulation
The Electric Insulation node, which is the default boundary condition, adds electric
insulation as the boundary condition:

n⋅J = 0

This boundary condition means that no electric current flows into the boundary. At
interior boundaries, it means that no current can flow through the boundary and that
the electric potential is discontinuous across the boundary. It is also applicable at
symmetric boundaries where the potential is known to be symmetric with respect to
the boundary.

Electric insulation as the default boundary condition is not applicable to interior

boundaries. To add electric insulation to an interior boundary, add an Electric
Insulation node in addition to the one that represents the default boundary condition.

Boundary Current Source

The Boundary Current Source node adds a current source Qj on the boundary.

n ⋅ ( J1 – J2 ) = Q j

THE ELECTRIC CURRENTS INTERFACE | 99

 It is applicable to interior boundaries that represent either a source or a sink of current.
Add a contribution as a Harmonic Perturbation by right-clicking the parent node or
click Harmonic Perturbation on the Physics toolbar. For more information see
Harmonic Perturbation — Exclusive and Contributing Nodes.

BOUNDARY CURRENT SOURCE

Enter a value or expression for the Boundary current source Qj (SI unit: A/m2). The
default is 0 A/m2.

Normal Current Density

The Normal Current Density node is applicable to exterior boundaries that represent
either a source or a sink of current. It provides a condition for specifying the normal
current density as an inward or outward current flow:

–n ⋅ J = Jn

Or alternatively, as a current density J0:

n ⋅ J = n ⋅ J0

The normal current density is positive when the current flows inward in the domain.
Add a contribution as a Harmonic Perturbation by right-clicking the parent node or
clicking Harmonic Perturbation on the Physics toolbar. For more information see
Harmonic Perturbation — Exclusive and Contributing Nodes.

NORMAL CURRENT DENSITY

Select a Type — Inward current density (the default) or Current density.

• For Inward current density enter a value or expression for the Normal current density
Jn (SI unit: A/m2). Use a positive value for an inward current flow or a negative
value for an outward current flow. The default is 0 A/m2.
• For Current density enter values or expressions for the components of the Current
density J0 (SI unit: A/m2). The defaults are 0 A/m2.

Distributed Impedance
The Distributed Impedance node adds a distributed impedance boundary condition to
a model.

100 | CHAPTER 3: AC/DC INTERFACES

The Harmonic Perturbation subnode (it is of the exclusive type) is available from the
context menu (right-click the parent node) or on the Physics toolbar, click the
Attributes menu and select Harmonic Perturbation. For more information see Harmonic
Perturbation — Exclusive and Contributing Nodes.

Use this boundary condition to model a thin sheet of a resistive material connected to
a reference potential Vref.

The layer impedance can be specified either with the bulk material conductivity σs, the
relative permittivity εr and layer thickness ds, or directly with the surface resistance ρs
and capacitance Cs. Assuming DC currents, the equation is:

σs
n ⋅ ( J 1 – J 2 ) = ----- ( V – V ref )
ds
1
n ⋅ ( J 1 – J 2 ) = ----- ( V – V ref )
ρs

DISTRIBUTED IMPEDANCE
Enter the reference potential Vref (SI unit: V). The default is 0 V.

Select a potentially complex-valued Layer specification — Thin layer (the default) or

Surface impedance.

• For Thin layer, enter values or expressions for the:

- Surface thickness ds (SI unit: m). The default is 5·10−3 m (5 mm).
- Electrical conductivity σ (SI unit: S/m) and Relative permittivity εr
(dimensionless). The defaults take values From material. For User defined, enter
different values or expressions. The default electrical conductivity is 1·10−2 S/m
and the default relative permittivity is 1.
• For Surface impedance, enter values or expressions for the Surface resistance ρs
(SI unit: Ω·m2) and the Surface capacitance Cs (SI unit: F/m2). The default surface
impedance is 1·10−8 Ω·m2 and the default surface capacitance is 0 F/m2.

Contact Impedance
Use the Contact Impedance node on interior boundaries to model a thin layer of
resistive material. It can also be added as a pair using a Pair Contact Impedance node.
The feature allows specifying the contact impedance either by entering the properties
of the material together with the layer thickness, or by entering the impedance
properties of the thin layer directly.

THE ELECTRIC CURRENTS INTERFACE | 101

 The feature applies the following conditions that relate the normal electric current
density with the jump in the electric potential:

σ
n ⋅ J 1 = ------ ( V 1 – V 2 )
ds
σ
n ⋅ J 2 = ------ ( V 2 – V 1 )
ds
1
n ⋅ J 1 = ----- ( V 1 – V 2 )
ρs
1
n ⋅ J 2 = ----- ( V 2 – V 1 )
ρs

The first two equations refer to a layer impedance specified using the bulk material
conductivity σs and the layer thickness ds, while the last two equations refer to the case
in which the surface resistance ρs is specified. The indices 1 and 2 refer to the two sides
of the boundary. These parameters work the same as with Distributed Impedance.

CONTACT IMPEDANCE
Select a potentially complex-valued Layer specification — Thin layer (the default) or
Surface impedance.

• For Thin layer, enter values or expressions for the:

- Surface thickness ds (SI unit: m). The default is 5·10−3 m (5 mm).
- Electrical conductivity σ (SI unit: S/m) and Relative permittivity εr
(dimensionless). The defaults take values From material. For User defined, enter
different values or expressions. The default electrical conductivity is 1·10−2 S/m
and the default relative permittivity is 1.
• For Surface impedance, enter values or expressions for the Surface resistance ρs (SI
unit: Ω·m2) and the Surface capacitance Cs (SI unit: F/m2). The default surface
impedance is 1·10−8 Ω·m2 and the default surface capacitance is 0 F/m2.

Thin-Film Resistance: Application Library path COMSOL_Multiphysics/

Electromagnetics/thin_film_resistance

Sector Symmetry
Select Sector Symmetry at interfaces between rotating objects where sector symmetry
is used. It is only available for pairs. A default subnode is added. Right-click to select

102 | CHAPTER 3: AC/DC INTERFACES

additional features from the Fallback Features submenu. In 2D, this feature assumes
rotation around the origin.

This feature is always used in conjunction with a on adjacent radial sector

boundaries. Note that the same periodic condition feature cannot be used
on both sides of where the sector symmetry boundaries connect with the
periodic boundaries. At least two periodic condition features are required
for the model to compute correctly.

PAIR SELECTION
When using nonconforming meshes on the source and destination of a pair, for
numerical stability, a finer mesh should be applied on the destination side for any pair
with a condition that imposes a coupling or a constraint across the pair. The sector
symmetry feature falls into this category.

SECTOR SETTINGS
Enter the Number of sectors (<50) nsect. The default is 2.

Select a Type of periodicity — Continuity (the default) or Antiperiodicity.

Based on space dimension, enter values or expressions in the table for the Axis of
rotation arot.

CONSTRAINT SETTINGS
To display this section, click the Show More Options button ( ) and select Advanced
Physics Options in the Show More Options dialog box.

Line Current Source

The Line Current Source node adds a line source to edges in 3D components and to
points in 2D and 2D axisymmetric components. The line source represents electric
current per unit length.

EDGE OR POINT SELECTION

Beware that constraining the potential on edges or points usually yields a

current outflow that is mesh dependent.

THE ELECTRIC CURRENTS INTERFACE | 103

 LINE CURRENT SOURCE
Enter a value or expression to apply a Line current source Qj (SI unit: A/m). This
source represents electric current per unit length. The default is 0 A/m.

Line Current Source (on Axis) for 2D axisymmetric components.

Line Current Source (on Axis)

The Line Current Source (on Axis) node adds a line source to boundaries in 2D
axisymmetric components. The line source represents electric current per unit length.

LINE CURRENT SOURCE (ON AXIS)

Enter a value or expression to apply a Line current source Qj (SI unit: A/m) to
boundaries. This source represents electric current per unit length.

Line Current Source

Point Current Source

The Point Current Source node adds a point source and represents an electric current
flowing out of the point. Add point sources to 3D components from the Points menu.
Add a contribution as a Harmonic Perturbation by right-clicking the parent node or
clicking Harmonic Perturbation on the Physics toolbar. For more information see
Harmonic Perturbation — Exclusive and Contributing Nodes.

POINT SELECTION

Beware that constraining the potential on points usually yields a current

outflow that is mesh dependent.

104 | CHAPTER 3: AC/DC INTERFACES

POINT CURRENT SOURCE
Enter a value or expression to apply a Point current source Qj (SI unit: A) to points.
This source represents an electric current flowing out of the point.

• Line Current Source for 2D components

• Point Current Source (on Axis) for 2D axisymmetric components

Point Current Source (on Axis)

The Point Current Source (on Axis) node adds a point source and represents an electric
current flowing out of the point in 2D axisymmetric components.

POINT SELECTION

Beware that constraining the potential on points usually yields a current

outflow that is mesh dependent.

POINT CURRENT SOURCE

Enter a value or expression to apply a Point current source Qj (SI unit: A) to points.
This source represents an electric current flowing out of the point.

• Point Current Source for 3D components

• Line Current Source for 2D components

Piezoresistive Material
The Piezoresistive Material is normally used together with a Piezoresistive Effect, Domain
Currents multiphysics coupling node. The node is added by default to the Electric
Currents interface when adding a Piezoresistivity, Domain Currents predefined

THE ELECTRIC CURRENTS INTERFACE | 105

 multiphysics coupling interface. It is also available from the context menu (right-click
the Electric Currents interface parent node) or from the Physics toolbar.

When the Piezoresistive Material node is added to the Electric Currents

interface in the absence of an active Piezoelectric Effect, Domain Currents
multiphysics coupling node, the material behaves similarly to a Current
Conservation node, with electric properties corresponding to the relative
permittivity and electrical conductivity entered. The piezoresistive effect
is not included in the corresponding equation system.

PIEZORESISTIVE MATERIAL PROPERTY

This node should be used together with an active Piezoresistive Effect, Domain Currents
multiphysics coupling node. Select a Constitutive model — Piezoresistance form or
Elastoresistance form. For each of the following, the default uses values From material.
For User defined enter other values in the matrix or field.

• Specify a Electrical conductivity, zero stress (SI unit: S/m). This typically comes from
the material added under the Materials node.
• For Piezoresistance form, select a Piezoresistance coupling matrix Πl (SI unit: m4/
(s⋅A2); note that this is equivalent to Ω⋅m/Pa).
• For a Elastoresistance form, select an Elastoresistance coupling matrix Ml
(SI unit: Ω⋅m).

106 | CHAPTER 3: AC/DC INTERFACES

T he E le c t r i c a l Ci rc u i t In t erfac e
The Electrical Circuit (cir) interface ( ), found under the AC/DC branch ( ) when
adding a physics interface, is used to model currents and voltages in circuits including
voltage and current sources, resistors, capacitors, inductors, and semiconductor
devices. Models created with the Electrical Circuit interface can include connections
to distributed field models. The physics interface supports stationary,
frequency-domain and time-domain modeling and solves Kirchhoff’s conservation
laws for the voltages, currents and charges associated with the circuit elements.

When this physics interface is added, it adds a default Ground Node feature and
associates that with node zero in the electrical circuit.

Circuit nodes are nodes in the electrical circuit (electrical nodes) and
should not be confused with nodes in the Model Builder tree of the
COMSOL Multiphysics software. Circuit node names are not restricted
to numerical values but can contain alphanumeric characters.

SETTINGS
The Label is the default physics interface name.

The Name is used primarily as a scope prefix for variables defined by the physics
interface. Refer to such physics interface variables in expressions using the pattern
<name>.<variable_name>. In order to distinguish between variables belonging to
different physics interfaces, the name string must be unique. Only letters, numbers, and
underscores (_) are permitted in the Name field. The first character must be a letter.

The default Name (for the first physics interface in the model) is cir.

RESISTANCE IN PARALLEL TO PN JUNCTIONS

For numerical stability, a large resistance is added automatically in parallel to the pn
junctions in diodes and BJT devices. Enter a default value for the Resistance in parallel
to pn junctions Rj (SI unit: Ω). The default value is 1·1012 Ω.

CREATE UNIQUE NODES FOR NEW DEVICES

When this setting is selected (the default), newly added devices will be assigned unused
node names. The devices will be disconnected from the rest of the circuit and the
nodes should be updated to reflect the actual circuit connections. When this setting is

THE ELECTRICAL CIRCUIT INTERFACE | 107

 deselected, new devices will be connected to the lowest-numbered nodes starting from
0.

ELECTRICAL CIRCUIT TOOLBAR

The following nodes are available from the Electrical Circuit ribbon toolbar (Windows
users), Electrical Circuit context menu (Mac or Linux users), or right-click to access the
context menu (all users):

For step-by-step instructions and general documentation

descriptions, this is the Electrical Circuit toolbar.

• Ground Node • Subcircuit Definition

• Voltmeter • Subcircuit Instance
• Ampère Meter • Mutual Inductance
• Resistor • Transformer
• Capacitor • Battery Open Circuit Voltage
• Inductor • Resistor-Capacitor Couple
• Voltage Source • NPN BJT and PNP BJT2
• Current Source • n-Channel MOSFET and
• Diode p-Channel MOSFET2

• Switch • External I vs. U3

• Voltage-Controlled Voltage Source1 • External U vs. I3

• Voltage-Controlled Current Source1 • External I-Terminal3

• Current-Controlled Voltage Source1 • SPICE Circuit Import

• Current-Controlled Current Source1 • SPICE Circuit Export

1
Selected from the Dependent Sources submenu when you right-click main node.
2
Selected from the Transistors submenu when you right-click main node.
3
Selected from the External Couplings submenu when you right-click main node.

Ground Node
The Ground Node ( ) feature adds a ground node with the default node number zero
to the electrical circuit. This is the default node in the Electrical Circuit interface. More

108 | CHAPTER 3: AC/DC INTERFACES

ground nodes can be added but those must have unique node numbers and are by
default given higher node numbers.

GROUND CONNECTION
Set the Node name for the ground node in the circuit. The convention is to use 0 (zero)
for the ground node. If adding more ground nodes, each must have a unique node
name (number).

Voltmeter
The Voltmeter ( ) feature connects a voltmeter (voltage measurement device)
between two nodes in the electrical circuit. A voltmeter behaves electrically as an open
circuit. The voltmeter node adds a Probe sampling the voltage across it.

NODE CONNECTIONS
Set the two Node names for the connecting nodes for the resistor.

Ampère Meter
The Ammeter ( ) feature connects an ammeter (current measurement device)
between two nodes in the electrical circuit. An ammeter behaves electrically as a short
circuit. The ammeter node adds a Probe sampling the current through it.

NODE CONNECTIONS
Set the two Node names for the connecting nodes for the resistor.

DEVICE PARAMETERS
Enter the Resistance of the resistor.

Resistor
The Resistor ( ) feature connects a resistor between two nodes in the electrical
circuit.

NODE CONNECTIONS
Set the two Node names for the connecting nodes for the resistor.

DEVICE PARAMETERS
Enter the Resistance of the resistor.

THE ELECTRICAL CIRCUIT INTERFACE | 109

 Capacitor
The Capacitor ( ) feature connects a capacitor between two nodes in the electrical
circuit.

NODE CONNECTIONS
Set the two Node names for the connecting nodes for the capacitor.

DEVICE PARAMETERS
Enter the Capacitance of the capacitor.

Inductor
The Inductor ( ) feature connects an inductor between two nodes in the electrical
circuit.

NODE CONNECTIONS
Set the two Node names for the connecting nodes for the inductor.

DEVICE PARAMETERS
Enter the Inductance of the inductor.

Voltage Source
The Voltage Source ( ) feature connects a voltage source between two nodes in the
electrical circuit.

NODE CONNECTIONS
Set the two Node names for the connecting nodes for the voltage source. The first node
represents the positive reference terminal.

DEVICE PARAMETERS
Enter the Source type that should be adapted to the selected study type. It can be
DC-source, AC-source, or a time-dependent Sine source or Pulse source. Depending on
the choice of source, also specify the following parameters:

• For a DC-source, the Voltage Vsrc (default value: 1 V). DC-sources are active in
Stationary and Time-Dependent studies.
• For an AC-source: the Voltage Vsrc (default value: 1 V) and the Phase Θ (default
value: 0 rad). AC-sources are active in Frequency Domain studies only.

110 | CHAPTER 3: AC/DC INTERFACES

• For a sine source: the Voltage Vsrc (default value: 1 V), the Offset Voff (default value:
0 V), the Frequency (default value: 1 kHz), and the Phase Θ (default value: 0 rad).
The sine sources are active in Time-Dependent studies and also in Stationary
studies, providing that a value for t has been provided as a model parameter or
global variable.
• For a pulse source: the Voltage Vsrc (default value: 1 V), the Offset Voff (default value:
0 V), the Delay td (default value: 0s), the Rise time tr and Fall time tf (default values:
0 s), the Pulse width pw (default value: 1 μs), and the Period Tper (default value: 2 μs).
The pulse sources are active in Time-Dependent studies and also in Stationary
studies, providing that a value for t has been provided as a model parameter or
global variable.

All values are peak values rather than RMS.

For the AC source, the frequency is a global input set by the solver. AC
sources should be used in Frequency-domain studies only. Do not use the
Sine source unless the model is time-dependent.

Current Source
The Current Source ( ) feature connects a current source between two nodes in the
electrical circuit.

NODE CONNECTIONS
Set the two Node names for the connecting nodes for the current source. The first node
represents the positive reference terminal from where the current flows through the
source to the second node.

DEVICE PARAMETERS
Enter the Source type that should be adapted to the selected study type. It can be
DC-source, AC-source, or a time-dependent Sine source or Pulse source. Depending on
the choice of source, also specify the following parameters:

• For a DC-source, the Current isrc (default value: 1 A). DC-sources are active in
Stationary and Time-Dependent studies.
• For an AC-source: the Current isrc (default value: 1 A) and the Phase Θ (default
value: 0 rad). AC-sources are active in Frequency Domain studies only.

THE ELECTRICAL CIRCUIT INTERFACE | 111

 • For a sine source: the Current isrc (default value: 1 A), the Offset ioff (default value:
0 A), the Frequency (default value: 1 kHz), and the Phase Θ (default value: 0 rad).
The sine sources are active in Time-Dependent studies and also in Stationary
studies, providing that a value for t has been provided as a model parameter or
global variable.
• For a pulse source: the Current isrc (default value: 1 A), the Offset ioff (default value:
0 A), the Delay td (default value: 0 s), the Rise time tr and Fall time tf (default values:
0 s), the Pulse width pw (default value: 1 μs), and the Period Tper (default value: 2 μs).
The pulse sources are active in Time-Dependent studies and also in Stationary
studies, providing that a value for t has been provided as a model parameter or
global variable.

All values are peak values rather than RMS.

For the AC source, the frequency is a global input set by the solver. AC
sources should be used in frequency-domain studies only. Do not use the
Sine source unless the model is time-dependent.

Voltage-Controlled Voltage Source

The Voltage-Controlled Voltage Source ( ) feature connects a voltage-controlled
voltage source between two nodes in the electrical circuit. A second pair of nodes
define the input control voltage.

NODE CONNECTIONS
Specify four Node names: the first pair for the connection nodes for the voltage source
and the second pair defining the input control voltage. The first node in a pair
represents the positive reference terminal.

DEVICE PARAMETERS
There are two options to define the relationship between the control voltage and
resulting voltage. The Use gain method defines the resulting voltage to be the control
voltage multiplied by the gain. The Custom expression method can define the
relationship with an arbitrary expression.

112 | CHAPTER 3: AC/DC INTERFACES

Voltage-Controlled Current Source
The Voltage-Controlled Current Source ( ) feature connects a voltage-controlled
current source between two nodes in the electrical circuit. A second pair of nodes
define the input control voltage.

NODE CONNECTIONS
Specify four Node names: the first pair for the connection nodes for the current source
and the second pair defining the input control voltage. The first node in a pair
represents the positive voltage reference terminal or the one from where the current
flows through the source to the second node.

DEVICE PARAMETERS
There are two options to define the relationship between the control voltage and
resulting current. The Use gain method defines the resulting current to be the control
voltage multiplied by the gain (SI units: S). The Custom expression method can define
the relationship with an arbitrary expression.

Current-Controlled Voltage Source

The Current-Controlled Voltage Source ( ) feature connects a current-controlled
voltage source between two nodes in the electrical circuit. The input control current
is the one flowing through a two-pin device.

NODE CONNECTIONS
Set two Node names for the connection nodes for the voltage source. The first node in
a pair represents the positive reference terminal.

DEVICE PARAMETERS
There are two options to define the relationship between the control current and
resulting voltage. The Use gain method defines the resulting voltage to be the control
current multiplied by the gain (SI units: Ω). The Custom expression method can define
the relationship with an arbitrary expression.

Current-Controlled Current Source

The Current-Controlled Current Source ( ) feature connects a current-controlled
current source between two nodes in the electrical circuit. The input control current
is the one flowing through a named device that must be a two-pin device.

THE ELECTRICAL CIRCUIT INTERFACE | 113

 NODE CONNECTIONS
Specify two Node names for the connection nodes for the current source. The first node
in a pair represents the positive reference terminal from where the current flows
through the source to the second node.

DEVICE PARAMETERS
There are two options to define the relationship between the control current and
resulting current. The Use gain method defines the resulting current to be the control
current multiplied by the gain. The Custom expression method can define the
relationship with an arbitrary expression.

Switch
The Switch ( ) feature is used to connect or disconnect the conducting path in a
circuit under specific conditions.

NODE CONNECTIONS
Specify two Node names for the connection nodes for the current source. The first node
in a pair represents the positive reference terminal from where the current flows
through the source to the second node.

SWITHCH CONDITIONS
There are three types of conditions, Voltage controlled, Current controlled, and Custom
expressions. For each type of condition there are two conditions, one for turn on and
one for turn off. The on condition is true if the On condition expression is larger than
zero, while the off condition is true if the Off condition is less than zero.

The Initial state list has three options, Use on condition, Use off condition, and Boolean
expression. The two former options mean that the switch will have an initial state
matching to the on or off condition. The third option makes the switch's initial state
match a custom Boolean expression. Separating on, off, and initial states makes the
switch more flexible and can support Schmitt-trigger style switches and various latches.

For the Voltage controlled switch, it is necessary to specify two nodes that defines the
voltage sens.v that the switch state depends on. The conditions must be written as a
function of this variable. Similarly, for the Current controlled switch it is necessary to
specify a two-pin device that defines the current sens.i that the switch state depends
on.

114 | CHAPTER 3: AC/DC INTERFACES

SWITCH PARAMETERS
When the switch is in the on state it has a non-zero resistance specified by the On
resistance expression. For the off state no current flows through the switch (infinite
resistance). There is also a transition time for the switch to turn on and off set by the
Switching time expression. The switch triggers an implicit event that updates a discrete
state variable (with suffix _state).

Subcircuit Definition
The Subcircuit Definition ( ) feature is used to define subcircuits, which can be
inserted as devices into the main circuit using Subcircuit Instance nodes. Create the
subcircuit by adding subnodes to the Subcircuit Definition node, either by using the
Physics toolbar, or by right-clicking the Subcircuit Definition.

SUBCIRCUIT PINS
Define the Pin names at which the subcircuit connects to the main circuit or to other
subcircuits when referenced by a Subcircuit Instance node. The Pin names refer to
circuit nodes in the subcircuit. The order in which the Pin names are defined is the
order in which they are referenced by a Subcircuit Instance node. The devices
constituting the subcircuit should be connected only to the subcircuit’s pins and to
themselves.

INPUT PARAMETERS
To display this section, click the Show More Options button ( ) and select Advanced
Physics Options. Specify input parameters to a subcircuit that can be changed from a
subcircuit instance. These input parameters can be used in all expression-style edit
fields that affect the parameters of a device, for example, resistance, capacitance, and
current gain. In this way, a subcircuit can represent a parameterized custom device
model.

Subcircuit Instance
The Subcircuit Instance ( ) feature represents an instance of a subcircuits defined by
a Subcircuit Definition feature.

NODE CONNECTIONS
Select the Name of subcircuit link from the list of defined subcircuits in the circuit model
and the circuit Node names at which the subcircuit instance connects to the main circuit
or to another subcircuit if used therein.

THE ELECTRICAL CIRCUIT INTERFACE | 115

 INPUT PARAMETERS
To display this section, click the Show More Options button ( ) and select Advanced
Physics Options. Specify input parameters to a subcircuit that can be changed from a
subcircuit instance. These input parameters can be used in all expression-style edit
fields that affect the parameters of a device, for example, resistance, capacitance, and
current gain. In this way, a subcircuit can represent a parameterized custom device
model.

NPN BJT and PNP BJT

The NPN BJT ( ) and the PNP BJT ( ) device models are large-signal models for
bipolar junction transistors (BJT). It is an advanced device model and no thorough
description and motivation of the many input parameters are attempted here. Many
device manufacturers provide model input parameters for this BJT model. For any
particular make of BJT, the device manufacturer should be the primary source of
information.

NODE CONNECTIONS
Specify three Node names for the connection nodes for the BJT device. These represent
the collector, base, and emitter nodes for the NPN transistor, and the emitter, base, and
collector nodes for the PNP transistor.

MODEL PARAMETERS
Specify the Model Parameters. Reasonable defaults are provided but for any particular
BJT, the device manufacturer should be the primary source of information.

The interested reader is referred to Ref. 1 for more details on

semiconductor modeling within circuits.

For an explanation of the Model Parameters see Bipolar Transistors.

n-Channel MOSFET and p-Channel MOSFET

The n-Channel MOSFET ( ) and the p-Channel MOSFET ( ) device models are
large-signal models for, respectively, an n-Channel MOS field-effect transistor
(MOSFET) and p-Channel MOSFET. These are advanced device models and no
thorough description and motivation of the many input parameters are attempted
here. Many device manufacturers provide model parameters for the MOSFET models.

116 | CHAPTER 3: AC/DC INTERFACES

For any particular make of MOSFET, the device manufacturer should be the primary
source of information.

NODE CONNECTIONS
Specify four Node names for the connection nodes for the n-Channel MOSFET or
p-Channel MOSFET device. These represent the drain, gate, source, and bulk nodes,
respectively.

MODEL PARAMETERS
Specify the Model Parameters. Reasonable defaults are provided but for any particular
MOSFET, the device manufacturer should be the primary source of information.

The interested reader is referred to for more details on semiconductor

modeling within circuits.

For an explanation of the Model Parameters see MOSFET Transistors.

Mutual Inductance
The Mutual Inductance allows specifying a coupling between two existing Inductor
features in the circuit. The mutual inductance of the coupling is

M = k L1 L2

where k is the coupling factor and L1 and L2 are the inductances of the inductors.

DEVICE PARAMETERS
Enter values or expressions for the:

• Coupling factor k (dimensionless). The value must be between 0 and 1, and the
default is 0.98.
• First inductance L1 (SI unit: H) and Second inductance L2 (SI unit: H). These must
be set to two different Inductor features in the circuit.

Transformer
The Transformer feature represents either a combination of two Inductor and a Mutual
Inductance features, or an ideal transformer.

THE ELECTRICAL CIRCUIT INTERFACE | 117

 NODE CONNECTIONS
Enter or edit the table in the Node names column for the primary and secondary node
connections.

DEVICE PARAMETERS
Choose a Transformer model — Specify inductors (the default) or Ideal transformer.

For Specify inductors enter values or expressions for the:

• Coupling factor k (dimensionless). The default is 0.98.

• First inductance L1 (SI unit: H). The default is 1 mH.
• Second inductance L2 (SI unit: H). The default is 1 mH.

For Ideal transformer enter values or expressions for the Winding ratio N1/N2
(dimensionless). The default is 10.

Battery Open Circuit Voltage

The Battery Open Circuit Voltage node defines a voltage source in the circuit that
depends on the state-of-charge of a battery. In time-dependent simulations the
state-of-charge is calculated by integrating the current passing through the circuit
element, using the Battery cell capacity and Initial state-of-charge parameters.

Use the table in the Open Circuit Voltage section to define how the voltage depends on
the state-of-charge.

The Temperature derivative of open circuit settings may be used to define a

temperature-dependent open circuit voltage, and an reversible (entropic) heat source.

Resistor-Capacitor Couple
The Resistor-Capacitor Couple node defines a resistor and capacitor coupled in parallel.
The device model has two modes of operation which are using either the Resistance
and capacitance values or the Resistance and time-constant values as input.

NODE CONNECTIONS
Specify two Node names for the positive and negative nodes for the Resistor-capacitor
couple device.

118 | CHAPTER 3: AC/DC INTERFACES

Diode
The Diode device model ( ) is a large-signal model for a diode. It is an advanced
device model and no thorough description and motivation of the many input
parameters are attempted here. The interested reader is referred to for more details on
semiconductor modeling within circuits. Many device manufacturers provide model
parameters for this diode model. For any particular make of diode, the device
manufacturer should be the primary source of information.

NODE CONNECTIONS
Specify two Node names for the positive and negative nodes for the Diode device.

MODEL PARAMETERS
Specify the Model Parameters. Reasonable defaults are provided but for any particular
diode, the device manufacturer should be the primary source of information.

For an explanation of the Model Parameters see Diode.

External I vs. U
The External I vs. U ( ) feature connects an arbitrary voltage measurement (for
example, a circuit terminal or circuit port boundary or a coil domain from another
physics interface) as a voltage source between two nodes in the electrical circuit. The
resulting circuit current from the first node to the second node is typically coupled
back as a prescribed current source in the context of the voltage measurement.

NODE CONNECTIONS
Specify the two Node names for the connecting nodes for the voltage source. The first
node represents the positive reference terminal.

EXTERNAL DEVICE
Enter the source of the Voltage. If circuit or current excited terminals or circuit ports
are defined on boundaries or domains or a multiturn coil domains is defined in other
physics interfaces, these display as options in the Voltage list. Also select the User defined
option and enter your own voltage variable, for example, using a suitable coupling
operator. For inductive or electromagnetic wave propagation models, the voltage
measurement must be performed as an integral of the electric field because the electric

THE ELECTRICAL CIRCUIT INTERFACE | 119

 potential only does not capture induced EMF. Also the integration must be performed
over a distance that is short compared to the local wavelength.

Except when coupling to a circuit terminal, circuit port, or coil, the

current flow variable must be manually coupled back in the electrical
circuit to the context of the voltage measurement. This applies also when
coupling to a current excited terminal. The name of this current variable
follows the convention cirn.IvsUm_i, where cirn is the tag of the
Electrical Circuit interface node and IvsUm is the tag of the External I vs.
U node. The tags are typically displayed within curly brackets {} in the
Model Builder.

Nonlocal Couplings and Coupling Operators in the COMSOL

Multiphysics Reference Manual

External U vs. I
The External U vs. I ( ) feature connects an arbitrary current measurement (for
example, a coil domain from another physics interface) as a current source between
two nodes in the electrical circuit. The resulting circuit voltage between the first node
and the second node is typically coupled back as a prescribed voltage source in the
context of the current measurement.

NODE CONNECTIONS
Specify the two Node names for the connecting nodes for the current source. The
current flows from the first node to the second node.

EXTERNAL DEVICE
Enter the source of the Current. Voltage excited terminals or lumped ports defined on
boundaries in other physics interfaces are natural candidates but do not appear as
options in the Voltage list because those do not have an accurate built-in current

120 | CHAPTER 3: AC/DC INTERFACES

measurement variable. A User defined option must be selected and a current variable
entered, for example, using a suitable coupling operator.

The voltage variable must be manually coupled back in the electrical

circuit to the context of the current measurement. This applies also when
coupling to a voltage excited terminal or lumped port. The name of this
voltage variable follows the convention cirn.UvsIm_v, where cirn is the
tag of the Electrical Circuit interface node and UvsIm is the tag of the
External U vs. I node. The tags are typically displayed within curly
brackets {} in the Model Builder.

Nonlocal Couplings and Coupling Operators in the COMSOL

Multiphysics Reference Manual

External I-Terminal
The External I-Terminal ( ) feature connects an arbitrary voltage-to-ground
measurement (for example, a circuit terminal from another physics interface) as a
voltage-to-ground assignment to a node in the electrical circuit. The resulting circuit
current from the node is typically coupled back as a prescribed current source in the
context of the voltage measurement. This node does not apply when coupling to
inductive or electromagnetic wave propagation models because then voltage must be
defined as a line integral between two points rather than a single point measurement
of electric potential. For such couplings, use the External I vs. U node instead.

NODE CONNECTIONS
Set the Node name for the connecting node for the voltage assignment.

EXTERNAL TERMINAL
Enter the source of the Voltage. If circuit- or current-excited terminals are defined on
boundaries in other physics interfaces, these display as options in the Voltage list. Also

THE ELECTRICAL CIRCUIT INTERFACE | 121

 select the User defined option and enter a voltage variable, for example, using a suitable
coupling operator.

Except when coupling to a circuit terminal, the current flow variable must
be manually coupled back in the electrical circuit to the context of the
voltage measurement. This applies also when coupling to a current
excited terminal. The name of this current variable follows the convention
cirn.termIm_i, where cirn is the tag of the Electrical Circuit interface
node and termIm is the tag of the External I-Terminal node. The tags are
typically displayed within curly brackets {} in the Model Builder.

Nonlocal Couplings and Coupling Operators in the COMSOL

Multiphysics Reference Manual.

SPICE Circuit Import

Right-click the Electrical Circuit ( ) feature node to import an existing SPICE netlist
(select Import Spice Netlist). A window opens — enter a file location or browse your
directories to find one. The default file extension for a SPICE netlist is .cir. The
SPICE circuit import translates the imported netlist into Electrical Circuit interface
nodes so these define the subset of SPICE features that can be imported.

See SPICE Import and Export about the supported SPICE commands.

SPICE Circuit Export

Right-click the Electrical Circuit ( ) feature node to export the current circuit to the
SPICE netlist file format (select Export Spice Netlist ). A window opens — enter a
file location or browse your directories to find one. The default file extension for a
SPICE netlist is .cir. The compatible circuit nodes are exported as SPICE devices

See SPICE Circuit Export for more details on the supported SPICE
commands.

122 | CHAPTER 3: AC/DC INTERFACES

T he o r y f o r th e E l ec t rost at i cs
Interface
is available for 3D, 2D in-plane, and 2D axisymmetric components. Applications with
electrostatic equations include high-voltage apparatus, electronic devices, and
capacitors. The term “statics” is not to be interpreted literally — it is the observation
time, or time scale at which the applied excitation changes, that is short compared to
the charge relaxation time; also, the electromagnetic wavelength and skin depth are
very large compared to the size of the domain of interest.

If you do not know whether to use the Electric Currents or the Electrostatics interface,
which both solve for the scalar electric potential V, consider using an explicit charge
transport model. See Charge Relaxation Theory.

Charge Relaxation Theory

COMSOL Multiphysics includes physics interfaces for the modeling of static electric
fields and currents. Deciding what specific physics interface and study type to select for
a particular modeling situation requires a basic understanding of the charge dynamics
in conductors.

The different physics interfaces involving only the scalar electric potential can be
interpreted in terms of the charge relaxation process. The fundamental equations
involved are Ohm’s law for the conduction current density

J c = σE

the equation of continuity

∂-----
ρ-
+ ∇ ⋅ Jc = 0
∂t

and Gauss’ law

∇ ⋅ ( εE ) = ρ

By combining these, one can deduce the following differential equation for the space
charge density in a homogeneous medium

THEORY FOR THE ELECTROSTATICS INTERFACE | 123

 ∂-----
ρ- σ
+ --- ρ = 0
∂t ε

This equation has the solution

–t ⁄ τ
ρ ( t ) = ρ0 e

where

ε
τ = ---
σ

is called the charge relaxation time. For a good conductor like copper, τ is of the order
of 10−19 s, whereas for a good insulator like silica glass, it is of the order of 103 s. For
a pure insulator, it becomes infinite.

When modeling real-world devices, there is not only the intrinsic time scale of the
charge relaxation time but also an external time scale t at which a device is energized
or the observation time. It is the relation between the external time scale and the
charge relaxation time that determines what physics interface and study type to use.
The results are summarized in Table 3-3 below,
TABLE 3-3: SUITABLE PHYSICS INTERFACE AND STUDY TYPE FOR DIFFERENT TIME-SCALE REGIMES.

CASE PHYSICS INTERFACE STUDY TYPE

τ>>t Electrostatics Stationary

τ<<t Electric Currents Stationary
τ~ t Electric Currents Time Dependent orFrequency Domain

FIRST CASE: τ >> T

If the external time scale is short compared to the charge relaxation time, the charges
do not have time to redistribute to any significant degree. Thus the charge distribution
can be considered as a given model input. The best approach is to solve the
Electrostatics formulation using the electric potential V.

By combining the definition of the potential with Gauss’ law, you can derive the
classical Poisson’s equation. Under static conditions, the electric potential V is defined
by the equivalence E = −∇V. Using this together with the constitutive relation D = ε0E
+ P between D and E, you can rewrite Gauss’ law as a variant of Poisson’s equation

– ∇ ⋅ ( ε 0 ∇V – P ) = ρ

124 | CHAPTER 3: AC/DC INTERFACES

This equation is used in the Electrostatics interface. It is worth noting that Gauss’ law
does not require the charge distribution to be static. Thus, provided dynamics are slow
enough that induced electric fields can be neglected and hence a scalar electric
potential is justified, the formulation can be used also in the Time Dependent study
type. That typically involves either prescribing the charge dynamics or coupling a
separate formulation for this.

Such separate charge transport formulations can be found in the Plasma

Module, the Semiconductor Module, and the Chemical Reaction
Engineering Module.

SECOND CASE: τ <<T

If the external time scale is long compared to the charge relaxation time, the stationary
solution to the equation of continuity has been reached. In a stationary coordinate
system, a slightly more general form of Ohm’s law than above states that

J c = σE + J e

where Je is an externally generated current density. The static form of the equation of
continuity then reads

∇ ⋅ J c = – ∇ ⋅ ( σ ∇V – J e ) = 0

To handle current sources, the equation can be generalized to

– ∇ ⋅ ( σ ∇V – J e ) = Q j

This equation is used in the static study type for the Electric Currents interface.

Electrostatics Equations
Under static conditions, the electric potential, V, is defined by the relationship:

E = – ∇V

Combining this equation with the constitutive relationship D = ε0E + P between the
electric displacement D and the electric field E, it is possible to represent Gauss’ law
as the following equation:

– ∇ ⋅ ( ε 0 ∇V – P ) = ρ

THEORY FOR THE ELECTROSTATICS INTERFACE | 125

 In this equation, the physical constant, ε0 (SI unit: F/m) is the permittivity of vacuum,
P (SI unit: C/m2) is the electric polarization vector, and ρ (SI unit: C/m3) is a space
charge density. This equation describes the electrostatic field in dielectric materials.

For in-plane 2D modeling, the Electrostatics interface assumes a symmetry where the
electric potential varies only in the x and y directions and is constant in the z direction.
This implies that the electric field, E, is tangential to the xy-plane. With this symmetry,
the same equation is solved as in the 3D case. The physics interface solves the following
equation where d is the thickness in the z direction:

– ∇ ⋅ d ( ε 0 ∇V – P ) = ρ

The axisymmetric version of the physics interface considers the situation where the
fields and geometry are axially symmetric. In this case, the electric potential is constant
in the ϕ direction, which implies that the electric field is tangential to the rz-plane.

The Electrostatics Interface in Time Dependent or Frequency Domain

Studies
can also be solved in a dynamic study (Time Dependent or Frequency Domain). The
equation system solved, however, is typically always the one presented in the previous
section for the stationary case, in which no transient electromagnetic effects are taken
into account. The difference is that the sources of the problem (charge densities,
electric potential) are assumed to be time-varying (in a Time Dependent study) or
time-harmonic (in a Frequency Domain study).

The support for dynamic studies simplifies the coupling of the Electrostatics interface
with other physics interfaces. Using the physics interface in a dynamic study is a valid
approximation only if the time-scale (or the frequency) of the study is so slow that
transient electromagnetic effects can be neglected; for example, in acoustic or
structural problems.

The Electrostatics interface also supports the small-signal analysis study sequence,
which can be used when a time-harmonic perturbation is superposed on a static bias
charge or voltage.

126 | CHAPTER 3: AC/DC INTERFACES

Theory for the Electric Currents
Interface
solves a current conservation problem for the scalar electric potential V and is available
for 3D, 2D in-plane, and 2D axisymmetric components. Electrolysis and the
computation of resistances of grounding plates are examples that involve conductive
media with electrical conductivities and electric currents. If you are uncertain of
whether to use the Electric Currents or the Electrostatics interface, which both solve
for the scalar electric potential V, refer to the section on .

Electric Currents Equations in Steady State

When handling stationary electric currents in conductive media you must consider the
stationary equation of continuity. In a stationary coordinate system, the point form of
Ohm’s law states that:

J = σE + J e

where σ is the electrical conductivity (SI unit: S/m), and Je is an externally generated
current density (SI unit: A/m2). The static form of the equation of continuity then
states:

∇ ⋅ J = – ∇ ⋅ ( σ ∇V – J e ) = 0

To handle current sources, you can generalize the equation to:

– ∇ ⋅ ( σ ∇V – J e ) = Q j

In planar 2D the Electric Currents interface assumes that the model has a symmetry
where the electric potential varies only in the x and y directions and is constant in the
z direction. This implies that the electric field, E, is tangential to the xy-plane. The
Electric Currents interface then solves the following equation, where d is the thickness
in the z direction:

– ∇ ⋅ d ( σ ∇V – J e ) = dQ j (3-1)

In 2D axisymmetry, the Electric Currents interface considers the situation where the
fields and geometry are axially symmetric. In this case, the electric potential is constant
in the ϕ direction, which implies that the electric field is tangential to the rz-plane.

THEORY FOR THE ELECTRIC CURRENTS INTERFACE | 127

128 | CHAPTER 3: AC/DC INTERFACES
Theory for the Electrical Circuit
Interface
The Electrical Circuit Interface theory is discussed in this section:

• Electric Circuit Modeling and the Semiconductor Device Models

• Bipolar Transistors
• MOSFET Transistors
• Diode
• Reference for the Electrical Circuit Interface

Connecting to Electrical Circuits

Electric Circuit Modeling and the Semiconductor Device Models

Electrical circuit modeling capabilities are useful when simulating all sorts of electrical
and electromechanical devices ranging from heaters and motors to advanced plasma
reactors in the semiconductor industry. There are two fundamental ways that an
electrical circuit model relates to a physical field model.

• The field model is used to get a better, more accurate description of a single device
in the electrical circuit model.
• The electrical circuit is used to drive or terminate the device in the field model in
such a way that it makes more sense to simulate both as a tightly coupled system.

The Electrical Circuit interface makes it possible to add nodes representing circuit
elements directly to the Model Builder tree in a COMSOL Multiphysics model. The
circuit variables can then be connected to a physical device model to perform
co-simulations of circuits and multiphysics. The model acts as a device connected to
the circuit so that its behavior is analyzed in larger systems.

The fundamental equations solved by the Electrical Circuit interface are Kirchhoff’s
circuit laws, which in turn can be deduced from Maxwell’s equations. The supported
study types are Stationary, Frequency Domain, and Time Dependent.

THEORY FOR THE ELECTRICAL CIRCUIT INTERFACE | 129

 There are three more advanced large-signal semiconductor device features available in
the Electrical Circuit interface. The equivalent circuits and the equations defining their
non-ideal circuit elements are described in this section. For a more complete treatise
on semiconductor device modeling see Ref. 1.

Bipolar Transistors
Figure 3-1 illustrates the equivalent circuit for the npn bipolar junction transistor.

Figure 3-1: A circuit for the bipolar transistor.

The pnp transistor model is similar in all regards to the npn transistor, with the
difference that the polarities of the currents and voltages involved are reversed. The
following equations are used to compute the relations between currents and voltages
in the circuit.

130 | CHAPTER 3: AC/DC INTERFACES

 R B – R BM
v rb = ----  R BM – -------------------------- i b
1
A  f bq 

 v be
 --------------
v bc
--------------  
  – 1
NF VT NR VT
= -----------------------------------------------  1 + 1 + 4I S  ----------------------- + ------------------------ 
1 e –1 e
f bq
v v   KF I A I A  
2  1 – ----------- – ----------- 
bc be KR
 V AF V AR    
v be v be
 I S  -------------
N V
-
  --------------
N V 
i be = A  -------  e F T – 1 + I SE  e E T – 1 
B
 F   
v bc v bc
 I S  --------------
N V   --------------
N V 
i bc = A  --------  e R T – 1 + I SC  e C T – 1 
B
 R   
v be v bc
 I S  -------------
N V
-
N V 
--------------
i ce = A  -------  e F T + e C T 
f
 bq  
k B T NOM
V T = ------------------------
q

There are also two capacitances that use the same formula as the junction capacitance
of the diode model. In the parameter names below, replace x with C for the
base-collector capacitance and E for the base-emitter capacitance.

 v bx  –M Jx
 1 – ---------
 -
 V Jx v bx < F C V Jx
C jbx = AC Jx × 
 v bx  v bx ≥ F C V Jx
 ( 1 – F ) – 1 – MJx  1 – F ( 1 + M ) + M ---------
-
 C  C Jx Jx V 
Jx

The model parameters are listed in the table below.

TABLE 3-1: BIPOLAR TRANSISTOR MODEL PARAMETERS

PARAMETER DEFAULT DESCRIPTION

BF 100 Ideal forward current gain

BR 1 Ideal reverse current gain
CJC 0 F/m2 Base-collector zero-bias depletion capacitance
CJE 0 F/m2 Base-emitter zero-bias depletion capacitance
FC 0.5 Breakdown current
IKF Inf (A/m2) Corner for forward high-current roll-off

THEORY FOR THE ELECTRICAL CIRCUIT INTERFACE | 131

 TABLE 3-1: BIPOLAR TRANSISTOR MODEL PARAMETERS

PARAMETER DEFAULT DESCRIPTION

IKR Inf (A/m2) Corner for reverse high-current roll-off

IS 1e-15 A/m2 Saturation current
2
ISC 0 A/m Base-collector leakage saturation current
2
ISE 0 A/m Base-emitter leakage saturation current
MJC 1/3 Base-collector grading coefficient
MJE 1/3 Base-emitter grading coefficient
NC 2 Base-collector ideality factor
NE 1.4 Base-emitter ideality factor
NF 1 Forward ideality factor
NR 1 Reverse ideality factor
2
RB 0 Ωm Base resistance
2
RBM 0 Ωm Minimum base resistance
RC 0 Ωm2 Collector resistance
2
RE 0 Ωm Emitter resistance
TNOM 298.15 K Device temperature
VAF Inf (V) Forward Early voltage
VAR Inf (V) Reverse Early voltage
VJC 0.71 V Base-collector built-in potential
VJE 0.71 V Base-emitter built-in potential

132 | CHAPTER 3: AC/DC INTERFACES

MOSFET Transistors
Figure 3-2 illustrates an equivalent circuit for the n-channel MOSFET transistor. The
p-channel MOSFET transistor is treated similarly, but the polarities of the involved
voltages are reversed.

Figure 3-2: A circuit for the MOSFET transistor.

The following equations are used to compute the relations between currents and
voltages in the circuit.

THEORY FOR THE ELECTRICAL CIRCUIT INTERFACE | 133

  KP
 W ( 1 + Λv ds )v ds ( 2v th – v ds ) v ds < v th
- -------
 ----
L 2

i ds =  W KP 2
 ----- ------- ( 1 + Λv ds )v th v ds ≥ v th
 L 2
 0 v ds < v th ≤ 0

v th = v gs – ( V TO + Γ ( Φ – v bs – Φ ) )
v bd
 -----------
NV
-

i bd = I S  e T – 1
 
v bs
 -----------
NV
-

i bs = I S  e T – 1
 
k B T NOM
V T = ------------------------
q

There are also several capacitances between the terminals

C gd = C gd0 W
C gs = C gs0 W

1 – v
–MJ
 bd
--------
-
  PB  v bx < F C P B
C jbd = C BD × 
 v bx v bx ≥ F C P B
 ( 1 – F ) – 1 – MJ  1 – F ( 1 + M ) + M -------
-
 C  C J JP 
B

The model parameters are as follows:

TABLE 3-2: MOSFET TRANSISTOR MODEL PARAMETERS

PARAMETER DEFAULT DESCRIPTION

CBD 0 F/m Bulk-drain zero-bias capacitance

CGDO 0 F/m Gate-drain overlap capacitance
CGSO 0 F/m Gate-source overlap capacitance
FC 0.5 Capacitance factor
IS 1e-13 A Bulk junction saturation current
KP 2e-5 A/V2 Transconductance parameter
L 50e-6 m Gate length
MJ 0.5 Bulk junction grading coefficient

134 | CHAPTER 3: AC/DC INTERFACES

TABLE 3-2: MOSFET TRANSISTOR MODEL PARAMETERS

PARAMETER DEFAULT DESCRIPTION

N 1 Bulk junction ideality factor

PB 0.75 V Bulk junction potential
RB 0Ω Bulk resistance
RD 0Ω Drain resistance
RDS Inf (Ω) Drain-source resistance
RG 0Ω Gate resistance
RS 0Ω Source resistance
TNOM 298.15 K Device temperature
VTO 0V Zero-bias threshold voltage
W 50e-6 m Gate width
0.5
Γ (GAMMA) 1V Bulk threshold parameter
Φ (PHI) 0.5 V Surface potential
Λ (LAMBDA) 0 1/V Channel-length modulation

THEORY FOR THE ELECTRICAL CIRCUIT INTERFACE | 135

 Diode
Figure 3-3 illustrates equivalent circuit for the diode.

Figure 3-3: A circuit for the diode.

The following equations are used to compute the relations between currents and
voltages in the circuit.

136 | CHAPTER 3: AC/DC INTERFACES

 i d = i dhl + i drec + i db + i c
vd
 -----------
NV
-
 1
i dhl = I S  e T – 1 ---------------------------------------------------
  vd
I S  -----------
NV T
-

1 + ---------  e – 1
I KF  
vd
 --------------
N V 
i drec = I SR  e R T – 1
 
vd + BV
– ------------------
N BV V T
i db = I BV e

 vd  –M
  1 – ------
- vd < FC VJ
  V J
C j = C J0 × 
 – 1 – M vd
 ( 1 – FC ) 1 – F C ( 1 + M ) + M ------- v d ≥ F C V J
  V J


k B T NOM
V T = ------------------------
q

where the following model parameters are required

TABLE 3-3: DIODE TRANSISTOR MODEL PARAMETERS

PARAMETER DEFAULT DESCRIPTION

BV Inf (V) Reverse breakdown voltage

CJ0 0F Zero-bias junction capacitance
FC 0.5 Forward-bias capacitance coefficient
IBV 1e-09 A Current at breakdown voltage
IKF Inf (A) Corner for high-current roll-off
IS 1e-13 A Saturation current
M 0.5 Grading coefficient
N 1 Ideality factor
NBV 1 Breakdown ideality factor
NR 2 Recombination ideality factor
RS 0Ω Series resistance
TNOM 298.15 K Device temperature
VJ 1.0 V Junction potential

THEORY FOR THE ELECTRICAL CIRCUIT INTERFACE | 137

 Reference for the Electrical Circuit Interface
1. P. Antognetti and G. Massobrio, Semiconductor Device Modeling with Spice, 2nd
ed., McGraw-Hill, 1993.

138 | CHAPTER 3: AC/DC INTERFACES

 4

Electrochemistry Interfaces

This chapter describes the physics interfaces found under the Electrochemistry
branch ( ).

In this chapter:

• The Primary and Secondary Current Distribution Interfaces

• The Tertiary Current Distribution, Nernst-Planck Interface
• Shared Physics Features in the Current Distribution Interfaces
• The Electrode, Shell Interface
• The Electroanalysis Model Wizard Entry
• Theory for the Current Distribution Interfaces
• Theory for Electrochemical Heat Sources
• Theory for the Electrode, Shell Interface
• Theory for Electroanalysis
• Electrode Potentials and Reference Electrodes

139
 The Primary and Secondary Current
Distribution Interfaces
In this section:

• The Primary Current Distribution • Electrode Line Current Source

and Secondary Current Distribution • Electrolyte Line Current Source
Interfaces
• Electrode Symmetry Axis Current
• Electrolyte Source
• Initial Values • Electrolyte Symmetry Axis Current
• Porous Electrode Source
• Periodic Condition • Electrode Point Current Source
• Thin Electrolyte Layer • Electrolyte Point Current Source
• Edge Electrode

Only the physics interface-specific nodes are described here. All other
nodes in the Primary Current Distribution and Secondary Current
Distribution interfaces are described in Shared Physics Features in the
Current Distribution Interfaces

The Primary Current Distribution and Secondary Current

Distribution Interfaces
The Primary Current Distribution (cd) interface ( ) and the Secondary Current
Distribution (cd) interface ( ) are both found under the Electrochemistry
branch ( ) when adding a physics interface.

Primary Current Distribution Interface

The Primary Current Distribution interface defines the transport of charged ions in an
electrolyte of uniform composition as well as current conduction in electrodes using
Ohm’s law in combination with a charge balance. The physics interface neglects
activation overpotentials due to charge transfer reactions.

140 | CHAPTER 4: ELECTROCHEMISTRY INTERFACES

Use this physics interface to estimate the ohmic losses in simplified models of
electrochemical cells, where the overpotentials of the electrode reactions are small
compared to the ohmic voltage drops in the electrolyte and electrodes.

Secondary Current Distribution Interface

The Secondary Current Distribution interface is similar to the Primary Current
Distribution interface with the difference that it accounts for activation overpotentials.
The relation between charge transfer and overpotential can be described using
arbitrary kinetic expressions, such as Butler–Volmer and Tafel equations.

Use this physics interface for generic modeling of electrochemical cells. It can be
combined with interfaces modeling mass transport to describe concentration
dependent (tertiary) current distributions.

Ohm’s law is used in combination with a charge balance to describe the conduction of
currents in the electrodes and electrolytes.

Use the Current Distribution Type setting on the physics interface node, described
below, to switch between a Primary Current Distribution and a Secondary Current
Distribution interface.

• Introduction to Electrochemistry Modeling

SETTINGS
The Label is the default physics interface name.

The Name is used primarily as a scope prefix for variables defined by the physics
interface. Refer to such physics interface variables in expressions using the pattern
<name>.<variable_name>. In order to distinguish between variables belonging to
different physics interfaces, the name string must be unique. Only letters, numbers, and
underscores (_) are permitted in the Name field. The first character must be a letter.

The default Name (for the first physics interface in the model) is cd.

DOMAIN SELECTION

Domains that do not conduct current should be omitted from the

Domain Selection: for example, the gas channels in a fuel cell.

THE PRIMARY AND SECONDARY CURRENT DISTRIBUTION INTERFACES | 141

 OUT-OF-PLANE THICKNESS

For 2D components, enter a value or expression for the out-of-plane

Thickness d (SI unit: m). The value of d determines the size of the domain
perpendicular to the modeled 2D cross section. This value yields, for
example, the correct total current when the current density is obtained
from a 2D simulation.

CROSS-SECTIONAL AREA

For 1D components, enter a Cross-sectional area Ac (SI unit: m2) to define

a parameter for the area of the geometry perpendicular to the 1D
component. The value of this parameter is used, among other things, to
automatically calculate the total current from the current density vector.
The analogy is valid for other fluxes. The default is 1 m2.

CURRENT DISTRIBUTION TYPE

The Current Distribution Type selected in the list is based on the choice made when
adding a physics interface — Primary or Secondary. The Primary Current Distribution
interface changes to a Secondary Current Distribution interface if the choice is
changed to Secondary, and vice versa.

The selection from this list also governs how electrode reactions are modeled on
interfaces between electrodes and electrolytes.

• Models using a Primary current distribution type use potential constraints (Dirichlet
boundary conditions), according to the equilibrium potential setting.
• Secondary current distribution models use current flux conditions (Neumann
boundary conditions) according to the sum of all electrode reaction current
densities.

PHYSICS VS. MATERIALS REFERENCE ELECTRODE POTENTIAL

The Physics vs. Materials Reference Electrode Potential setting on the physics interface
node can be used to combine material library data for current densities and equilibrium
potentials with an arbitrary reference electrode scale in the physics. The setting affects
the electrode potentials used for model input into the materials node, as well as all
equilibrium potential values output from the materials node.

142 | CHAPTER 4: ELECTROCHEMISTRY INTERFACES

Note that the setting will only impact how potentials are interpreted in communication
between the physics and the Materials node. If the From material option is not in use
for equilibrium potentials or electrode kinetics, the setting has no impact.

DEPENDENT VARIABLES
This physics interface defines dependent variables (fields) for the Electrolyte potential
and Electric potential. The names can be changed but the names of fields and
dependent variables must be unique within a model.

DISCRETIZATION
To see all settings in this section, click the Show More Options button ( ) and select
Advanced Physics Options in the Show More Options dialog box.

• Electrochemical Reactions and the Difference Between a Primary and

a Secondary Current Distribution
• Domain Equations for Primary and Secondary Current Distributions
• Shared Physics Features in the Current Distribution Interfaces
• Theory for the Current Distribution Interfaces

Secondary Current Distribution: Orange Battery: Application Library

path Battery_Design_Module/Batteries,_General/orange_battery

Electrolyte
Use the Electrolyte node to define an electrolyte domain that only conducts current in
the ion conducting phase.

Note that electrolyte in this case does not refer to the pore electrolyte in porous
electrodes (which should be defined by a Porous Electrode node instead).

The Electrolyte conductivity, σl (SI unit: S/m), parameter will define how the current
in the domain depends on the gradient of the potential.

• Domain Equations for Primary and Secondary Current Distributions

• Electrolyte Theory

THE PRIMARY AND SECONDARY CURRENT DISTRIBUTION INTERFACES | 143

 Initial Values
Use this node to specify the Initial Values of the electrolyte potential and the electric
potential for the solver.

For many electrochemical problems that use nonlinear electrode kinetics, such as
Butler-Volmer kinetics, providing reasonable initial values can significantly improve
solver convergence.

A good value for the Electric potential (SI unit: V) in electrode and porous electrode
domains can usually be derived from the boundary conditions. For instance, if a
boundary has been grounded or set to a cell potential, use that value as the initial value
also in the adjacent domain. For the Electrolyte potential (SI unit: V) a good initial
value is often the negative of the equilibrium potential of the grounded electrode.

Porous Electrode
The Porous Electrode node sets up charge balances for the electrode and the pore
electrolyte in a porous electrode. Note that the node should be used for porous
domains that conduct current in both an electrolyte and an electrode phase. For the
case of domains that do not contain a pore electrolyte — for instance, the gas diffusion
layer (GDL) in a PEMFC electrode — use an Electrode node instead.

Use Porous Electrode Reaction subnodes to define the charge transfer reactions that
occur on the interface between the electrolyte and electrode phases within the porous
electrode. For the Secondary Current Distribution interface, the Porous Matrix
Double Layer Capacitance subnode is also available.

The conductivities are taken From material by default. From the respective material list
you may any material in the model, if present. By default they are set to the Domain
material (which is the material applied to the active domain in the Materials node).

You may use the Effective conductivity correction factors to account for the lowered
effective conductivities of the electrode and electrolyte phases due to the lower volume
fractions of each phase, and the tortuosity of the porous matrix.

The Electrode volume fraction is used to calculate the effective electrical conductivity of
the porous matrix when the correction factor is set to Bruggeman or Tortuosity.
Additionally, it is used in calculating the active specific surface area of the porous matrix
when Particle-based area option is selected in the child nodes.

144 | CHAPTER 4: ELECTROCHEMISTRY INTERFACES

DISSOLVING-DEPOSITING SPECIES
Use the settings of this section to define species that participate in
dissolution-deposition electrode reactions within the porous electrode, for instance
metal deposition/dissolution or oxide formation.

Use the Add ( ) and Delete ( ) buttons as needed in the tables to control the
number of species.

Dependent variables for the volumetric molar concentration are added for each
dissolving-depositing species. These variables can be used to keep track of the amount
of reacted material in the porous electrode. The total molar dissolution/deposition
rate depends on the reaction rates and stoichiometry, defined in the Porous Electrode
Reaction subnodes.

The Density and Molar mass determine the electrode growth velocity and the resulting
dissolved/deposited layer thickness. By multiplying by the electrode surface area (in
the case of multiple electrode reaction the average surface area is used), the change in
electrode and electrolyte volume fractions can be also be calculated. By use of the Add
volume change to electrode volume fraction (not available for Separator node of Tertiary
Current Distribution interface) and Subtract volume change from electrolyte volume
fraction check boxes you may define how these volume changes should be included in
the model.

Thickness variables, based on the surface area, are also defined that you for instance
can use to couple to the Film Resistance (see below).

FILM RESISTANCE
See the Electrode Surface node.

• Domain Equations for Primary and Secondary Current Distributions

• Porous Electrode Theory

Capacity Fade of a Lithium-Ion Battery: Application Library path

Battery_Design_Module/Batteries,_Lithium-Ion/capacity_fade

THE PRIMARY AND SECONDARY CURRENT DISTRIBUTION INTERFACES | 145

 Periodic Condition
Use the Periodic Condition to define a periodic relation between two boundaries — for
instance, in a model describing a repetitive unit cell. For more information, see
Periodic Boundary Conditions in the COMSOL Multiphysics Reference Manual.

Thin Electrolyte Layer

The Thin Electrolyte Layer node can be used to model a thin insulating or resistive
sheet, located on an interior boundary in an electrolyte domain. The node can be used
as an alternative to drawing the actual layer domain in the model geometry, which may
significantly reduce meshing and solver time, especially in 3D models.

Thin insulating sheets are commonly inserted in the electrolyte in various types of
electrochemical cells. For example they may be used for optimizing the current
distribution in a corrosion protection application, of for optimizing the local
deposition rate in a deposition bath.

The layer may be set to be either Insulating or Resistive.

For the case of Resistive, the Surface Resistance can either be set directly, or calculated
from Thickness and Conductivity values.

Edge Electrode
The Edge Electrode can be used in 3D problems to define electrodes such as long pipes
and thin wires where the electric potential variation within the electrode in the normal
direction to the electrode surface is negligible. This assumption allows for the thin
electrode domain to be replaced by a lumped one-dimensional partial differential
equation formulation on the edge, describing an electrode surface along the edge with
a given Edge electrode radius. In this way the problem size can be reduced, and
potential problems with mesh anisotropy in the thin layer can be avoided.

The electric current conduction in the tangential direction of an edge can be described
by Ohm’s law or a Fixed electric potential or a Floating potential assuming infinite
conductivity of the edge or an External short electric potential which allows to connect
two electrodes over an external connector with a given bulk resistance.

An Edge Electrode can only be applied to edges within, or adjacent to, Electrolyte
domains.

146 | CHAPTER 4: ELECTROCHEMISTRY INTERFACES

A default Electrode Reaction subnode is added by default to the feature. Double Layer
Capacitance, Electric Ground, Electric Potential, and Electrode Current subnodes can also
be added to the feature.

FILM RESISTANCE
See the Electrode Surface node. The section is only available when a Secondary current
distribution has been selected on the parent node.

CONSTRAINT SETTINGS
To display this section, click the Show More Options button ( ) and select Advanced
Physics Options in the Show More Options dialog box.

The mesh size in the perpendicular direction to the edge should

preferably be in the same order of magnitude as the Edge electrode
diameter in order to achieve good numerical accuracy.

Electrode Line Current Source

For 3D components, use the Electrode Line Current Source on edges.

For 2D components use it on points.

For 2D axisymmetric components, it can only be selected on points

outside the symmetry axis.

ELECTRODE CURRENT SOURCE

Enter the Electrode current source ql,s (SI unit: A/m). The default is 0 A/m.

Electrolyte Line Current Source

For 3D components, use the Electrolyte Line Current Source on edges.

For 2D components use it on points.

For 2D axisymmetric components, it can only be selected on points

outside the symmetry axis.

THE PRIMARY AND SECONDARY CURRENT DISTRIBUTION INTERFACES | 147

 ELECTROLYTE CURRENT SOURCE
Enter the Electrolyte current source ql,l (SI unit: A/m). The default is 0 A/m.

Electrode Symmetry Axis Current Source

For 2D axisymmetric components apply an Electrode Symmetry Axis

Current Source along the symmetry axis boundary.

ELECTRODE CURRENT SOURCE

Enter the Electrode current source ql,s (SI unit: A/m). The default is 0 A/m.

Electrolyte Symmetry Axis Current Source

For 2D axisymmetric components apply an Electrolyte Symmetry Axis

Current Source along the symmetry axis boundary.

ELECTROLYTE CURRENT SOURCE

Enter the Electrolyte current source ql,l (SI unit: A/m). The default is 0 A/m.

Electrode Point Current Source

For 3D components, use the Electrode Points Current Source on edges.

For 2D axisymmetric components, it can only be selected on points

located on the symmetry axis.

ELECTRODE CURRENT SOURCE

Enter the Electrode current source qp,s (SI unit: A). The default is 0 A.

148 | CHAPTER 4: ELECTROCHEMISTRY INTERFACES

Electrolyte Point Current Source

For 3D components, use the Electrolyte Points Current Source on edges.

For 2D axisymmetric components, it can only be selected on points

located on the symmetry axis.

ELECTROLYTE CURRENT SOURCE

Enter the Electrolyte current source qp,l (SI unit: A). The default is 0 A.

Electrode Current
Use this node to define a current source in a point of an Edge Electrode node.

This node is available as a subnode to the Edge Electrode node, when Ohm’s Law has
been selected as the electric potential model.

THE PRIMARY AND SECONDARY CURRENT DISTRIBUTION INTERFACES | 149

 The Tertiary Current Distribution,
Nernst-Planck Interface
In this section:

• The Tertiary Current Distribution, • Separator

Nernst-Planck Interface • Reactions
• Electrolyte • Thin Electrolyte Layer
• Porous Electrode • Initial Values

Various nodes are also available and described for the Transport of Diluted Species
interface. See Domain, Boundary, and Pair Nodes for the Transport of Diluted Species
Interface

All other nodes in the Tertiary Current Distribution, Nernst-Planck

interface are described in Shared Physics Features in the Current
Distribution Interfaces

The Tertiary Current Distribution, Nernst-Planck Interface

The Tertiary Current Distribution, Nernst-Planck (tcd) interface ( ), found under the
Electrochemistry branch ( ) when adding a physics interface, describes the current
and potential distribution in an electrochemical cell taking into account the individual
transport of charged species (ions) and uncharged species in the electrolyte due to
diffusion, migration and convection using the Nernst-Planck equations. The physics
interface supports different descriptions of the coupled charge and mass transport in
the electrolyte (see Electrolyte Charge Conservation below). The electrode kinetics for
the charge transfer reactions can be described by using arbitrary expressions or by using
the predefined Butler-Volmer and Tafel expressions.

Ohm’s law is used in combination with a charge balance to describe the flow of
currents in the electrodes. The charge transfer reactions can be defined as boundary

150 | CHAPTER 4: ELECTROCHEMISTRY INTERFACES

conditions or as sources or sinks within a domain in order for the case of porous
electrodes.

Introduction to Electrochemistry Modeling

SETTINGS
The Label is the physics interface node name that will be shown in the model builder
tree.

The Name is used primarily as a scope prefix for variables defined by the physics
interface. Refer to such physics interface variables in expressions using the pattern
<name>.<variable_name>. In order to distinguish between variables belonging to
different physics interfaces, the name string must be unique. Only letters, numbers, and
underscores (_) are permitted in the Name field. The first character must be a letter.

The default Name (for the first physics interface in the model) is tcd.

DOMAIN SELECTION
The domains that do not conduct current should be omitted from the selection list,
for example, the gas channels in a fuel cell.

OUT-OF-PLANE THICKNESS
For 2D components, the Thickness field (default value: 1 m) defines a parameter for the
thickness of the geometry perpendicular to the two-dimensional cross-section. The
value of this parameter is used, among other things, to automatically calculate the total
current from the current density vector. The analogy is valid for other fluxes.

CROSS-SECTIONAL AREA
For 1D components, enter a Cross-sectional area Ac (SI unit: m2) to define a parameter
for the area of the geometry perpendicular to the 1D component. The value of this
parameter is used, among other things, to automatically calculate the total current
from the current density vector. The analogy is valid for other fluxes. The default is
1 m2.

ELECTROLYTE CHARGE CONSERVATION

The physics interface features five different descriptions of the coupled charge and
mass transport in the electrolyte.

THE TERTIARY CURRENT DISTRIBUTION, NERNST-PLANCK INTERFACE | 151

 Use the Electroneutrality or the Electroneutrality, water based charge conservation
option to model cells with significant concentration gradients of the current-carrying
species (ions). The electroneutrality condition implicitly assumes that all major
current-carrying ions are included in the model. In addition to the electroneutrality
condition, the Electroneutrality, water based option also adds the water auto-ionization
equilibrium condition, including proton and hydroxide transport, when defining the
electrolyte equations. Note that this option adds the concentration variables for
protons ([Link]) and hydroxide ([Link]) automatically, and that dependent variables
for these two species should not be added under Dependent Variables below. With this
setting, to control the initial pH in a simulation, set the initial concentrations of the
other ions in the simulation such that the matching concentration of protons and
hydroxide ions matches the pH desired. For pH less than 7, add and set the
concentration of anions. For pH more than 7, add and set the concentration of cations.
For example, for a water-based system with only Cl-, an initial concentration for Cl- of
10-5 M will result in an initial pH of 5. This is analogous to acidifying the solution
using HCl.

A Supporting electrolyte describes a situation where the major part of the charge is
transferred by ions whose concentration can be described as constant.

Use the Electroanalysis (no potential gradients) option to model electroanalytical

problems with electrolyte solutions containing a large quantity of inert supporting
electrolyte, with a conductivity so high that ohmic losses can be assumed to be
negligible. The electroanalysis option will not solve for the electrolyte potential as a
dependent variable, setting it to a constant value of 0. Migration effects are hence
neglected. Domain and boundary nodes only applicable to the electrolyte phase
potential will be disabled when using electroanalysis.

The Poisson option couples the Nernst-Planck equations for mass transport to the
Poisson equation for describing the potential distribution in the electrolyte, without
any assumption of electroneutrality. This option is typically used when modeling
problems where charge separation effects are of interest, typically within nanometers
from an electrode surface.

For the Electroneutrality option, the From electroneutrality list sets the species that is
calculated from the corresponding condition. Note that the choice of species to be
taken from electroneutrality affects the specific boundary conditions that can be set on
the eliminated species. For example, flux and concentration settings cannot be set for
the eliminated species, and initial values cannot be provided. The choice can also have
an impact on the numerics of the problem.

152 | CHAPTER 4: ELECTROCHEMISTRY INTERFACES

A general advice is to choose a relatively inert ion with high mole fraction to be taken
from electroneutrality for best numerical results.

PHYSICS VS. MATERIALS REFERENCE ELECTRODE POTENTIAL

The Physics vs. Materials Reference Electrode Potential setting on the physics interface
node can be used to combine material library data for current densities and equilibrium
potentials with an arbitrary reference electrode scale in the physics. The setting affects
the electrode potentials used for model input into the materials node, as well as all
equilibrium potential values output from the materials node.

Note that the setting will only impact how potentials are interpreted in communication
between the physics and the Materials node. If the From material option is not in use
for equilibrium potentials or electrode kinetics, the setting has no impact.

DEPENDENT VARIABLES
This physics interface defines these dependent variables (fields), the Concentrations of
the species, the Electrolyte potential, and the Electric potential.

The names can be changed but the names of fields and dependent variables must be
unique within a model.

DISCRETIZATION
Concentrations basis function orders higher than Quadratic are not recommended if
transport by convection is dominating in the model.

To see all settings in this section, click the Show More Options button ( ) and select
Advanced Physics Options from the Show More Options dialog box.

CONSISTENT STABILIZATION AND INCONSISTENT STABILIZATION

To display these sections, click the Show More Options button ( ) and select
Stabilization from the Show More Options dialog box. There are two consistent
stabilization methods available and selected by default — Streamline diffusion and
Crosswind diffusion. There is one inconsistent stabilization method, Isotropic diffusion,

THE TERTIARY CURRENT DISTRIBUTION, NERNST-PLANCK INTERFACE | 153

 which is not selected by default. Any settings unique to this physics interface are listed
below.

• When the Crosswind diffusion check box is selected, a weak term that reduces
spurious oscillations is added to the transport equation. The resulting system is
nonlinear. There are two options for Crosswind diffusion type:
- Do Carmo and Galeão — the default option. This type of crosswind diffusion
reduces undershoot and overshoot to a minimum but can in rare cases give
equations systems that are difficult to fully converge.
- Codina. This option is less diffusive compared to the Do Carmo and Galeão
option but can result in more undershoot and overshoot. It is also less effective
for anisotropic meshes. The Codina option activates a text field for the Lower
gradient limit glim (SI unit: mol/m4). It defaults to 0.1[mol/m^3)/[Link],
where [Link] is the local element size.
• For both consistent stabilization methods, select an Equation residual. Approximate
residual is the default setting and it means that derivatives of the diffusion tensor
components are neglected. This setting is usually accurate enough and is faster to
compute. If required, select Full residual instead.

In the COMSOL Multiphysics Reference Manual see Table 2-4 for links
to common sections and Table 2-5 to common feature nodes. You can
also search for information: press F1 to open the Help window or Ctrl+F1
to open the Documentation window.

• The Nernst-Planck Equations

• Domain Equations for Tertiary Current Distributions Using the
Nernst-Planck Equations and Electroneutrality
• Shared Physics Features in the Current Distribution Interfaces
• Theory for the Current Distribution Interfaces

Vanadium Redox Flow Battery: Application Library path

Battery_Design_Module/Flow_Batteries/v_flow_battery

154 | CHAPTER 4: ELECTROCHEMISTRY INTERFACES

Electrolyte
Use the Electrolyte node to define an electrolyte domain that only conducts current in
the ion conducting phase. The combined charge and mass transfer in the electrolyte is
defined by the node.

What settings are available in this node depends on the Electrolyte Charge
Conservation setting, available on the top node. The Electrolyte conductivity (SI unit:
S/n) setting is only available for the Supporting Electrolyte option. Diffusivity and
mobility settings for H+ and OH- are only available for the Electroneutrality,
water-based option.

The Convection section is available when the Convection check box is selected on the
interface top node. The Velocity field u (SI unit: m/s) of the solvent is specified as a
feature input. Select the source of velocity field from the velocity field list.

By default the Mobility (SI unit: s·mol/kg) for each species is set to be calculated based
on the Diffusion coefficients (SI unit: m2/s) and the temperature using the
Nernst-Einstein relation.

The mobility setting will only have an impact on the transport by migration of charged
species, as defined by the Charge number zc (dimensionless, specify negative charges
using a minus sign). For the Electroneutrality charge conservation model you need at
least one positively and one negatively charged species (ion) in the electrolyte.

Specify the temperature (if you are using mobilities based on the Nernst-Einstein
relation) in the Model Inputs section.

The Water Self-ionization section is available for the Electroneutrality, water-based

option. The section allows the water self-ionization constant to be set. Using the Built
in option, the constant will be set to account for temperature, giving the pH of the
simulation the correct temperature dependence.

Note that the electrolyte in this case does not refer to the pore electrolyte in porous
electrodes (which should be defined by a Porous Electrode node instead). For porous
separators, use the Separator instead.

• Electrolyte Theory
• Domain Equations for Tertiary Current Distributions Using the
Nernst-Planck Equations and Electroneutrality

THE TERTIARY CURRENT DISTRIBUTION, NERNST-PLANCK INTERFACE | 155

 Porous Electrode
The Porous Electrode node sets up charge balances for the electrode and the pore
electrolyte in a porous electrode, and as well as the mass balance for the species in the
electrolyte.

Note that the node should be used for porous domains that conduct current in both
an electrolyte and an electrode phase. For the case of domains that do not contain a
pore electrolyte — for instance, the gas diffusion layer (GDL) in a PEMFC electrode
— use an Electrode node instead.

Use Porous Electrode Reaction child nodes to define the charge transfer reactions that
occur on the interface between the electrolyte and electrode phases within the porous
electrode. The Porous Matrix Double Layer Capacitance subnode is also available.

See the Electrolyte node for more information about the Diffusion and Migration in
Electric Field settings of this node.

Correction factors may be specified in the Effective Transport Parameter Correction

section to account for the lowered effective conductivities of the electrode and
electrolyte phases due to the lower volume fractions of each phase, and the tortuosity
of the porous matrix.

The Electrode volume fraction is used to calculate the effective electrical conductivity of
the porous matrix when the correction factor is set to Bruggeman or Tortuosity.
Additionally, it is used in calculating the active specific surface area of the porous matrix
when Particle-based area option is selected in the child nodes.

DISSOLVING-DEPOSITING SPECIES
See the Porous Electrode node of The Primary and Secondary Current Distribution
Interfaces

FILM RESISTANCE
See the Electrode Surface node.

• Porous Electrode Theory

• Porous Electrode Reactions Theory
• Domain Equations for Tertiary Current Distributions Using the
Nernst-Planck Equations and Electroneutrality

156 | CHAPTER 4: ELECTROCHEMISTRY INTERFACES

Separator
Use a Separator node to model electrolyte charge and mass transport in an
electronically isolating porous matrix. Use correction factors to account for the
lowered diffusion coefficients in the electrolyte and the lowered conductivities of the
electrode, due to the lower volume fractions of each phase and the tortuosity of the
porous matrix.

See also the Electrolyte node for more information about the Diffusion and Migration in
Electric Field settings of this node.

DISSOLVING-DEPOSITING SPECIES
See the Porous Electrode node of The Primary and Secondary Current Distribution
Interfaces

Reactions
Use the Reactions node to define non-electrochemical reactions in an electrolyte
domain.

The node is found from the Additional Sources submenu.

REACTING VOLUME
When specifying reaction rates in the Rc2 (SI unit: mol/m3·s) fields for a species in a
Porous Electrode domain, the specified reaction rate expression may either refer to the
total volume or the pore (electrolyte) volume. For nonporous domains the settings of
the Reacting Volume section has no impact.

For Total volume the reaction expressions are used as specified (multiplied by unity).

For Pore volume this results in the specified reaction expressions being multiplied by
the domain electrolyte volume fraction εl. (εl equals unity for nonporous domains).

Initial Values
Use this node to specify the Initial Values of the concentration, electrolyte potential and
electric potential dependent variables to be used by the solver.

For many electrochemical problems that use nonlinear electrode kinetics, such as
Butler-Volmer kinetics, providing reasonable initial values can significantly improve
solver convergence.

THE TERTIARY CURRENT DISTRIBUTION, NERNST-PLANCK INTERFACE | 157

 A good value for the Electric potential (SI unit: V) in electrode and porous electrode
domains can usually be derived from the boundary conditions. For instance, if a
boundary has been grounded or set to a cell potential, use that value as the initial value
also in the adjacent domain. For the Electrolyte potential (SI unit: V) a good initial
value is often the negative of the equilibrium potential of the grounded electrode.

For the Concentration initial values, at least one positive and one negative charged
species should have a nonzero and positive initial value (after considering the
electroneutrality condition). The initial value for the ion calculated from the
electroneutrality condition cannot be set explicitly.

Ion Exchange Membrane

Use the ion exchange membrane node to specify a domain with a permanent fixed
space charge. The node is typically used for defining permselective membranes, used
for various applications such as dialysis cells or flow batteries.

The node models the transport of all species added at the interface top node, and adds
a fixed space charge to the electroneutrality condition.

The Fixed space charge specifies the charge ions fixed in the membrane polymer matrix.
Use negative space charges for cation selective membranes and positive charges for
anion selective membranes, respectively.

Select the Apply Donnan Boundary Conditions check box to enable Donnan equilibrium
conditions on all interior boundaries between the domain selected by the node and all
adjacent domains selected by the interface (except Electrode nodes). The boundary
conditions are applied for all species and the electrolyte potential dependent variable.
This option is not available for the Poisson charge conservation model option.

For the remaining settings of this node, see the Electrolyte and Separator nodes.

Ion Exchange Membrane Boundary

Use the Ion Exchange Membrane boundary node to specify an external boundary over
which the flux of a charge-carrying species is continuous but the electrolyte potential
shifts with a specified value. This condition is typically used in electrochemical cells
containing both free electrolytes and ion exchange membranes, for instance in dialysis
or flow battery problems. The node is typically used to couple two separate current
distribution interfaces, where one of the interfaces models free electrolyte domain, and
the other interface models the ion-exchange membrane domain.

158 | CHAPTER 4: ELECTROCHEMISTRY INTERFACES

Note that using the Ion Exchange Membrane domain node often is a more convenient
modeling approach if the transported species in the free electrolyte and ion exchange
membrane are the same.

The node is applicable to external boundaries to electrolyte domains. For defining

ion-exchange membranes on an interior boundary between two electrolyte domains,
use the Thin Electrolyte Layer node.

The choice of Charge-carrying species concentration species specifies that the current
flowing over the boundary will be carried by this species (which must have a nonzero
charge number). Use the Membrane potential setting to set the electrolyte potential on
the membrane side of the boundary. Note that if this potential is set to the electrolyte
potential of a Primary or Secondary Current Distribution interface, no additional
settings are needed in that interface to set up the correct boundary condition.

The potential condition may be either Donnan, which will calculate the potential shift
over the boundary based on the membrane charge carrying species concentration, or
can be User defined.

Thin Electrolyte Layer

Use this node to specify a thin layer on an interior boundary between two electrolyte
domains. The node can be used as an alternative to drawing the actual layer as a
domain in the model geometry, which may significantly reduce meshing and solver
time, especially in 3D models.

The layer may either be Insulating, Resistive (supporting electrolytes only), or an Ion
exchange membrane.

For Resistive or Ion exchange membrane, the potential drop over the membrane is
determined either from the Surface resistivity or the Thickness and conductivity.

For Ion exchange membrane, the choice of Charge-carrying species concentration species
specifies that the current flowing over the layer will be carried by this species (which
must have a nonzero charge number). The potential condition may be either Donnan,
which will calculate the potential shift over the boundary based on the membrane
charge carrying species concentration, or User defined.

THE TERTIARY CURRENT DISTRIBUTION, NERNST-PLANCK INTERFACE | 159

 Shared Physics Features in the
Current Distribution Interfaces
Domain, Boundary, Pair, Edge, and Point Nodes for the
Electrochemistry Interfaces
Electrochemistry Interfaces interfaces have these domain, boundary, edge, point, and
pair nodes, listed in alphabetical order, available from the Physics ribbon toolbar
(Windows users), Physics context menu (Mac or Linux users), or right-click to access
the context menu (all users).

Most nodes and features described in this section are available for all the
Electrochemistry branch interfaces unless otherwise indicated.

In general, to add a node, go to the Physics toolbar, no matter what

operating system you are using. Subnodes are available by (right) clicking
the parent node and selecting it from the Attributes menu.

160 | CHAPTER 4: ELECTROCHEMISTRY INTERFACES

• Double Layer Capacitance • Electrolyte Current Source
• Charge-Discharge Cycling • Electrolyte Potential
• Circuit Terminal • External Short
• Electric Ground • Harmonic Perturbation
• Electric Potential • Highly Conductive Porous
• Electric Reference Potential Electrode

• Electrode • Initial Values for

Dissolving-Depositing Species
• Electrode Current
• Insulation
• Electrode Current Density
• Internal Electrode Surface
• Electrode Current Source
• Line Mass Source1
• Electrode-Electrolyte Boundary
Interface • Non-Faradaic Reactions

• Electrode Power • Point Mass Source1

• Electrode Potential • Porous Electrode Reaction

• Electrode Reaction • Porous Matrix Double Layer

Capacitance
• Electrode Surface
• Reference Electrode
• Electrolyte Current Density
• Symmetry
• Thin Electrode Layer
1
For the Tertiary Current Distribution, Nernst-Planck interface, these nodes are
available and described for the Transport of Diluted Species interface.

In the COMSOL Multiphysics Reference Manual see Table 2-4 for links
to common sections and Table 2-5 to common feature nodes. You can
also search for information: press F1 to open the Help window or Ctrl+F1
to open the Documentation window.

Theory for the Current Distribution Interfaces

SHARED PHYSICS FEATURES IN THE CURRENT DISTRIBUTION INTERFACES | 161

 Electrode
Use the Electrode node to define an electrode domain that only conducts current in
the electron conducting phase.

The node is typically used for modeling solid metal electrodes, current collectors,
current feeders, gas diffusion layers and gas backings.

The Electrical conductivity σs (SI unit: S/m) parameter will define how the current in
the domain depends on the gradient of the potential.

Electrode Theory

Highly Conductive Porous Electrode

The Highly Conductive Porous Electrode node defines a charge balance of the pore
electrolyte in a porous electrode, and, for interfaces solving for electrolyte species, the
corresponding mass balance for the species in the electrolyte. Use this node when
electrical conductivity is high enough to assume uniform potential in the electron
conducting phase of the porous electrode.

See the Electrode Surface node for a description of the Electrode Phase Potential
Condition and Harmonic Perturbation sections.

See the Porous Electrode node for a description of the remaining settings.

Electrode Current Source

Use the Electrode Current Source node to define contributions to the current density
from electron current sources. The Current source, Qs (SI unit: A/m3), is added
according to the following equation:

∇ ⋅ is = Qs

where

i s = – σ s ∇φ s

and σs denotes the electrode’s conductivity and φ s the electric potential.

162 | CHAPTER 4: ELECTROCHEMISTRY INTERFACES

To use this feature, click the Show More Options button ( ) and select Advanced
Physics Options in the Show More Options dialog box. Then add the node from the
Additional Sources submenu.

Electrolyte Current Source

Use the Electrolyte Current Source node to define contributions to the current density
in the electrolyte from, for example reactions, or other effects.

The Current source, Ql (SI unit: A/m3), is added according to the following equation:

∇ ⋅ il = Ql

To use this feature, click the Show More Options button ( ) and select Advanced
Physics Options in the Show More Options dialog box. Then add the node from the
Additional Sources submenu.

Porous Electrode Reaction

The Porous Electrode Reaction node defines the electrode kinetics for a charge transfer
reaction that occurs at the interface between the pore electrolyte and the electrode
matrix a porous electrode. The node can be added as subnode to a Porous Electrode
node. Add multiple nodes to the same Porous Electrode node to model multiple
reactions, for instance in mixed potential problems.

See the Electrode Reaction node for a description of the Equilibrium Potential,
Electrode Kinetics, Stoichiometric Coefficients and Heat of Reaction sections.

ACTIVE SPECIFIC SURFACE AREA

The Active specific surface area, av (SI unit: m2/m3) specifies the area of the
electrode-electrolyte interface that is catalytically active for this porous electrode
reaction. av is multiplied by iloc, defined in the Electrode Kinetics section, to produce
a current source in the domain.

This section is not available for primary current distribution interfaces.

• Porous Electrode Reactions Theory

• Electrode Kinetics Expressions.

SHARED PHYSICS FEATURES IN THE CURRENT DISTRIBUTION INTERFACES | 163

 Porous Matrix Double Layer Capacitance
Use the Porous Matrix Double Layer Capacitance subnode to define a non-faradaic
double layer current density at the interface between the porous electrode matrix and
the electrolyte. The node can be added as subnode to a Porous Electrode node.

The resulting double layer current source in the Porous Electrode domain depends on
the time derivative of the potentials and is proportional to both the Electrical double
layer capacitance Cdl (SI unit: F/m2) and the Double layer area av,dl (SI unit: 1/m).

Note that for stationary problems the double layer current is zero.

This node is not available for the Primary Current Distribution interface.

Use the settings of the Stoichiometry section (not available in the Primary or Secondary
Current Distribution interfaces) to control what species are participating in the double
layer charging — that is, the mass exchange between the double layer and the
electrolyte outside the double layer.

Insulation
The Insulation boundary condition describes the walls of a cell or the boundaries of the
cell that do not face a conductor. The boundary condition imposes the following
equation:

ik ⋅ n = 0

where ik denotes the current density vector and k = l, s is an index for the electrolyte
and electrode, respectively.

Symmetry
For the Primary Current Distribution and Secondary Current Distribution interfaces,
the Symmetry boundary condition is identical to the Insulation condition.

For the Tertiary Current Distribution, Nernst-Planck interface, the Symmetry

boundary condition imposes a no flux condition for the molar flux of species at a
boundary.

Symmetry Theory

164 | CHAPTER 4: ELECTROCHEMISTRY INTERFACES

Electrode Surface
Use the Electrode Surface node to model an electrochemical electrode-electrolyte
interface between an electrolyte domain and an electrode boundary where the
electrode is not included explicitly as a domain in the model geometry. Set the electric
potential of the electrode or specify a current condition that the potential of the
electrode shall fulfill, and use subnodes to specify the Electrode Reaction and the
Double Layer Capacitance at the interface.

This node can only be applied on outer boundaries to electrolyte domains. For interior
boundaries to electrolyte domains, use the Perforated Electrode Surface node. For
interior boundaries between electrolyte and electrode domains, use the Internal
Electrode Surface node.

DISSOLVING-DEPOSITING SPECIES
Use the settings of this section to define species that participate in
dissolution-deposition electrode reactions, for instance metal deposition/dissolution
or oxide formation.

Use the Add ( ) and Delete ( ) buttons as needed in the tables to control the
number of species.

The Density and Molar mass, in conjunction with the reaction rates and stoichiometry,
defined in the Electrode Reaction subnodes, determine the normal electrode growth
rate.

When the Solve for species concentrations variables check box is checked, dependent
variables for the molar surface concentration of the dissolving-depositing species are
added. These can be used to model the thickness of an dissolving/depositing layer in
a time-dependent simulation where the resulting deformation in the model geometry
is small and will have negligible impact on the current distribution.

When solving for the species concentration variables, corresponding thickness variables
are defined that you for instance can use to couple to the Film Resistance (see below).

Deposition-Dissolution Rates, Growth Velocities, and Thicknesses on an

Electrode Surface

Use The Surface Reactions Interface to model surface diffusion.

SHARED PHYSICS FEATURES IN THE CURRENT DISTRIBUTION INTERFACES | 165

 FILM RESISTANCE
Use a film resistance if you want to include an additional potential drop due to an
ohmic resistance at the interface between the electrode and the electrolyte, for instance
due to build-up of insulating deposits.

Specify either a Surface resistance Rfilm (SI unit: Ω·m2) directly or choose the Thickness
and conductivity option to calculate the surface resistivity based on a depositing film
thickness.

HARMONIC PERTURBATION
Use this section in conjunction with AC Impedance study types to control the
perturbation amplitude in the frequency domain.

The perturbation parameter is either Electric potential, Electrode potential, Total

current, or Average current density, based on the Boundary condition selected in the next
section.

The frequency spectrum is specified in the study node.

ELECTRODE PHASE POTENTIAL CONDITION

This section specifies the potential in the electrode phase of the electrolyte-electrode
interface. The electrode potential is used (via the overpotential) by the Electrode
Reaction subnodes.

Use the Electric potential option to set the value of the potential explicitly with respect
to ground whereas the Electrode potential will set the potential value with respect to a
reference potential. Total current, Average current density, and External short all add an
extra global degree of freedom for the potential in the electrode phase, set to comply
with the chosen condition.

When using the Total current option in 1D or 2D, the boundary area is based either
on the Cross-sectional area (1D), or the Out-of-Plane thickness (2D) properties, set on
the physics interface top node.

See also the documentation for the Electrode Potential and External Short nodes for
further information about these boundary condition.

166 | CHAPTER 4: ELECTROCHEMISTRY INTERFACES

Cyclic Voltammetry
The Cyclic voltammetry setting varies the electric potential linearly in time as follows
when used in conjunction with a Cyclic Voltammetry study step:

End potential
Cycle 1 Cycle 2

Vertex 1

Vertex 2

Start potential

Figure 4-1: Electric potential vs time generated by the cyclic voltammogram boundary
condition. The linear sweep rate is 100 mV/s, the number of cycles is 2. Potentials levels are
also shown.

More advanced waveforms can be obtained using the Electric potential option with a
parameter setting based on Functions found in the Definitions menu.

Counter Electrode (Electroanalysis only)

This boundary condition is only available for the Electroanalysis charge conservation
model in the Tertiary Current Distribution, Nernst-Planck (tcd) interface.

The Counter electrode option will set a potential to ensure an overall charge balance of
the cell so that the integral of all electrode reaction currents of all electrode surface
node sums up to zero.

See also Counter Electrodes and Overall Charge Balance

ADVANCED CYCLIC VOLTAMMETRY SETTINGS

To display this section, click the Show More Options button ( ) and select Advanced
Physics Options in the Show More Options dialog box.

If Cyclic voltammetry is selected as the Boundary condition, the Smoothing of cyclic

voltammetry wave functions check box is selected by default and the Smoothing factor

SHARED PHYSICS FEATURES IN THE CURRENT DISTRIBUTION INTERFACES | 167

 defaults to 1·10-3. When enabled, smoothing is applied on the triangular wave around
the vertex potentials. The smoothing zone corresponds to the product of the
smoothing factor with half the duration of one period of the triangular wave.

EQUILIBRIUM POTENTIAL HANDLING (PRIMARY CONDITION)

This setting only has an effect if there are multiple Electrode Reaction subnodes
present and if either a Current Distribution Initialization study step (using a Primary
Current distribution type) or the Primary Current Distribution interface is used.

The setting determines which equilibrium potential value will be used for defining the
primary current distribution constraint. When the First reaction has been selected, the
first electrode reaction subnode must be active in the model.

To display this section, click the Show More Options button ( ) and select Advanced
Physics Options in the Show More Options dialog box.

CONSTRAINT SETTINGS
For primary current distributions, the use of weak constraints will in some cases give a
more accurate value of the local current density during the solver process. This may in
turn render more accurate results when coupling to the local current density variable
to describe other phenomena in the model, for instance when modeling geometry
deformation due to electrode dissolution/deposition.

The section is available in the Primary Current Distribution and Secondary Current
Distribution interfaces when the Current Distribution Model property has been set to
Primary.

This section is only available in the Primary Current Distribution and Secondary
Current Distribution interfaces when the Current Distribution Model property has been
set to Primary. To display this section, click the Show More Options button ( ) and
select Advanced Physics Options in the Show More Options dialog box.

• Electrode Reactions Theory

• Film Resistance

Electrode Reaction
The Electrode Reaction subnode defines the electrode kinetics for a charge transfer
reaction that occurs on an electrolyte-electrode interface boundary. Use multiple
nodes to model multiple reactions, for instance in mixed potential problems.

168 | CHAPTER 4: ELECTROCHEMISTRY INTERFACES

The parent node may be either an Internal Electrode Surface or an Electrode Surface.

Note that all settings described below are not available for all Electrochemistry
interfaces.

• Electrode Reactions Theory

EQUILIBRIUM POTENTIAL
The Equilibrium potential, Eeq (SI unit: V), is used in the electrode kinetics expressions
in the Electrode Kinetics section (via the definition of the overpotential), or for setting
up primary current distribution potential constraints.

The equilibrium potential may be defined either in the Materials node (From material),
by using the Nernst Equation, or by using a User defined expression.

If the Nernst Equation is used, the concentration dependence is calculated

automatically based on the Reference equilibrium potential Eeq, ref (V).

For all interfaces except the Tertiary Current Distribution interface, the concentration
dependence is based on the user-defined Reduced species expression CR (unitless) and
Oxidized species expression CO (unitless) parameters. CR and CO should be defined so
that the quotient between them is 1 for the reference state (for which Eeq=Eeq, ref).

In the Tertiary Current Distribution interface, the concentration dependence of the

Nernst Equation is based entirely on the settings in the Stoichiometric Coefficients and
the Reference Concentrations sections.

When using Nernst Equation, additional options are available in the Butler-Volmer
expression type in the Electrode Kinetics section.

• Equilibrium Potentials and the Nernst Equation

REFERENCE CONCENTRATIONS
This section is only available in the Tertiary Current Distribution interface, if the
equilibrium potential has been selected to be defined by the Nernst Equation.

The reference concentrations define the reference state for which Eeq = Eeq, ref.

SHARED PHYSICS FEATURES IN THE CURRENT DISTRIBUTION INTERFACES | 169

 ELECTRODE KINETICS
The settings of this section will define the local current density, iloc (SI unit: A/m2), at
the interface between the electrolyte and the electrode. Note that iloc for all built-in
kinetics expression types will depend on the overpotential, which in turn depend on
the Equilibrium potential defined in the previous section.

The Local current density expression, iloc, expr (SI unit: A/m2), may be defined either
in the Materials node (From material), by using the From kinetics expression, or by using
a User defined expression.

For all kinetic expressions the Exchange current density i0 (SI unit: A/m2) is a measure
of the kinetic activity. The exchange current density is typically concentration
dependent.

Most kinetic expression types feature the Limiting Current Density option in order to
impose an upper limit on the local current density magnitude. The feature can be used
to model additional mass transport limitations that are not already included in the local
current density expression. For Limiting Current Density enter a value for ilim
(SI unit: A/m2).

In the Tertiary Current Distribution interface, the Linearize concentration dependence

for low concentrations option is used to set a Concentration linearization limit clim
(SI unit: mol/m3) for linearizing the concentration dependence of kinetics for low
concentrations, in order to improve convergence for non-unit stoichiometries. Note
that this option is available for Nernst Equation equilibrium potential and Butler-Volmer
kinetics with either Mass action law or Lumped multistep selected as the exchange
current density type.

Butler-Volmer or Linearized Butler-Volmer

The Butler-Volmer kinetics expression is the most common way to define
electrochemical kinetics. The Linearized Butler-Volmer is valid when the overpotentials
of the reactions are small (<<25 mV). The linearized version can also be used to
troubleshoot a model with convergence problems.

When using the Nernst Equation for defining the equilibrium potential (see above), the
concentration dependence of the Exchange current density i0 may be defined in a
thermodynamically consistent way in accordance with the Nernst equation, in
combination with a Reference exchange current density i0,ref (A/m2), which is the
exchange current density when Eeq=Eeq, ref.

For all interfaces except the Tertiary Current Distribution interface, the concentration
dependence when using From Nernst Equation will use CR and CO as pre-exponential

170 | CHAPTER 4: ELECTROCHEMISTRY INTERFACES

factors for the anodic and cathodic terms, respectively. In the Tertiary Current
Distribution interface, the Lumped multistep option can be used to define i0 by the use
of either Generic exponentials, or Anodic or Cathodic reaction orders. The Mass action
law will define the reaction orders according to the reaction stoichiometry and the law
of mass action.

The Anodic transfer coefficient, αa (dimensionless), and Cathodic transfer coefficient, αc

(dimensionless), parameters will impact how much iloc will change upon changes in the
overpotential. In order to ensure thermodynamic consistency, αc cannot be user
defined when i0 is calculated From Nernst Equation (or by Mass action law in the Tertiary
Current Distribution interface). For this case, αc is defined automatically, based on the
and the number of participating electrons in the reaction, defined in the stoichiometry
section.

Anodic Tafel Equation

This kinetics expression type neglects the cathodic (negative) term in the
Butler-Volmer equation. It is only valid for electrode reactions with high anodic
overpotentials (>>100 mV).

The Anodic Tafel slope, Αa (SI unit: V), defines the required increase in overpotential
to result in a tenfold increase in the current density.

Cathodic Tafel Equation

This kinetics expression type neglects the anodic (positive) term in the Butler-Volmer
equation. It is only valid for electrode reactions with significant cathodic overpotentials
(<<-100 mV).

The Cathodic Tafel slope, Αc (SI unit: V), describes the required decrease in
overpotential to result in a tenfold increase in the current density magnitude. Αc
should be a negative value.

Concentration Dependent Kinetics

This expression type is not available if Nernst equation has been selected in the
Equilibrium Potential section.

Note that the combination of Nernst equation and the Butler Volmer kinetics type will
in most cases render identical kinetics as for the Concentration Dependent Kinetics. It
is recommended to always use Nernst Equation + Butler Volmer whenever possible,
since this combination is guaranteed to be thermodynamically consistent.

The Concentration Dependent Kinetics expression type may be used in concentration

dependent (tertiary) current distribution problems. One or both of the Oxidizing

SHARED PHYSICS FEATURES IN THE CURRENT DISTRIBUTION INTERFACES | 171

 species expression CO (dimensionless) and Reducing species expression CR
(dimensionless) parameters may be concentration dependent, and should typically be
defined so that CO = CR at equilibrium.

• Electrode Kinetics Expressions

Fast Irreversible Electrode Reaction

This kinetics expression type is typically used in tertiary current distribution problems
for reactions occurring far away from the equilibrium potential.

The kinetics expression type defines an irreversible electrode reaction where the
kinetics is so fast that the only factor limiting the reaction rate is the transport of a
species to the reacting surface.

The node will set the Rate limiting species concentration to zero at the boundary, and
balance the fluxes of the species participating in the reaction and the current densities
according to the Stoichiometric Coefficients settings.

Thermodynamic Equilibrium (Primary Condition)

This choice imposes a zero overpotential for the electrode reaction by applying a
constraint on the potential variables in order to comply with the equilibrium potential.
Use this kinetics for very fast reactions.

In the Secondary Current Distribution interface the condition set by this expression
type is mathematically identical to what is applied when a Primary Current
Distribution is chosen on the interface top node. The expression type can hence be
used to mix primary and secondary current distributions on different electrodes. The
Thermodynamic equilibrium (primary condition) cannot not be used when defining
the kinetics for multiple electrode reactions at the same electrode in the Secondary
Current Distribution interface.

STOICHIOMETRIC COEFFICIENTS
Specify the Number of participating electrons nm in the electrode reaction and the
Stoichiometric coefficient (vc1, vc2, and so forth) for each of the involved species
according to the following generic electrochemical reaction:

 νox Sox + ne  νred Sred

-
⇔ (4-1)
ox red

172 | CHAPTER 4: ELECTROCHEMISTRY INTERFACES

Set νi as positive (νred) for the reduced species and negative (νox) for the oxidized
species in an electrochemical reaction. The number of participating electrons, n,
should be positive.

If the concentration of a species in the charge conservation model for the electrolyte is
based on an algebraic expression (such as the electroneutrality condition, or the water
auto ionization), the stoichiometric coefficient for this species cannot be set explicitly.
The stoichiometric coefficient will instead be set implicitly, based on the number of
electrons and the stoichiometric coefficients of the other species participating in the
reaction.

An easy way to determine the stoichiometric coefficients for a reaction is

to write the reaction as a reduction reaction (with the electrons on the
left), irrespectively on the expected actual direction of the reaction in the
model. The species on the left side then have negative coefficients and the
species on the right have positive coefficients.

• Mass Fluxes and Sources Due to Electrochemical Reactions

HEAT OF REACTION
The Heat of Reaction section provides two options: Temperature derivative and
Thermoneutral voltage to calculate the reversible heat source of the electrode reaction,
which in turn can be used for coupling to heat transfer physics.

The Temperature derivative of equilibrium potential parameter, dEeq/dT (SI unit:

V/K), can be specified in case of Temperature derivative selection. Note that dEeq/dT
parameter value has no impact on the equilibrium potential variable.

The Thermoneutral voltage parameter, Etherm (SI unit: V), can be specified in case of
Thermoneutral voltage selection.

• Heating Due to Electrochemical Reactions

SHARED PHYSICS FEATURES IN THE CURRENT DISTRIBUTION INTERFACES | 173

 Double Layer Capacitance
The Double Layer Capacitance subnode describes the non-faradaic currents due to
charge and discharge of the double layer situated at the interface between the electrode
and the electrolyte. The resulting double layer current density on the boundary
depends on the time derivative of the potentials and is proportional to the Electrical
double layer capacitance Cdl (SI unit: F/m2). For stationary problems the double layer
current density is zero.

Use this node to simulate transient analysis techniques, such as AC-impedance analysis
and current interrupt studies.

The parent node may be either an Internal Electrode Surface or a Electrode Surface.

This subnode is not available for the Primary Current Distribution interface.

Use the settings of the Stoichiometry section (not available in the Primary or Secondary
Current Distribution interfaces) to control what species are participating in the double
layer charging — that is, the mass exchange between the double layer and the
electrolyte outside the double layer.

Internal Electrode Surface

The Internal Electrode Surface node defines the electrochemical electrode-electrolyte
interface between an electrode domain and the electrolyte domain. Use this node as a
parent node for Electrode Reactions and the Double Layer Capacitance of an
electrolyte-electrode interface when you explicitly model the electron conducting
electrode as a domain in your model.

Electrode domain
φs
Electrolyte domain
φl

Internal Electrode Surface

174 | CHAPTER 4: ELECTROCHEMISTRY INTERFACES

The node can only be applied at interior boundaries between electrode and electrolyte
domains. Note that, due to the high conductivity of many electrode materials, an
Electrode domain can many times be replaced an external condition at the electrolyte
boundary. For such cases, consider using the Electrode Surface instead.

For a description of the Film Resistance, Dissolving-Depositing Species and Constraint

Settings sections, see the Electrode Surface node.

• Electrode Reactions Theory

For an example of this feature see Orange Battery: Application Library

path Battery_Design_Module/Batteries,_General/orange_battery.

Electrolyte Potential
Add the Electrolyte Potential node from Electrolyte submenus for boundaries, edges,
and points to set a fixed potential at a position in the electrolyte. This node can be used
to model half-cells, or to set the electrolyte potential at the position of, for example, a
reference electrode.

The node sets the potential in the electrolyte, φ l, to be equal to the Boundary
electrolyte potential, φ l, bnd (SI unit: V).

By right-clicking this node you may add a Harmonic Perturbation subnode.

CONSTRAINT SETTINGS
To display this section, click the Show More Options button ( ) and select Advanced
Physics Options in the Show More Options dialog box.

Electrolyte Current
The Electrolyte Current boundary condition sets the total current or average current
density of a boundary. The condition sets the total inward current without imposing
the current density distribution. It will set a constant electrolyte potential along the
given boundary, that satisfies the current value setting.

SHARED PHYSICS FEATURES IN THE CURRENT DISTRIBUTION INTERFACES | 175

 When using the Total current option in 1D or 2D, the boundary area is based either
on the Cross-sectional area (1D) or the Out-of-Plane thickness (2D) properties, set on
the physics interface top node.

CONSTRAINT SETTINGS
To display this section, click the Show More Options button ( ) and select Advanced
Physics Options in the Show More Options dialog box.

• Electrolyte Current Theory

Electrolyte Current Density

Use the Electrolyte Current Density node to specify the current density distribution
along a boundary.

Note that using this node in 2D or 3D may result in an uneven potential distribution
along the boundary. To mitigate such effects you may use the Electrode Current node
instead.

By right-clicking this node you may enable Harmonic Perturbation. This means that the
node will only be active when solving for Frequency Domain study steps (typically used
in AC Impedance studies). The frequency spectrum is specified in the study node.

Thin Electrode Layer

The Thin Electrode Layer node can be used to model a thin insulating or resistive sheet,
located on an interior boundary in an electrode domain. The node can be used as an
alternative to drawing the actual layer domain in the model geometry, which may
significantly reduce meshing and solver time, especially in 3D models.

A thin electrode layer can be used to model, for instance, a contact impedance between
two electronic conductors.

The layer may be set to be either Insulating or Resistive.

For the case of Resistive, the Surface Resistance can either be set directly, or calculated
from Thickness and Conductivity values.

176 | CHAPTER 4: ELECTROCHEMISTRY INTERFACES

Electrode-Electrolyte Boundary Interface
Note that this is an advanced physics feature that is normally not used. To display this
feature in the context menu, click the Show More Options button ( ) and then select
Advanced Physics Options in the Show More Options dialog box. Then add the
Electrode-Electrolyte Boundary Interface node from the Electrode or Pairs>Electrode
submenu.

Use this node to model an electrochemical interface between an electrolyte and a

electrode where the electrolyte domain is not included explicitly in the model. The
node can only be applied on outer boundaries to electrode domains. Set the potential
of the electrolyte either explicitly, or specify a current condition that the potential of
the electrode shall fulfill.

Electrode Reaction and Double Layer Capacitance subnodes are available from the
context menu (right-click the parent node) or from the Physics toolbar, Attributes
menu.

This node is available for the Secondary Current Distribution and Tertiary Current
Distribution, Nernst-Planck [Link] is also available and described here for the
Battery interface.

BOUNDARY CONDITION
This section specifies the potential of the electrolyte phase for the electrolyte-electrode
interface. The electrolyte potential is used (via the overpotential) by the Electrode
Reaction subnodes.

The Electrolyte potential will set the potential value directly, whereas Total current or
Average current density both add an extra global degree of freedom for the potential in
the electrolyte phase, set to comply with the chosen condition.

When using the Total current option in 1D or 2D, the boundary area is based either
on the Cross-sectional area (1D) or the Out-of-Plane thickness (2D) properties, set on
the physics interface top node.

Electric Ground
This node to sets the electric potential to zero.

The node is typically used to ground the voltage at an external boundary in a model
that contains either electrode or porous electrode domains.

SHARED PHYSICS FEATURES IN THE CURRENT DISTRIBUTION INTERFACES | 177

 CONSTRAINT SETTINGS
To display this section, click the Show More Options button ( ) and select Advanced
Physics Options in the Show More Options dialog box.

Electric Potential
This node sets the electric potential in the electrode (or a porous electrode), φ s, to a
value, φ s, bnd according to the following:

φ s = φ s, bnd

The node is typically used to set the cell voltage at an external boundary in a model
that contains either electrode or porous electrode domains.

By right-clicking this node you may add a Harmonic Perturbation subnode.

CONSTRAINT SETTINGS
To display this section, click the Show More Options button ( ) and select Advanced
Physics Options in the Show More Options dialog box.

Electrode Current Density

The Electrode Current Density boundary condition can be applied at an external
boundary of a model that contains either electrode or porous electrode domains.

Note that using this node in 2D or 3D may result in an uneven potential distribution
along the boundary. To mitigate such effects you may use the Electrode Current node
instead.

By right-clicking this node you may enable Harmonic Perturbation. This means that the
node will only be active when solving for Frequency Domain study steps (typically used
in AC Impedance studies). The frequency spectrum is specified in the study node.

Electrode Current
Use the Electrode Current node to set the total current or average current density over
an external electrode or porous electrode boundary — typically at the interface
between the electrode and the current collector or current feeder. The condition sets
the total inward current without imposing the current density distribution. The
potential along the boundary is calculated in order to satisfy the total value of the
current.

178 | CHAPTER 4: ELECTROCHEMISTRY INTERFACES

When using the Total current option in 1D or 2D, the boundary area is based either
on the Cross-sectional area (1D), or the Out-of-Plane thickness (2D) properties, set on
the physics interface top node.

CONSTRAINT SETTINGS
To display this section, click the Show More Options button ( ) and select Advanced
Physics Options in the Show More Options dialog box.

• Electrode Current Theory

Electrode Power
The Electrode Power boundary condition sets the power drawn from, or inserted to, an
electrical cell at external electrode boundary.

When using the Total power option in 1D or 2D, the boundary area is based either on
the Cross-sectional area (1D), or the Out-of-Plane thickness (2D) properties, set on the
physics interface top node.

Electrode Power Theory

Harmonic Perturbation
Use the Harmonic Perturbation subnode to specify the voltage amplitude perturbation
in the frequency domain. The harmonic perturbation is only applied when solving for
a Frequency-Domain study type, which is typically used in AC Impedance studies.

The Harmonic Perturbation subnode can be added to the Electric Potential, Electrolyte
Potential. The subnode is available from the context menu (right-click the parent
node) or from the Physics toolbar in the Contextual group.

The frequency spectrum is specified in the study node.

SHARED PHYSICS FEATURES IN THE CURRENT DISTRIBUTION INTERFACES | 179

 You may also specify harmonic perturbations to the Electrode Current Density,
Electrolyte Current Density and Electrode Surface nodes.

Frequency Domain Perturbation Study Step in the COMSOL

Multiphysics Reference Manual

Electrode Potential
Use the Electrode Potential node to set a boundary condition for the electric potential
with respect to a defined reference potential.

Electric potentials defined by the Electric Reference Potential and Reference Electrode
point nodes can be used as input when specifying the Electric reference potential φ vs,ref
(SI unit: V).

CONSTRAINT SETTINGS
To display this section, click the Show More Options button ( ) and select Advanced
Physics Options in the Show More Options dialog box.

Electrode Potentials and Reference Electrodes

External Short
Use the External Short node to connect two electrodes over an external connector with
a given Resistance R (SI unit: ohm).

The boundary selected in the External Short node will be set to a constant potential,
φ s, here , and the integrated current over the boundary will be computed according to
Ohm’s law:

φ s = φ s, here

φ s, here – φ s, there
φ s, here :  ( n ⋅ Is )ddΩ = – ---------------------------------------
R
-
dΩ

where φ s, there (V) is the potential of the connected electrode. Use the Connected
Potential list to choose among available connection potentials for the value of φ s, there .

180 | CHAPTER 4: ELECTROCHEMISTRY INTERFACES

Initial Values for Dissolving-Depositing Species
The node sets the initial values for the dissolving-depositing surface concentrations
dependent variables.

This node is available as a subnode for the Internal Electrode Surface and
Electrode-Electrolyte Boundary Interface. The node is not available if no
dissolving-depositing species are present or if the Solve for dissolving-depositing species
concentrations check box is cleared in the parent node.

Non-Faradaic Reactions
Use the Non-Faradaic Reactions node to define the reaction rate for
dissolving-depositing species due to non-faradaic (not electrochemical) reactions that
occur on the boundary.

This node is available as a subnode to an Electrode Surface if there are

dissolving-depositing species present in the parent node.

Reference Electrode
The Reference Electrode node is a point feature applicable to electrolyte domains. It
defines a global electric reference potential and can be used in the Electrode Potential
node for setting the electric potential of an electrode boundary with respect to the
reference potential.

EQUILIBRIUM POTENTIAL
See Electrode Reaction for information about the settings of this section.

Electrode Potentials and Reference Electrodes

Electric Reference Potential

The Electric Reference Potential node is a point feature applicable to electrode domains.
It defines a global electric reference potential equal to the electric potential in the point

SHARED PHYSICS FEATURES IN THE CURRENT DISTRIBUTION INTERFACES | 181

 and can be used in the Electrode Potential feature for setting the electric potential of
an electrode boundary with respect to the reference potential.

Electrode Potentials and Reference Electrodes

Charge-Discharge Cycling
Use the Charge-Discharge Cycling node to specify a load cycling boundary condition in
time-dependent simulations, where the switch between charge and discharge depends
on the resulting cell voltage (or current). The node may for instance be used for
constant-current/constant-voltage (CCCV) cycling in battery simulations.

The node is applicable to external boundaries to electrode domains, and should

typically be applied on the positive electrode of the cell.

Depending on the Start Mode setting, the node will either start in Charge or Discharge
mode.

Each cycle always start with a constant Discharging/Charging current period, which ends
when the corresponding Minimum/Maximum voltage is reached (the voltage is defined
with respect to ground).

After the constant Discharging/Charging current period, you may also Include
constant voltage discharging/charging periods, which will end when the specified
Lower/Upper cut-off currents are reached. At the end of each cycle, you can also Include
rest periods, specifying the Resting time.

The node also defines a cycle counter variable (xxx.cdc1.cycle_counter, where xxx
is the physics interface tag), which may be used in postprocessing or when defining
Stop Condition in the time-dependent solver to end the simulation when a specified
number of cycles has been reached.

182 | CHAPTER 4: ELECTROCHEMISTRY INTERFACES

Note: For more complex load cycles you may use The Events Interface to set up the
cycling behavior.

For an example how to use this node, see Capacity Fade of a

Lithium-Ion Battery

The Events Interface

Circuit Terminal
This feature is only available with an AC/DC Module or a Battery Design Module
license.

Use the Circuit Terminal node to specify a coupling to the External I vs U node in the
Electrical Circuit interface.

• Connecting to Electrical Circuits

SHARED PHYSICS FEATURES IN THE CURRENT DISTRIBUTION INTERFACES | 183

 T he E le c tr o de, S h el l In t erfac e
The Electrode, Shell (els) interface ( ), found under the Electrochemistry
branch ( ) when adding a physics interface, models electric current conduction in
the tangential direction on a boundary.

The physics interface is suitable for modeling thin electrodes where the potential
variation in the normal direction to the electrode is negligible. This assumption allows
for the thin electrode domain to be replaced by a partial differential equation
formulation on the boundary. In this way the problem size can be reduced, and
potential problems with mesh anisotropy in the thin layer can be avoided.

Ohm’s law is used in combination with a charge balance to describe the conduction of
currents in the shell electrode.

When this physics interface is added, these default nodes are also added to the Model
Builder — Electrode, Electric Insulation (the default edge or point condition), and Initial
Values. Then, from the Physics toolbar, add other nodes that implement, for example,
edge or point conditions and current sources. You can also right-click Electrode, Shell
to select physics features from the context menu.

SETTINGS
The Label is the default physics interface name.

The Name is used primarily as a scope prefix for variables defined by the physics
interface. Refer to such physics interface variables in expressions using the pattern
<name>.<variable_name>. In order to distinguish between variables belonging to
different physics interfaces, the name string must be unique. Only letters, numbers, and
underscores (_) are permitted in the Name field. The first character must be a letter.

The default Name (for the first physics interface in the model) is els.

THICKNESS

For 2D components, enter a value or expression for the Out-of-plane

thickness d (SI unit: m). The default value is 1 m.

184 | CHAPTER 4: ELECTROCHEMISTRY INTERFACES

DEPENDENT VARIABLES
The dependent variable (field variable) is for the Electric potential. The name can be
changed but the names of fields and dependent variables must be unique within a
model.

DISCRETIZATION
To see all settings in this section, click the Show More Options button ( ) and select
Advanced Physics Options in the Show More Options dialog box.

• Theory for the Electrode, Shell Interface

• Boundary, Edge, Point, and Pair Nodes for the Electrode, Shell
Interface

In the COMSOL Multiphysics Reference Manual see Table 2-4 for links
to common sections and Table 2-5 to common feature nodes. You can
also search for information: press F1 to open the Help window or Ctrl+F1
to open the Documentation window.

Boundary, Edge, Point, and Pair Nodes for the Electrode, Shell
Interface
The Electrode, Shell Interfacehas these boundary, edge, point, and pair nodes, listed
in alphabetical order, available from the Physics ribbon toolbar (Windows users),
Physics context menu (Mac or Linux users), or right-click to access the context menu
(all users).

In general, to add a node, go to the Physics toolbar, no matter what

operating system you are using. Subnodes are available by clicking the
parent node and selecting it from the Attributes menu.

THE ELECTRODE, SHELL INTERFACE | 185

 These physics nodes are described in this section:

• Boundary Current Source • Electric Potential

• Current Source • External Current Density
• Electrode • Ground
• Electric Insulation • Initial Values
• Normal Current Density

These nodes are available and described for the Current Distribution interfaces, where
edges (3D components) or points (2D and 2D axisymmetric components) are selected
instead of boundaries.

• Electrode Potential
• Electric Reference Potential

For axisymmetric components, COMSOL Multiphysics takes the axial

symmetry boundaries (at r = 0) into account and automatically adds an
Axial Symmetry node to the component that is valid on the axial symmetry
boundaries only.

In the COMSOL Multiphysics Reference Manual see Table 2-4 for links
to common sections and Table 2-5 to common feature nodes. You can
also search for information: press F1 to open the Help window or Ctrl+F1
to open the Documentation window.

Electrode
The Electrode node defines the current conduction in the tangential plane. Use the
node to define the electrode thickness and electrical conductivity.

ELECTRODE
The Electrode thickness s (SI unit: m) defaults to 10−14 m.

The default Electrical conductivity σ (SI unit: S/m) uses values From material. Or select
User defined. For User defined enter values or expressions for an isotropic or anisotropic
conductivity. Select Isotropic, Diagonal, Symmetric, or Full depending on the properties

186 | CHAPTER 4: ELECTROCHEMISTRY INTERFACES

of the electrolyte. To use another type of temperature dependence than a linear
temperature relation, enter any expression for the conductivity as a function of
temperature. Then enter a value or expression in the field or matrix.

Theory for the Electrode, Shell Interface

Initial Values
The Initial Values node adds the electric potential that can serve as an initial guess for
a nonlinear solver. If more than one initial value is needed, add Initial Values nodes from
the Physics toolbar.

INITIAL VALUES
Enter values or expressions for the Electric potential (SI unit: V). The default value
is 0 V.

External Current Density

Use the External Current Density node to define the external current density.

EXTERNAL CURRENT DENSITY

Based on space dimension, enter the vector components (x, y, and z for 3D
components, x and y for 2D, or r and z for 2D axisymmetric components) of the
External current density ie (SI unit: A/m2). The defaults are 0 A/m2.

Current Source
The Current Source node adds a source term to Equation 4-7. Use this node to define
the current source.

ELECTRODE CURRENT SOURCE

Enter a value or expression for the Current source Qi (SI unit: A/m3). The default is
0 A/m3.

THE ELECTRODE, SHELL INTERFACE | 187

 Normal Current Density
The Normal Current Density node is applicable to exterior boundaries that represent
either a source or a sink of current. It sets a condition for the current density according
to:

∇T ⋅ is = in

The node can be used to couple the Electrode, Shell interface to the electrode
reactions in an Electrochemistry interface that describes the electrolyte currents in the
adjacent domain.

NORMAL CURRENT DENSITY

Enter a value for the Electrode current source in (SI unit: A/m2). The default is
0 A/m2.

Electric Insulation
The Electric Insulation node is the default edge (3D components) and point (2D and
2D axisymmetric components) condition and describes the edges of the shell
(boundary) that do not conduct electricity.

Boundary Current Source

The Boundary Current Source node is available on edges (3D components) and points
(2D and 2D axisymmetric components) and sets a condition for the current density
according to:

i s ⋅ n = i s, 0

BOUNDARY CURRENT SOURCE

Enter a value or expression for the Inward current density is,0 (SI unit: A/m2). The
default is 0 A/m2.

Ground
The Ground node is available on edges (3D components) and points (all components)
and sets the potential according to φ s = 0 .

188 | CHAPTER 4: ELECTROCHEMISTRY INTERFACES

EDGE OR POINT SELECTION

Beware that constraining the potential on edges or points in 3D or on

points in 2D usually yields a current outflow that is mesh dependent.

CONSTRAINT SETTINGS
To display this section, click the Show More Options button ( ) and select Advanced
Physics Options in the Show More Options dialog box.

Electric Potential
The Electric Potential node is available on edges (3D components) and points (all
components) and sets the potential according to φ s = φ s, 0 .

EDGE OR POINT SELECTION

Beware that constraining the potential on edges or points in 3D or on

points in 2D usually yields a current outflow that is mesh dependent.

ELECTRIC POTENTIAL
Enter the value or expression for the Electric potential φ s, 0 (SI unit: V).

CONSTRAINT SETTINGS
To display this section, click the Show More Options button ( ) and select Advanced
Physics Options in the Show More Options dialog box.

THE ELECTRODE, SHELL INTERFACE | 189

 The Electroanalysis Model Wizard
Entry
The Electroanalysis (tcd) ( ) model wizard entry, found under the Electrochemistry
branch ( ) adds a Tertiary Current Distribution, Nernst-Planck interface to the model
with the Electrolyte Charge Conservation Model set to Electroanalysis by default.

The Electroanalysis option is suitable for modeling mass transport of diluted species in
electrolytes using the diffusion-convection equation, solving for electroactive species
concentration(s).

The Tertiary Current Distribution, Nernst-Planck Interface also features options for
modeling cyclic voltammetry and electrochemical impedance spectroscopy.

Use this model wizard entry to model electroanalytical problems with electrolyte
solutions containing a large quantity of inert “supporting” electrolyte. Ohmic loss is
assumed to be negligible.

The model wizard entry is available in 1D, 2D, and 3D as well as for axisymmetric
components in 1D and 2D.

The default dependent variables are the molar concentrations, c1 and c2, of the two
electroactive species in a redox couple and the electric potential, phis, which is solved
for either in the Electrode or Porous Electrode domain feature.

• The Tertiary Current Distribution, Nernst-Planck Interface

• Introduction to Electrochemistry Modeling
• Theory for Electroanalysis

190 | CHAPTER 4: ELECTROCHEMISTRY INTERFACES

Theory for the Current Distribution
Interfaces
In this section:

• The Nernst-Planck Equations

• Domain Equations for Primary and Secondary Current Distributions
• Electrochemical Reactions and the Difference Between a Primary and a Secondary
Current Distribution
• Domain Equations for Tertiary Current Distributions Using the Nernst-Planck
Equations and Electroneutrality
• Mass Fluxes and Sources Due to Electrochemical Reactions
• Deposition-Dissolution Rates, Growth Velocities, and Thicknesses on an Electrode
Surface
• Stoichiometric Coefficients for Double Layer Capacitive Charging
• Film Resistance
• Electrode Kinetics Expressions
• Theory for Specific Current Distribution Feature Nodes

This theory is also relevant to the Current Distribution on Edges, BEM

interface. However, due to the use of BEM, current source terms in the
electrolyte, and porous electrodes, cannot be used in this interface.

The Nernst-Planck Equations

The general mass balance for the diluted species in an electrolyte is described by the
following equations for each species i:

∂c i
+ ∇ ⋅ N i = R i, tot
∂t

where Ni is the total flux of species i (SI unit: mol/(m2·s)). The flux in an electrolyte
is described by the Nernst-Planck equations and accounts for the flux of charged solute

THEORY FOR THE CURRENT DISTRIBUTION INTERFACES | 191

 species (ions) by diffusion, migration, and convection; these are respectively the first,
second, and third term on right side in the equation below.

N i = – D i ∇c i – z i u m, i Fc i ∇φ l + c i u = J i + c i u

where

• ci represents the concentration of the ion i (SI unit: mol/m3),

• zi its valence,
• Di the diffusion coefficient (SI unit: m2/s),
• um,i its mobility (SI unit: s·mol/kg),
• F denotes the Faraday constant (SI unit: C/mol),
• φ l the electrolyte potential,
• u is, the velocity vector (SI unit: m/s), and
• Ji denotes the molar flux relative to the convective transport.

J i = – D i ∇c i – z i u m, i Fc i ∇φ l (4-2)

The net current density can be described using the sum of all species fluxes:

il = F  zi Ni
where il denotes the current density vector (SI unit: A/m2) in the electrolyte.

Domain Equations for Primary and Secondary Current

Distributions
Assuming electroneutrality (which cancels out the convection term) and negligible
concentration gradients of the current-carrying ion (which cancels out the diffusion
term), the following expression is left for the current density vector in an electrolyte:

 zi um, i ci ∇φl .
2 2
il = –F

Further, assuming approximately constant composition of charge carriers, we can

define a constant electrolyte conductivity as:

 z i u m, i c i
2 2
σl = F

the current density in the electrolyte can be written as

192 | CHAPTER 4: ELECTROCHEMISTRY INTERFACES

 i l = – σ l ∇φ l

This equation takes the same form as Ohm’s law; in an electrolyte, charge transport is
ohmic, subject to the above assumptions.

Conservation of charge yields the domain equation usually used for the electrolyte in
the Primary and Secondary Current Distribution interfaces:

∇ ⋅ il = 0

In a pore electrolyte, the homogenization used in porous electrode

theory introduces a source or sink term in the pore electrolyte current
balances due to the charge transfer reactions at the electrode-electrolyte
interface within the porous material. In such cases, a source term, Ql, is
introduced on the right-hand side of the equation above.

The Primary and Secondary Current Distribution interfaces define two dependent
variables: one for the potential in the electrolyte and one for the electric potential in
the electrode. The conduction of current in the electrolyte is assumed to take place
through transport of ions as described above, while electrons conduct the current in
the electrode.

Since Ohm’s law is also used for current conduction in the solid electrode phase, the
general equation in these interfaces is according to the following:

∇ ⋅ ik = Qk

with

i k = – σ k ∇φ k

where Qk denotes a general source term, k denotes an index that is l for the electrolyte
or s for the electrode, σk denotes the conductivity (SI unit: S/m) and φ k the potential
(SI unit: V).

Electrochemical Reactions and the Difference Between a Primary and

a Secondary Current Distribution
Both the primary and secondary current distribution models assume an electrolyte that
conducts current according to Ohm's law, with a constant conductivity. The difference
between a primary and a secondary current distribution lies in the description of the

THEORY FOR THE CURRENT DISTRIBUTION INTERFACES | 193

 electrochemical charge transfer reaction at the interface between an electrolyte and
an electrode. The charge transfer reactions can be defined as boundary conditions, or
as sources or sinks in a domain for the case of porous electrodes.

The rate of the electrochemical reactions can be described by relating the reaction rate
to the activation overpotential. For an electrode reaction, with index m, the activation
overpotential, denoted ηm, is the following:

η m = φ s – φ l – E eq, m

where Eeq,m denotes the equilibrium potential (also known as a reduction potential)
for reaction m.

In the Primary Current Distribution interface, the electrochemical reactions are

assumed to be fast enough that their kinetics have negligible influence on the cell
voltage. Consequently, the activation overpotential, ηm, in this physics interface is
equal to zero, and the difference in potential between the electrode and the electrolyte
is always equal to the equilibrium potential, Eeq, m. This condition is implemented as
the following constraint on boundaries between electrodes and electrolyte domains:

φ l = φ s – E eq, m

A good modeling practice is to estimate the influence of finite reaction

kinetics on the cell voltage and to compare the associated activation losses
to the ohmic losses in a cell to check the validity of the primary current
distribution assumption.

In the Secondary Current Distribution interface, the electrochemical reactions are

described as a function of the overpotential. The physics interface uses several relations
for the charge transfer current density and the overpotential, such as Butler-Volmer
and Tafel expressions. The most general expression is of Butler-Volmer type:

α a Fη – α c Fη
i loc,m = i 0  exp  --------------- – exp  ----------------- 
RT RT

194 | CHAPTER 4: ELECTROCHEMISTRY INTERFACES

where iloc,m denotes the local charge transfer current density for reaction m, i 0 the
exchange current density, αa the anodic transfer coefficient, αc the cathodic charge
transfer coefficient, F Faraday’s constant, and R the universal gas constant.

Both the exchange current density and the overpotential are typically
concentration dependent. It is possible include the dependence of
kinetics on concentration in the expression above. It also possible to use
other kinetics expressions.

See Equilibrium Potentials and the Nernst Equation and Electrode

Kinetics Expressions.

The sum of all electrode reaction currents is implemented as a current density

condition on the boundary between an electrode and an electrolyte domain according
to:

il ⋅ n =  iloc, m
m

is ⋅ n = –  iloc, m
m

Both the Primary Current Distribution and Secondary Current Density Distribution
interfaces allow for a domain definition for porous electrodes. For the Primary Current
Distribution interface, the same constraint as above is applied.

In porous electrodes for the Secondary Current Distribution interface, the sum of all
reaction currents appears as a source in the domain equations:

∇ ⋅ il =  Av, m iloc, m
m

∇ ⋅ is = –  Av, m iloc, m
m

where Av,m is the surface area.

The only reason to add Porous Electrode descriptions to the Primary

Current Distribution interface is to be able to expand a model to include
charge transfer resistance.

THEORY FOR THE CURRENT DISTRIBUTION INTERFACES | 195

 Domain Equations for Tertiary Current Distributions Using the
Nernst-Planck Equations and Electroneutrality
The domain equations can be derived by starting with The Nernst-Planck Equations.
The material balance equation for the species i in the electrolyte is given by the
continuity equation, with a flux given by the Nernst-Planck equation:

∂c i
+ ∇ ⋅ ( J i + c i u ) = R i, tot
∂t

where

• ci denotes the concentration of species i (SI unit: mol/ m3),

• u is, the velocity vector (SI unit: m/s), and
• Ji denotes the molar flux relative to the convective transport(see Equation 4-2)

The current balance includes the sum of the flux of all charged species, which yields
the current density in the electrolyte:

n n

il = F  zi ( –Di ∇ci – zi um, i F ci ∇φl ) = F  zi Ji

i=1 i=1

The concentration gradients are not assumed to be negligible here, and

so the contribution of ion diffusion to overall current density can be
nonzero. (Compare with the Domain Equations for Primary and
Secondary Current Distributions.)

In the equations above, il denotes the current density vector in the electrolyte. The
current balance in the electrolyte then becomes:

∇ ⋅ il = Ql

where Ql can here be any source or sink. (Ql is typically nonzero for porous
electrodes). The current balance and the material balances give one equation per
unknown species concentration. However, there is still one more unknown, the
electrolyte potential, which requires an additional equation. This equation is the
electroneutrality condition, which follows from dimensional analysis of Gauss’s law. In
a typical electrolyte solution, it is accurate over lengths greater than a few nanometers:

196 | CHAPTER 4: ELECTROCHEMISTRY INTERFACES

  zi ci = 0

These formulations are also valid for the pore electrolyte in porous electrodes, except
for the transport properties that have to be corrected for porosity and tortuosity. In
such cases, the source or sink, Ql, denotes the charge transfer reactions in the porous
electrode and/or the non-Faradaic source or sink due to double layer charge and
discharge.

The charge transfer reaction can be parameterized by arbitrary functions of the

concentrations of the species in the redox couple and the local electric and electrolyte
potentials. The most common way to describe the reaction kinetics is to use a
Butler-Volmer expression for the charge transfer current density. See The
Butler-Volmer Equation.

In the current balance in a porous electrode, the local current density multiplied by the
specific surface area of an electrode gives a contribution to the source or sink, Ql, due
to electrochemical reactions.

Mass Fluxes and Sources Due to Electrochemical Reactions

When relating the species fluxes at an electrode surface to the electrical currents, the
general electrochemical reaction formula:

 νox Sox + ne  νred Sred

-
⇔
ox red

is used to define the stoichiometric coefficients, νi, with νi being positive (νred) for
products and negative (νox) for the reactants in a reduction reaction. The number of
participating electrons, n, is always positive.

The molar species fluxes, Ni (SI unit: mol/(m2·s)), perpendicular to an

electrode-electrolyte interface are calculated by summing all the flux contributions
from the electrode reactions of index m, according to Faraday’s laws:

ν i, m i loc, m
Ni =  --------------------------
nm F
-
m

where iloc, m is the local current density (SI unit: A/m2) of the electrochemical
reaction, nm the number of participating electrons and F (SI unit: C/mol) is the

THEORY FOR THE CURRENT DISTRIBUTION INTERFACES | 197

 Faraday constant. Note that iloc, m denotes the current density perpendicular to the
electrode surface.

The molar species flux, Ni, is obtained from the normal component of the molar
species flux vector over the electrode-electrolyte interface:

Ni = Ni ⋅ n

where n is the normal vector of the boundary pointing into the domain.

For a porous electrode, the electrochemical reactions result in species source terms
calculated from:

ν i, m i loc, m
R i, molar = –  av, m --------------------------
nm F
-
m

where av,m (SI unit: m2/m3) is the specific surface area.

Deposition-Dissolution Rates, Growth Velocities, and Thicknesses on

an Electrode Surface
The rate of dissolution or deposition on due to an electrode reaction is defined based
on the reaction stoichiometry, νi,m, and the local current density, iloc,m, as described
in Mass Fluxes and Sources Due to Electrochemical Reactions.

If the reaction rate is known, the total growth vdep, tot (m/s) is defined as the sum of
the velocity contributions for all species and electrode reactions according to:

Mi ν i, m i loc, m
v dep, tot =  ------
ρi  nm F
- -------------------------- (4-3)
i m

Where Mi (SI unit: kg/mol) is the molar mass and ρi (SI unit: kg/m3) the density of
the species. (i is the species index, and m the index of the electrode reaction).

This velocity may be used in deforming geometry models as a boundary condition for
the geometry deformation by assuming that dissolution or deposition always occurs in
the normal direction to an electrode boundary, with the velocity being directed into
the electrolyte domain:

∂x
⋅ n = v dep, tot
∂t

198 | CHAPTER 4: ELECTROCHEMISTRY INTERFACES

In a time-dependent simulation one may also introduce a surface concentration
variable, cs,i (mol/m2) on the boundary and calculate the accumulated surface
concentration change by using a local ordinary differential equation (ODE):

dc s, i ν i, m i loc, m
dt
=  -------------------------
nm F
-
m

The total deposited thickness stot(m) can then be defined as

Mi
s tot =  ------
-c .
ρ i s, i
i

Stoichiometric Coefficients for Double Layer Capacitive Charging

A negative capacitive current corresponds to the accumulation of negative charge on
the electrode surface, and a corresponding counterbalanced positive charge
accumulating in the double layer. This can be understood in terms of conservation of
current: cathodic capacitive current at the electrode corresponds to the overall
injection of negative charge (from the double layer) into the electrolyte, just as a
cathodic Faradaic current would add negative charge to the electrolyte through
electron transfer.

Consider an overall reaction as:

- + -
2e (electrical circuit) + A (solution) + X (double layer)

- + -
2e (electrode surface) + A (double layer) + X (solution)

This corresponds to a negative charge of 2F being moved from double layer to

solution. Following the convention that the reaction is written in the order of cathodic
current (as above), then with respect to the free solution species, the cation is a reactant
(negative stoichiometry) and the anion is a product (positive stoichiometry). This
suggests νA = −1, νX = +1, and n = 2 for an ideal double layer where both anion and
cation have similar contributions to the double layer charge.

Film Resistance
If a resistive film forms on the interface between an electrode and an electrolyte, this
results in additional potential losses. To model a film resistance, an extra dependent

THEORY FOR THE CURRENT DISTRIBUTION INTERFACES | 199

 variable for the potential drop over the film, Δ φ s,film, is introduced. The governing
equation is:

Δφ s, film = i tot R film

Where Rfilm (SI unit: ohm·m2) is a generalized film resistance and itot the sum of all
currents over the interface. The activation overpotentials, ηm, for all occurring
electrode reactions on the electrode with the film receive an extra potential
contribution due to the film resistance according to:

η m = φ s – Δφ s, film – φ l – E 0, m

If the thickness and conductivity of the film are known, the resistance can be written as:

s 0 + Δs
R film = ------------------
σ film

where s0 is the reference/initial film thickness, Δs the electrode thickness change, and
σfilm the conductivity (SI unit: S/m) of the film.

Equilibrium Potentials and the Nernst Equation

Consider an arbitrary, possibly multi-electron step, redox reaction involving a number
of species Si defined as

 
-
ν i S i + ne ↔ νi Si
i:ν i < 0 i:ν i > 0

where νi is the stoichiometric coefficient of the reacting species of index i and n is the
number of participating electrons.

The equilibrium potential of the electrode reaction, Eeq (V), is the electrode potential
(the difference between the electrode phase and electrolyte phase potentials, φ s – φ l )
for which the net reaction rate (and the local current density, iloc) is zero.

The equilibrium potential is directly related to the change of Gibbs free energy of the
reacting species, ΔG, as

ΔG
E eq = – --------
nF

200 | CHAPTER 4: ELECTROCHEMISTRY INTERFACES

Since the free energy of the reacting species is concentration dependent, also the
equilibrium potential is concentration (activity) dependent. Eeq is usually defined
according to the Nernst equation as

ai νi
∏  ------------
RT
E eq = E eq, ref – -------- ln
nF a i, ref
i

where Eeq, ref (V) is the equilibrium potential for a reference state for which all species
activities ai (unitless) are equal to a chosen set of reference activities ai, ref (unitless).

For ideal solutions, the activities are replaced by concentrations. Standard conditions
correspond to reference concentrations of 1M for soluble species in the electrolyte,
partial pressures of 1 atm for gaseous species. Constant activities of 1 is used for solid
(metal) species and solvents.

Electrode Kinetics Expressions

A number of different analytical expressions for the current density perpendicular to
the electrode surface, iloc,m, are available. In the following paragraphs, the index m is
dropped. All parameters are understood to refer to a specific reaction.

THE EQUILIBRIUM POTENTIAL AND THE OVERPOTENTIAL

The rate of the electrochemical reactions can be described by relating the reaction rate
to the activation overpotential. For an electrode reaction, the activation overpotential,
denoted η (V), is the following:

η = φ s – φ l – E eq

where Eeq denotes the equilibrium potential.

THE BUTLER-VOLMER EQUATION

A common expression for the current density as a function of the activation
overpotential, in modeling of electrochemical systems, is the Butler-Volmer equation:

α a Fη – α c Fη
i loc = i 0  exp  --------------- – exp  ----------------- 
  RT   RT  

where αc (unitless) denotes the cathodic charge transfer coefficient, αa (unitless) the
anodic charge transfer coefficient, and i0 (SI unit: A/m2) is the exchange current
density.

THEORY FOR THE CURRENT DISTRIBUTION INTERFACES | 201

 It should be noted that, although used extensively for all sorts of reactions in the
electrochemical community, the Butler-Volmer equation was originally derived for
single-electron transfer reactions (for instance implying that the reaction does not
involve the breaking or creation of a chemical bond).

Concentration Dependence and the Exchange Current Density

The exchange current density is generally concentration dependent. For certain
conditions, it is possible to derive analytical expressions for i0. Assuming a
concentration dependent equilibrium potential defined by the Nernst equation (see
previous section Equilibrium Potentials and the Nernst Equation), the kinetics to
follow the law of mass action, and the condition that αa + αc = n, then the exchange
current density becomes as follows:

αc νi –αa ν i
---------
- --------------
ai 
 ------------
n ai 
 ------------
n
i 0 = i 0, ref   a i, ref   a i, ref
i:ν i > 0 i:ν i < 0

where i0, ref is the exchange current density (SI unit: A/m2) at the reference state. The
above expression can be derived from the mass action law, which gives the following
expression for the local current density:

 ai  νi
 ------------ α a Fη ref a i  –ν i – α c Fη ref 
- exp  --------------------  ------------ exp  ----------------------- 
i loc = i 0, ref 
   a i, ref  RT 
- –
  a i, ref
-
 RT  
i:ν i > 0 i:ν i < 0

where the overpotential ηref (SI unit: V) is measured using relative to a reference state,
which yields:

η ref = φ s – φ l – E eq, ref .

This latter form of the Butler-Volmer equation, where the concentration overpotential
and the exchange current density are related to the same reference state, is less error
prone and preferable in a modeling context.

The law of mass action is not always the most practical way for treating complex
reactions involving multiple electron steps. For certain multi-electron reactions, where
one electron transfer step is rate limiting, it is possible to derive a lumped
Butler-Volmer expressions using the following relation for the exchange current
density (see Ref. 1):

ai γi
i 0 = i 0, ref   ------------
a i, ref
-
i

202 | CHAPTER 4: ELECTROCHEMISTRY INTERFACES

where γi are generic exponential coefficients. For this case, αa and αc may be
independently defined. By rearranging the Butler-Volmer expression using ηref
similarly to what was done for the mass action law case above, the γi coefficients relate
to the anodic, ξa,i, or cathodic, ξc,i, reaction orders according to

αa νi
ξ a, i = γ i + -----------
n

and

αc νi
ξ c, i = γ i – ----------- .
n

Exchange Current Density and Rate Constants

In electroanalysis, one commonly defines electrode kinetics in terms of rate constants
rather than exchange current densities.

For instance, for a one electron redox couple of concentrations co and cr, with the same
reference concentration cref for both species, and i0, ref = k0Fcref, the mass action law
expression above can be rewritten as

α a Fη – α c Fη
i loc = k 0 F  c r exp  --------------- – c o exp  ----------------- 
RT RT

where k0 (m/s) is the heterogeneous rate constant.

Generic Concentration Dependent Butler-Volmer Type Kinetics

This expression type gives more freedom for the user to define concentration
dependent Butler-Volmer types of expressions, where the anodic and cathodic terms
of the current density expression, typically depending on the local concentrations of
the electroactive species at the electrode surface, may be individually defined:

α a Fη – α c Fη
i loc = i 0  C R exp  --------------- – C O exp  ----------------- 
RT RT

Here CR and CO are dimensionless expressions, describing the dependence on the

reduced and oxidized species in the reaction. Note that if CO ≠ CR when η = 0, this
kinetics expression results in iloc ≠ 0, thus violating the concept of equilibrium. This
may result in thermodynamical inconsistencies, for instance when coupling an
electrochemical model to heat transfer.

THEORY FOR THE CURRENT DISTRIBUTION INTERFACES | 203

 SIMPLIFICATIONS OF THE BUTLER-VOLMER EQUATION

Linearized Butler-Volmer
The charge transfer reaction can be expressed by a linearized Butler-Volmer expression,
which can be used for small overpotentials (η << RT/F) and is usually referred to as
the low-field approximation. This approximation gives the following linearized
equation:

( α a + α c )F
i loc = i 0  ---------------------------- η
 RT 

Anodic and Cathodic Tafel Equations

By assuming either high anodic or cathodic overpotentials for a given current (that is,
slow kinetics or low i0), one of the terms in the original Butler-Volmer potentials can
be neglected.

The anodic Tafel equation is implemented as follows:

η ⁄ Aa
i loc = i 0 ⋅ 10

where Aa (SI unit: V) is the so-called Tafel slope. Aa relates to the corresponding
transfer coefficient as follows

RT ln 10
A a = ----------------------
αa F

The cathodic Tafel expression is defined according to:

η ⁄ Ac
i loc = – i 0 ⋅ 10

where the sign accounts for the negative cathodic charge transfer current. Here, Ac is
required to be negative and relates to the transfer coefficient according to

RT ln 10
A c = – ----------------------
αc F

LIMITING CURRENT DENSITY

The steady-state rate of electrode reactions can never exceed the rate at which reactants
and products can be transported to and from the electrode surface. When explicitly
including mass transport in a model, this dependence is typically described in

204 | CHAPTER 4: ELECTROCHEMISTRY INTERFACES

concentration dependence of the equilibrium potential and the exchange current
density as described above.

When not explicitly including mass transfer in the domain equations one can still
include the effect of transport limitations by the assumption of a Nernst diffusion layer
at the electrode surface, and a first order dependence between the charge transfer
current and the local concentration of a reacting species, resulting in the following
kinetics expression:

i expr
i loc = --------------------------
i expr
1 + -----------
i lim

where iexpr (A/m2) is the current density expression in the absence of mass transport
limitations for the species, and ilim (A/m2) is the limiting current density that
corresponds to the maximum transport rate of the species. The derivation of this
expression assumes high overpotentials so that either the anodic or an cathodic term
in the Butler-Volmer equation may be neglected.

LINEARIZE CONCENTRATION DEPENDENCE FOR LOW CONENTRATIONS

Consider a concentration-based kinetic expression

dc ν
= r = – kc
dt

where ν and k are positive numbers and the desired behavior is that the rate r and the
concentration c should equal zero in the converged solution at infinite time. However,
if c, due to numerical fluctuations in the solver process, becomes negative during
iterating, issues may arise.

First consider the case when ν equals 1 (or any odd positive integer). Negative values
of c will then cause the rate to become positive, resulting in a “self stabilizing” situation
where c will be approaching 0 with time.

A second case to consider is when ν is an even integer larger than 1. The rate then will
become increasingly negative for negative values of c, resulting in an “exploding”
solution, iterating c towards minus infinity. The standard solution for these cases,
which also works for non-integer ν's larger than 1, is to change the expression c in the
rate term to max(c,eps), where eps is a small number. This will avoid the “exploding”
behavior, but result in poor convergence rate for negative c values since the Jacobian
of the rate with respect to c then becomes zero for negative c's.

THEORY FOR THE CURRENT DISTRIBUTION INTERFACES | 205

 The third case is when ν is a non-integer between 0 and 1. Note now that Jacobian
with respect to c of the rate expression now contains cν−1, which will approach minus
infinity when c approaches zero from the positive side. This may result in poor
convergence, and the max() wrapping will not improve convergence in this case.

The solution for the third case is to linearize the concentration dependence for low
concentrations, i.e., to use

ν
r = – kc c > c lim

υ–1
r = – kcc lim c < = c lim

which results in the desired convergence behavior for low and negative concentrations.
Note however that the linearization may result in thermodynamic inconsistencies so
that, for instance, relations like the Nernst equation for the equilibrium potential are
no longer fulfilled. The linearization may also improve convergence of the second case
above.

Theory for Specific Current Distribution Feature Nodes

ELECTROLYTE THEORY
The Electrolyte node defines a current balance in the electrolyte. The domain equation
is:

∇ ⋅ il = 0

where il denotes the current density vector. In free electrolyte, there is no source or
sink of charge.

The definition of the current density vector depends on the equation formulation of
the electrolyte charge transport, as discussed above in Domain Equations for Primary
and Secondary Current Distributions and Domain Equations for Tertiary Current
Distributions Using the Nernst-Planck Equations and Electroneutrality.

• For the Primary and Secondary Current Distribution interfaces, see

Electrolyte.
• For the Tertiary Current Distribution, Nernst-Planck interface, see
Electrolyte.

206 | CHAPTER 4: ELECTROCHEMISTRY INTERFACES

POROUS ELECTRODE THEORY
A porous electrode is a mixed material with one electrode phase and one electrolyte
phase. (A special case of a porous electrode is the gas diffusion electrode, as found in
a fuel cell. These contain a gas pore phase which is inert to charge transfer.) To model
a porous electrode we define two separate current balances according to the following
equations:

∇ ⋅ i l = Q l and ∇ ⋅ i s = Q s

In these equations, il denotes the current density vector in the electrolyte, as discussed
above in Domain Equations for Primary and Secondary Current Distributions and
Domain Equations for Tertiary Current Distributions Using the Nernst-Planck
Equations and Electroneutrality.

In addition to the current balances, it is necessary to also formulate mass balance

equations for the species in the electrolyte phase for the tertiary case.

It is also common to used corrected conductivities and diffusion parameter values in a

porous electrode to account for the lowered volume fraction of the conducting phase,
and the longer transport distance due to the tortuosity of the pores.

The current balances in the pore electrolyte and in the electrode matrix contain sources
and sinks according to the charge transfer reactions that take place in the electrode
catalyst. For example, if only one charge transfer reaction takes place in the porous
electrode, the domain equations are the following:

∇ ⋅ i l = A v i loc
∇ ⋅ i s = – A v i loc

where Av denotes the specific surface area (dimension L2/L3), and iloc the local
current density defines the rate of the charge transfer reactions, for instance according
to the Butler-Volmer equation. For various ways of defining iloc see Electrode Kinetics
Expressions.

If the porous electrode is a cathode, then the charge transfer reaction is a source for
the current balance in the electrode, because it receives current from the pore
electrolyte. The charge transfer reaction is then a sink for the current balance in the
pore electrolyte, because the current is transferred from the pore electrolyte to the
electrode in a cathodic reaction.

The corresponding sources and sinks in the current balances that are due to the charge
transfer reactions are also coupled to the material balances for the charged species. This

THEORY FOR THE CURRENT DISTRIBUTION INTERFACES | 207

 means that the local current density expression above is also included in the material
balances as a reaction term, Ri, by using Faraday’s laws for each of the species that take
part in charge transfer reactions.

• For the Primary and Secondary Current Distribution interfaces, see

Porous Electrode.
• For the Tertiary Current Distribution, Nernst-Planck interface, see
Porous Electrode.

ELECTRODE REACTIONS THEORY

Charge transfer reactions occurring at an interface between an electrode and an
electrolyte domain gives rise to a normal current flux that equals the sum of all reaction
currents according to

il ⋅ n =  iloc, m
m

is ⋅ n = –  iloc, m
m
where iloc,m (A/m2) is the Electrode Reaction current density of the charge transfer
electrode reaction of index m, il the current density vector in the electrolyte and is the
current density vector in the electrode.

POROUS ELECTRODE REACTIONS THEORY

For a porous electrode, the electrode reaction current densities are multiplied by the
surface area to yield a source or sink in the current balance domain equation according
to:

∇ ⋅ il =  Av iloc, m
m

∇ ⋅ is = –  Av iloc, m
m

where Av is the specific surface area of the electrocatalyst.

Porous Electrode Reaction

208 | CHAPTER 4: ELECTROCHEMISTRY INTERFACES

ELECTRODE THEORY
Electron conduction in an Electrode is modeled using Ohm’s law. The domain
equation is the following:

∇ ⋅ is = 0

where is denotes the current density vector according to:

i s = – σ s ∇φ s

and where σs denotes the electrical conductivity and φ s the potential of the electron
conducting (metal) phase.

ELECTROLYTE CURRENT DENSITY THEORY

An applied current density can be defined as its component perpendicular to the
boundary according to:

i l ⋅ n = i n, l

The current density can also be defined including all its components:

i l = i l, bnd

where il, bnd is a given expression for the current density vector.

Electrolyte Current Density

ELECTROLYTE CURRENT THEORY

The Electrode Current boundary condition sets the total current at a given position in
the electrolyte without imposing a current density distribution. The conditions yields
a constant electrolyte potential, along the given boundary, that satisfies the total value
of the current. The boundary condition is a good choice in the middle of a cell with
planar electrodes, where the isopotential level can be a plane (or close to a plane in 3D,
or line in 2D) but where the current density distribution is unknown.

The feature adds one unknown variable, the electrolyte potential, φ l, bnd, along the
boundary. It then adds one additional equation for the total current, which is an
integral over the boundary:

THEORY FOR THE CURRENT DISTRIBUTION INTERFACES | 209

  i l ⋅ n ds = I n, l
∂Ω

The average current density condition imposes the same equation but multiplies the
current density by the area of the boundary to obtain the value of the total current In, l.

ELECTRODE CURRENT THEORY

The Electrode Current adds one unknown variable, the electric potential, φ s, bnd,
along the boundary. It then adds one additional equation for the total current, which
is an integral over the boundary:

 i s ⋅ n ds = I n, s
∂Ω

where

i s = – σ s ∇φ s

and σs denotes the electrode conductivity and φ s the electric potential. The average
current density condition imposes the same equation but multiplies the current density
by the area of the boundary to obtain the value of the total current, In,s.

SYMMETRY THEORY
The Symmetry boundary condition, in the Primary Current Distribution and
Secondary Current Distribution interfaces is identical to the Insulation condition and
is expressed according to the equation below.

ik ⋅ n = 0

where ik denotes the current density vector and k = l, s is an index for the electrolyte
and electrode, respectively.

The Symmetry boundary condition for the Tertiary Current Distribution,

Nernst-Planck interface imposes a no-flux condition for the molar flux of species at a
boundary. The condition is expressed as follows:

Ji ⋅ n = 0

ELECTRODE CURRENT DENSITY THEORY

An applied Electrode Current Density can be defined as its component perpendicular
to the boundary according to:

210 | CHAPTER 4: ELECTROCHEMISTRY INTERFACES

 i s ⋅ n = i n, s

where

i s = – σ s ∇φ s

and σs denotes the electrode conductivity and φ s the electric potential.

The current density can also be defined including all its components:

i s = i s, bnd

where is, bnd is a given expression for the current density vector.

ELECTRODE POWER THEORY

The Electrode Power boundary condition is used to specify either the total electrode
power or the average electrode power density drawn from or inserted into an
electrochemical cell at an electrode boundary.

For a total power condition, the boundary electric potential of an electrode is set to a
potential φ s, bnd, defined by the condition for the total power on the boundary ∂Ω
according to:

φ s = φ s, bnd on ∂Ω

 ( φs, bnd – φs, ground ) ( is ⋅ n ) dS = Ptotal

∂Ω

where φ s, ground is the ground potential of the cell, and Ptotal (W) is the power to be
drawn.

For an average power condition, Ptotal is calculated by:

P total = P avg A

where Pavg is the average power density on the boundary, and A is the boundary area.

For a galvanic cell, such as a battery during discharge or a fuel cell, there
is a maximum power level, beyond which a further current increase causes
a lowered output power due to increasing voltage losses. A result of this
is that there can be two existing solutions for the same power setting. In
these cases the choice of initial values determines the final solution.

THEORY FOR THE CURRENT DISTRIBUTION INTERFACES | 211

 Electrode Power

ION EXCHANGE MEMBRANE THEORY

Ion-exchange membranes typically contain a polymer matrix with a number of fixed
ionic groups.

Since these charges are fixed, there is no need to explicitly model the transport of these
charges, but when calculating the sum of charges, used in the Nernst-Planck (with
electroneutrality) or the Nernst-Planck-Poisson set of equations, one need to add this
fixed space charge.

For Nernst Planck with electroneutrality, the electroneutrality condition reads

ρ fix + F  zi ci = 0

For the Nernst-Planck-Poisson case, the total space charge density becomes

ρ v = ρ fix + F  zi ci
ION EXCHANGE MEMBRANE BOUNDARY THEORY
The electrochemical potential μi of a charged species of index i is

μ i = RT ln a i + φ l z i F

where T(K) is the temperature, R (mol/(J K)) the molar gas constant, ai is the species
activity, φ l is the electrolyte potential, zi the species charge, and F(C/mol) is Faraday's
constant.

At equilibrium the electrochemical potentials on each side of the free electrolyte -

ion-exchange membrane interface are equal.

Setting the species activity to equal the concentration and denoting the liquid
electrolyte phase and a ion-exchange membrane phases as 1 and 2, respectively, the
Donnan potential, Δφ (V), describes the relation between the concentration of a
species, ci (mol/m3), at each side of the boundary and the electrolyte potentials:

c i, 1
Δφ l = φ l, 1 – φ l, 2 = – -------- ln  ---------
RT
zi F  c i, 2

which may be rearranged to

212 | CHAPTER 4: ELECTROCHEMISTRY INTERFACES

 z i F ( φ l, 1 – φ l, 2 )
c i, 2 = c i, 2 exp  – ---------------------------------------
 RT 

The molar flux of each species in the liquid electrolyte is continuous over the
membrane-liquid interface

n ⋅ J i, 1 = n ⋅ J i, 2

Since the total current density is the sum of all species fluxes, times the individual
species charges, the current densities Il in the normal direction n of the
membrane-liquid interface boundary is also continuous:

n ⋅ I l, 1 = n ⋅ I l, 2

References
1. J. O’M. Bockris, A.K.N. Reddy, and M. Gamboa-Aldeco, Modern Electrochemistry,
vol. 2A, 2nd ed., ch. 7, sec. 7.6, Kluwer Academic/Plenum Press, New York, 2000.

THEORY FOR THE CURRENT DISTRIBUTION INTERFACES | 213

 Theory for Electrochemical Heat
Sources
Irreversible voltage losses in an electrochemical cell can occur due to the following
phenomena:

• Charge transport in the electrolyte (Joule heating)

• Charge transport in the solid conductor materials (Joule heating)
• Activation overpotentials in the electrode reactions
• Heat of mixing

In addition, reversible heat sources and sinks can appear due to the entropy changes in
the electrode reactions.

Most Electrochemistry interfaces define and announce heat source variables that for
instance can be used by the General Source and the Boundary Heat source nodes in
the Heat Transfer interfaces.

An alternative way to couple an electrochemical interface to a heat transfer interface is

by the use of the Multiphysics nodes that become available in the model builder tree if
there is both a Heat Transfer interface and an Electrochemistry interface available in
the same component.

The Electrochemical Heating multiphysics node defines a domain heat source in the
heat transfer interface, based on the sum of irreversible (Joule heating and activation
losses) and reversible heat in the electrochemistry interface.

You can also use the heat source variables defined by the electrochemistry interfaces
when setting up manual heat couplings between different components in a model. For
instance if you are using a 1D electrochemical cell model to calculate an average heat
source in a 3D heat transfer model. The names of the heat source variables are [Link]
(domain, Joule heating and porous electrode reactions) and [Link] (boundary,
electrode surface reactions), where xxx is the electrochemistry interface identifier.

• Electrochemistry Interfaces
• Multiphysics Coupling Nodes

214 | CHAPTER 4: ELECTROCHEMISTRY INTERFACES

Joule Heating Due to Charge Transport
The charge transport in the solid conductor material and electrolyte create joule
heating source terms according to

Q JH = – ( i s ⋅ ∇φ s + i l ⋅ ∇φ l ) (4-4)

Heating Due to Electrochemical Reactions

For an electrochemical reaction process one can write the total heat balance as:

• Heat generated = Total reaction enthalpy – Electrical energy leaving the system
Using Faraday’s law for an electrode reaction, m, at the interface between the electron
and ion conducting phase this corresponds to

ΔH m ΔG m
Q m =  ------------- –  ------------- – η m, tot  i m (4-5)
nm F nm F

where ΔHm is the enthalpy change of the reaction, and ΔGm is the Gibbs free energy
of the reaction, ΔGm, defined as

ΔG m = ΔH m – TΔS m

where ΔSm is the net entropy change. Equation 4-5 may now be rearranged into

TΔS m
Q m =  η m, tot + ---------------- i m (4-6)
 nm F 

where the first term represents the irreversible activation losses, and the second term
is the reversible heat change due to the net change of entropy in the conversion
process.

In Equation 4-5 we have used the total overpotential, ηm,tot,(including potential

effects from film resistances and similar), defined as

η m, tot = φ s – φ l – E eq, m

The equilibrium potential is related to ΔGm in the following way:

ΔG m
E eq, m = – -------------
nm F

THEORY FOR ELECTROCHEMICAL HEAT SOURCES | 215

 By the relation between the temperature derivative of the equilibrium potential and the
entropy:

∂E eq, m ΔS m
------------------
- = -----------
-
∂T nm F

the local heat source due to the electrochemical conversion process becomes

∂E eq, m
Q m =  η m, tot + T ------------------- i m
 ∂T 

Alternatively, by defining the thermoneutral voltage of the reaction as

ΔH m
E therm, m = – -------------
nm F

one may also define the heat source as

Q m = ( η m, tot + ( E eq, m – E therm, m ) )i m

The total heat source due to the electrochemical reactions, QEC, for an electrode
surface is the sum of all individual heat sources of the electrode reactions according to

Q EC =  Qm
m

For a porous electrode joule heating and electrochemical sources are summed up for a
total heat source in the domain according to

Q TOT, p =  av, m Qm + QJH

m

Heating Due to Heat of Mixing

If the enthalpy varies with the local concentration of the reacting species of the
reaction, there are also heat of mixing sources associated with the concentration
gradients and resulting molecular flux of the reacting species from the bulk to the
surface that have to been to included for a correct thermal balance of the cell. The heat
of mixing effects are typically small (zero for ideal gases) and are generally not included

216 | CHAPTER 4: ELECTROCHEMISTRY INTERFACES

in the Electrochemistry interfaces, except for intercalating porous electrodes in the
battery interfaces (see next section).

Heat of Mixing in Intercalating Electrodes

For intercalating porous electrodes in the battery interfaces, the heat of mixing qmix,i
(W/m3) of a species of index i is defined as (see Electrochemical Systems, Newman
and Thomas-Alyea, Chapter 13 Thermal Effects.)

q mix, i = – J i ⋅ ∇H i

where Ji (mol/(m2s)) is the molar flux and Hi (J/mol) is the molar enthalpy.

This expression could be seen as a species transport version of Joule heating in an

electronic conductor, for which the heat source is defined as the current density
multiplied by the gradient of the potential.

Generally, for an intercalation material, two species are considered: the intercalated
species, denoted with index s, and the holes, denoted with index θ.

The flux of the two species are equal and opposite.

Js = –JΘ

We now define the total heat of mixing as the sum of the contributions from the two
species and write

q mix = q mix, s + q mix, Θ = – J s ⋅ ∇ ( H s – H Θ )

The absolute value of the individual molar enthalpies are generally not known.
However, the difference of the gradients of the molar enthalpies are related to the
thermoneutral voltage, Etherm (V) of the intercalation reaction.

The thermonetrual voltage is defined as

ΔH ( ΔG + TΔS ) dE eq
E therm = – --------- = – -------------------------------- = E eq – T -------------
F F dT

where ΔH is the change of molar enthalpy of the redox reaction.

In the case of lithium intercalation the redox reaction is

+ -
Li + e ⇔ Li(s)

THEORY FOR ELECTROCHEMICAL HEAT SOURCES | 217

 with index s=Li(s) so that

ΔH = H Li(s) – H Li + – H θ

We now note that, if assuming the equilibrium potential to be independent of the

electrolyte lithium ion concentration,

dE eq, therm
∇ ( H s – H θ ) = – ∇ ( FE eq, therm ) = – F --------------------------- ∇c s
dc s

and finally we get

dE eq, therm
q mix = – J s ⋅  – F --------------------------- ∇c s
 dc s 

which is added to the expression for QTOT,p above.

218 | CHAPTER 4: ELECTROCHEMISTRY INTERFACES

Theory for the Electrode, Shell
Interface
The Electrode, Shell Interfacedefines electrode current conduction on a thin shell on
a boundary. The electrolyte current distribution in the adjacent domain is typically
solved for by a separate physics interface.

In this section:

• Governing Equations
• Coupling to Other Physics Interfaces

Governing Equations
The Electrode, Shell interface solves for the electric potential φ s (SI unit: V) on a
boundary, using the following governing equation:

∇ T ⋅ ( si s ) = – i n (4-7)

where ∇T is the tangential gradient operator, s (SI unit: m) is the electrode layer
thickness, and in (SI unit: A/m2) are the sum of all currents flowing out from the
electrode (in the normal direction to the boundary). Furthermore, is (SI unit: A/m2)
is the tangential current density vector along the electrode boundary, defined as

i s = – ∇T σ s φ s (4-8)

where σs is the electric conductivity (SI unit: S/m). The next section discusses
Coupling to Other Physics Interfaces.

Coupling to Other Physics Interfaces

ELECTRODE POTENTIAL IN OTHER PHYSICS INTERFACES

Typically the boundary electric potential in the Electrode Surface node is set to the
electric potential in the Electrode, Shell interface.

ELECTRODE REACTION CURRENTS

The sum of currents can be coupled to other electrochemistry interfaces, calculating
in as

THEORY FOR THE ELECTRODE, SHELL INTERFACE | 219

 i n = i tot

where itot (SI unit: A/m2) is the sum of all electrode currents in the coupled
Electrochemistry interface.

ELECTRODE LAYER THICKNESS

The electrode thickness, s, can typically be coupled to an External Depositing
Electrode (External Corroding Electrode) node in the Electrodeposition, Moving
Mesh (Corrosion, Moving Mesh) interface, in that case s is calculated as

s = s 0 + Δs tot (4-9)

where s0 is the initial electrode layer thickness, and Δstot is the electrode thickness
change, calculated by the coupled Electrochemistry interface.

HEAT SOURCE
The electron conduction gives rise to a Joule heating source QH (SI unit: W/m2)
according to

Q H = – si s ⋅ ∇ t φ s

220 | CHAPTER 4: ELECTROCHEMISTRY INTERFACES

Theory for Electroanalysis
The theory related to the Electroanalysis charge conservation model in The Tertiary
Current Distribution, Nernst-Planck Interface (tcd) is described in this section:

• Electroanalytical Methods
• Supporting Electrolyte
• Domain Equations for the Electroanalysis Case
• Electrode Boundary Conditions in the Electroanalysis Model
• The Electroanalytical Butler-Volmer Equation
• Counter Electrodes and Overall Charge Balance

Electroanalytical Methods
Electroanalysis is the science of quantitative electrochemical measurement of the
composition or properties of a chemical system. Common electroanalytical methods
include: (cyclic) voltammetry, (chrono)amperometry, potentiometry, coulometry, and
electrochemical impedance spectroscopy (EIS). These methods are experiments
performed either in a static electrolyte solution or in an electrolyte solution subject to
a forced fluid flow. The results sought in electroanalysis include:

• Measurement of the concentration of an analyte — for example, glucose, or a

gas-phase species that dissolves in the electrolyte solution. This technique is often
referred to as electrochemical sensing. The most common sensing method is by
recording the concentration-dependent current due to an analyte-specific reaction:
this is called amperometric sensing.
• Measurement of the kinetic and/or thermodynamic parameters describing an
electrochemical reaction on a given electrode surface.
• Measurement of the transport properties of an electroactive chemical species.
• Investigation of the mechanism of an electrochemical reaction and the further
reactivity of the electrochemically generated chemical species.

Supporting Electrolyte
When performing electroanalytical experiments, it is conventional to add a large
quantity of inert salt to the solution — this artificially added salt is called supporting

THEORY FOR ELECTROANALYSIS | 221

 electrolyte. The purpose of the supporting electrolyte is to increase the conductivity of
the solution, and hence to eliminate the electric field from the electrolyte.

A negligible electric field provides two advantages for electroanalysis:

• The voltage due to the resistance of the electrolyte when the cell draws current
(“ohmic drop”) is minimal. Therefore, the potential difference applied across the
electrochemical cell is localized at the electrode–electrolyte interfaces, and so the
activation overpotential perceived by the redox couple at this interface is almost
exactly proportional to the applied cell voltage. The kinetic behavior of the
electrochemical cell then has no explicit dependence on the magnitude of the drawn
current.
• The contribution of migration to the transport of charged chemical species is
negligible compared to the contribution of diffusion (and of convection, in a forced
flow). Therefore the transport properties of the system are linearized, and they do
not depend on the magnitude of the drawn current.

These properties greatly simplify the design and analysis of electroanalytical

experiments. Therefore, the use of a supporting electrolyte is very common in
electrochemical sensing and electroanalysis.

The amount of supporting electrolyte required for the assumption of zero

electric field to be sound is dependent on the system. Typically it becomes
valid when the concentration of inert salt exceeds the concentration of
analyte by a factor of 10–100, but this is not always the case.

Even for the conductivities of electrolyte solutions in the presence of excess supporting
electrolyte, the electric field is not negligible if significant current density is drawn.
Electroanalysis typically draws small currents because the purpose is measurement. In
processes where an electrochemical reaction is driven — such as electrolysis,
electrodeposition, batteries, and fuel cells — current densities are typically much larger,
so that the desired extent of reaction is achieved in a reasonable time. Under these
conditions, significant electric fields are likely and other charge conservation models
should be used instead of the Electroanalysis option.

Domain Equations for the Electroanalysis Case

The Electroanalysis option assumes that the electric field is zero, and so the electrolyte
potential is constant. Since you can arbitrarily choose to ground the electrolyte
potential at any point, set it to φ l = 0 .

222 | CHAPTER 4: ELECTROCHEMISTRY INTERFACES

This is equivalent to the assumption of infinite electrolyte conductivity. Therefore the
Electroanalysis option does not solve for charge transfer within domains, because
current density is not meaningfully defined within the electrolyte.

The transport of chemical species in an electrolyte solution obeys the Nernst–Planck

equation for the flux of species i:

N i = – D i ∇c i – z i u m, i Fc i ∇φ l + c i u = J i + c i u

Here Ji denotes the molar flux relative to the convective transport.

At zero electric field, this reduces to:

N i = – D i ∇c i + c i u (4-10)

where the only contributions to the flux of a chemical species are from diffusion and
convection respectively. In the absence of convection (no fluid flow, u = 0), this is also
known as Fick’s first law of diffusion:

N i = J i = – D i ∇c i

A mass balance also applies to each chemical species:

∂c i
+ ∇ ⋅ N i = R i, tot (4-11)
∂t

The Electroanalysis charge conservation model solves Equation 4-10 and

Equation 4-11 for the unknown concentrations of each chemical species under
analysis.

This combination is often written as a single equation for the unknown ci. For zero
convection, zero reaction, and a constant diffusion coefficient, the domain equation is:

∂c i 2
= Di ∇ ci (4-12)
∂t

THEORY FOR ELECTROANALYSIS | 223

 Equation 4-12 is Fick’s second law of diffusion.

The Electroanalysis charge conservation model is not suitable to explicitly

model the transport of the supporting electrolyte, since the migration of
the supporting electrolyte is always its dominant mode of mass transport.
For a coupled model including the chemical species of all charge-carrying
species, use the electroneutrality model in Tertiary Current Distribution,
Nernst–Planck interface.

You can also include additional chemical species and reactions that are not
involved in the electrochemical reaction.

• Electrode Potentials and Reference Electrodes

• The Tertiary Current Distribution, Nernst-Planck Interface

Electrode Boundary Conditions in the Electroanalysis Model

The activation overpotential at an electrode–electrolyte interface with respect to the
electrode reaction m is defined as:

η m = φ s – φ l – E eq, m

This is the potential difference perceived by a redox couple, measured against the
equilibrium potential of the couple; it provides the thermodynamic driving force for
an electrochemical reaction by faradaic charge transfer between the electrode and the
electrolyte domains.

Subject to the approximation of constant electrolyte potential ( φ l = 0 ), this equation

reduces to:

η m = φ s – E eq, m

The activation overpotential is independent of the properties of the adjacent

electrolyte. It only depends on the applied electrode potential φs and the equilibrium
potential of the redox couple, where both are measured against a common reference
potential.

224 | CHAPTER 4: ELECTROCHEMISTRY INTERFACES

The current density due to an electrode reaction at a point on an electrode surface is
computed using an electrochemical rate expression. For most practical electroanalytical
applications, the rate depends on the local concentration which varies during the study,
and so the most relevant expression is The Electroanalytical Butler-Volmer Equation.

Electrode Kinetics Expressions

The flux Ni of the chemical species i (SI unit: mol/m2) across an electrode surface
depends on the current densities im associated with the electrode reactions m
according to Faraday’s laws of electrolysis. These can be written as:

ν i, m i m
Ni =  -----------------
nm F
- (4-13)
m

where νi,m is the stoichiometric coefficient of species i with respect to reaction m (in
the reductive direction), and nm is the number of transferred electrons. F is the
Faraday constant, which is the charge on a mole of electrons (96485.3365 C/mol).

The surface flux is applied as a boundary condition:

Ni = Ni ⋅ n (4-14)

Equation 4-13 and Equation 4-14 constitute the coupling between charge balance
and mass balance. This coupling only applies at the electrode–electrolyte interface,
which is a boundary to the domain where the electroanalysis charge conservation
model solves for chemical species transport.

The total current density is the sum of Faradaic (electrode reaction) components and
non-Faradaic components (inf) such as current due to Double Layer Capacitance:

i total =  iloc, m + inf

m

The experimentally measurable total current I (SI unit: A) drawn at an electrode can
be computed by integration of the local current density (SI unit: A/m2) across the
electrode area:

THEORY FOR ELECTROANALYSIS | 225

 I total =  itotal ds
∂Ω

Domain Equations for the Electroanalysis Case

The Electroanalytical Butler-Volmer Equation

A one-electron electrochemical reaction between two solution-phase species can be
–
written as a reduction Ox + e ↔ Red .

Ox and Red represent the oxidized and reduced forms of the chemical species,
respectively.

The most general equation to describe the rate of this reaction as it proceeds at an
electrode surface is the electroanalytical Butler-Volmer equation:

α a Fη – α c Fη
i loc = k 0 F  c Red exp  --------------- – c Ox exp  -----------------  (4-15)
  RT   RT  

where k0 is the heterogeneous rate constant (SI unit: m/s) and αc is the (cathodic)
transfer coefficient (dimensionless). For a one-electron reduction, the anodic and
cathodic transfer coefficients are related as follows α a + α c = 1 .

When the current is zero, the electroanalytical Butler-Volmer equation can be

rearranged to the thermodynamic Nernst equation relating the equilibrium
concentrations of the reacting species:

– FE eq
c Red = c Ox exp  ----------------
RT

Where the flux of the reacting species is negligible compared to the concentration of
these species, the concentrations are roughly constant (cRed ~ cOx ~ c). This converts
Equation 4-15 into the Butler-Volmer equation written in terms of an exchange
current density i0 (SI unit: A/m2):

α a Fη – α c Fη
i loc = i 0  exp  --------------- – exp  ----------------- 
RT RT

The exchange current density i0 (SI unit: A/m2) is then related to the heterogeneous
rate constant as i 0 = k 0 Fc .

226 | CHAPTER 4: ELECTROCHEMISTRY INTERFACES

Counter Electrodes and Overall Charge Balance
The Electroanalysis charge conservation model does not solve explicitly for the
electrolyte potential in the domains. This has the implication that an overall charge
balance of a modeled cell does not follow naturally as a result of the domain potential
equation (as is the case for instance when solving for Ohm’s law in the Secondary
Current Distribution interface).

In order to model a charge balance of a cell with an arbitrary number of working

electrodes and counter electrodes, the solution is to add an extra degree of freedom
for the counter electrode potential, φ s, CE, and then solve for this potential to fulfill
the following current balance over all electrode surfaces:

φ s, CE :  i tot dS = 0 (4-16)
electrodes

The counter electrode potential is used in the overpotential, η, in the kinetics

expression(s) on the counter electrode.

η m = φ s, CE – E eq, m (4-17)

Note that only one counter electrode potential degree of freedom is added in the
model, regardless of the number of counter electrodes that are active.

Domain Equations for the Electroanalysis Case

THEORY FOR ELECTROANALYSIS | 227

 Electrode Potentials and Reference
Electrodes
In all the Electrochemistry branch interfaces, the dependent potential variables are φ s
(SI unit: V), the electric potential of the electrode phase (the electron conductor, such
as metal), and φ l (SI unit: V), the potential of the electrolyte phase (ion conductor).

Typically the kinetics of the electrochemical reactions are defined using the
overpotential, η (SI unit: V), defined as

η = φ s – φ l – E eq (4-18)

where Eeq (SI unit: V) is the equilibrium potential. If it is to apply for all
overpotentials, a general kinetic expression for an electrode reaction must be set up so
that the charge-transfer current over the electrolyte-electrode interface is zero for zero
overpotential (equilibrium conditions).

An implication of Equation 4-18 is that it is the potential difference, φ s – φ l , that

governs the kinetics, not the absolute individual values of φ s and φ l. A global change
in the reference for both potentials has no impact on the electrode kinetics. As a result
of this, the potentials have to be “boot-strapped” in a model in some way, typically by
making an arbitrary choice of electric ground — for example, on an external boundary
— in order to ensure that there is a unique solution to the problem.

In this section:

• Reference Electrodes
• Boundary Conditions Using Reference Electrode Potentials
• Nodes for Handling Electrode Potentials and Reference Electrodes

Reference Electrodes
In experimental electrochemistry, it is common to use a reference electrodes when
controlling current or voltage with a potentiostat. Potential differences in the system
are recorded with respect to the equilibrium potential of the redox couple at the
reference electrode. A good reference electrode is designed so that no net charge
transfer takes place at its electrode-electrolyte interface. Then the overpotential of the
reference is zero, so:

228 | CHAPTER 4: ELECTROCHEMISTRY INTERFACES

 φ s, ref = φ l + E eq, ref (4-19)

where φ s , ref (SI unit: V) is the electric potential of the reference electrode and Eeq, ref
(SI unit: V) is the equilibrium potential of the reference electrode reaction.

The electric potentials of the electrodes in the electrochemical cell can then be defined
with respect to the reference electrode according to:

E vs ref = φ s – φ s, ref (4-20)

where Evs ref (SI unit: V) is the electrode potential versus the reference potential.

It is important to realize that the presence of an ideal reference electrode in the system
has no impact on the physics; the only purpose of the reference electrode is to define
a stable reference point for the potential levels.

Boundary Conditions Using Reference Electrode Potentials

The set of boundary conditions defined in a model of an electrochemical cell needs to
ensure that no current flows through the reference electrode. A constraint for the
potential on the actual reference electrode is not suitable in general since it can create
unwanted local sources or sinks of current.

When modeling the control of an electrochemical cell by a potentiostat, which

monitors and controls the potential of an electrodes versus a reference electrode, the
electric potential conditions should be applied to the boundaries over which the
current flows in the cell. One electrode (the counter electrode) is typically grounded,
whereas an electric potential condition is set on all other (working) electrode
boundaries according to

φ s, bnd = E vs ref + φ s, ref (4-21)

where φ s , bnd (SI unit: V) is the applied electric boundary potential on the electrode.

Nodes for Handling Electrode Potentials and Reference Electrodes

The Reference Electrode node is a point feature applicable to electrolyte domains (in
all the Electrochemistry interfaces). It defines a global electric reference potential
φ s , ref (SI unit: V) according to Equation 4-19. The φ s , ref can be used in the
Electrode Potential feature for setting the electric potential of an electrode boundary
with respect to the reference potential. The variable Evs ref (SI unit: V), according to
Equation 4-20, is also defined in all electrode domains.

ELECTRODE POTENTIALS AND REFERENCE ELECTRODES | 229

 The Electric Reference Potential node is a point feature applicable to electrode
domains (in all the Electrochemistry interfaces). It defines a global electric reference
potential φ s , ref (SI unit: V) equal to the dependent variable φ s (SI unit: V) in the
point. The φ s , ref can be used in the Electrode Potential feature for setting the electric
potential of an electrode boundary with respect to the reference potential.

Whenever a φ s , ref is defined, the variable Evs ref (SI unit: V), according to
Equation 4-20, is also defined in all electrode domains.

The Electrode Potential is a boundary condition feature, applicable to external

boundaries of electrode domains (in all the Electrochemistry interfaces). It sets a
boundary condition for the electric potential with respect to a defined reference
potential according to Equation 4-21. Electric potentials defined by the Electric
Reference Potential and Reference Electrode point feature can be used as input when
specifying the Electrode Potential feature.

An Electrode Potential alternative in the Boundary Condition settings list is also

available for the Electrode Surface node.

The variable Evs ref (SI unit: V), according to Equation 4-20, is also defined on these
features.

230 | CHAPTER 4: ELECTROCHEMISTRY INTERFACES

 5

Battery Interfaces

This chapter describes the physics interfaces found under the

Electrochemistry>Battery Interfaces branch ( ).

In this chapter:

• The Lithium-Ion Battery Interface

• The Battery with Binary Electrolyte Interface
• The Lead-Acid Battery Interface
• The Single Particle Battery Interface
• The Lumped Battery Interface
• The Battery Equivalent Circuit Model Wizard Entry
• Shared Nodes for Battery Interfaces
• Theory for the Lithium-Ion Battery Interface
• Theory for the Battery with Binary Electrolyte Interface
• Theory for the Lead-Acid Battery Interface
• Theory for the Single Particle Battery Interface
• Theory for the Lumped Battery Interface

231
 The Lithium-Ion Battery Interface
The Lithium-Ion Battery (liion) interface ( ), found under the
Electrochemistry>Battery Interfaces branch ( ) when adding a physics interface, is
used to compute the potential and current distributions in a lithium-ion battery.
Multiple intercalating electrode materials can be used, and voltage losses due to
solid-electrolyte-interface (SEI) layers are also included.

The physics interface is based on the works of Newman and others. Ohm’s law is used
to describe the charge transport in the electrodes. For the electrolyte, concentrated
electrolyte theory for a quiescent aprotic (1:1) electrolyte is used to describe charge
and mass transport in the electrolyte phase.

Alternatively, a single-ion conductor charge balance, used by default by the Lithium-Ion

Battery, Single-Ion Conductor (liion) ( ) entry in the model wizard, may be used for
the electrolyte. This option is typically applicable to solid electrolytes.

An extra dimension is included in the porous electrode domains to describe the

transport of solid lithium in the solid electrode phase using Fick’s law.

Dependent Variables and Extra Dimensions

Different combinations of four dependent variables are valid and solved in different
domains. The four dependent variables are:

• φ l, electrolyte potential,
• φ s, electric potential in the electrodes,
• cl, salt concentration in the electrolyte, and
• cs, solid lithium concentration in the electrode particles in the Porous Electrode and
Additional Porous Electrode Material nodes.

The cl variable is not solved for when using the single-ion conductor charge balance
model.

The cs variable is solved for in an extra dimension, using an internal discretization in

the particle dimension, not visible in the ordinary model geometry. The cs dependent
variable, named liion.cs_xxx (where xxx is the tag of the node, for instance pce1),
can be used to set for instance concentration varying diffusion coefficients in the
particle. The spatial variable of the particle is named xs_liion_xxx (for instance,
xs_liion_pce1).

232 | CHAPTER 5: BATTERY INTERFACES

The concentration variation along the extra dimension, at a given position in the real
dimension, can be accessed using the atxd1, atxd2, and atxd3 operators. See also
Using Extra Dimensions and Plotting Results in Extra Dimensions in the COMSOL
Multiphysics Reference Manual.

The surface, center and average values of cs can also be evaluated in the real dimension
by the variable names liion.cs_surface, liion.cs_center, and
liion.cs_average, respectively.

Default Nodes
When this physics interface is added, these default nodes are also added to the Model
Builder — Electrolyte, Insulation, and Initial Values. Then, from the Physics toolbar, add
other nodes that implement, for example, Porous Electrodes and nonporous Electrodes,
and boundary conditions. You can also right-click Lithium-Ion Battery to select physics
features from the context menu.

All nodes are described in Shared Nodes for Battery Interfaces.

SETTINGS
The Label is the default physics interface name.

The Name is used primarily as a scope prefix for variables defined by the physics
interface. Refer to such physics interface variables in expressions using the pattern
<name>.<variable_name>. In order to distinguish between variables belonging to
different physics interfaces, the name string must be unique. Only letters, numbers, and
underscores (_) are permitted in the Name field. The first character must be a letter.

The default Name (for the first physics interface in the model) is liion.

DOMAIN SELECTION

Exclude domains that do not conduct current.

OUT-OF-PLANE THICKNESS
See Out-of-Plane Thickness.

THE LITHIUM-ION BATTERY INTERFACE | 233

 CROSS-SECTIONAL AREA
See Cross-Sectional Area.

CHARGE BALANCE MODEL

The Binary 1:1 liquid electrolyte option uses concentrated electrolyte theory to solve
for the lithium salt concentration and the potential as dependent variables in the
electrolyte phase. The option applicable to liquid (or plasticized) organic solvent-based
lithium salt electrolytes.

The Single-ion conductor solves for the electrolyte potential by assuming that all charge
in the electrolyte phase is carried by the positive lithium ions only, so that the
concentration of lithium ions in the electrolyte can be assumed to be constant. The
option is typically applicable to solid phase electrolytes, or electrolytes where the
electrolyte conductivity is not changing as a result of the ion transport in the cell. Since
the electrolyte concentration is not solved for, the single-ion conductor option reduces
the computational load and complexity.

Note that the single-ion conductor option will disable all settings in domain and
boundary nodes applicable to the electrolyte concentration dependent variable.

TRANSPORT MECHANISMS
Convection can be added as an additional transport mechanism. By default, the check
box Convection is not selected. Select the check box to enable convective transport.

Note that this section is not applicable if the Single-ion conductor option is selected in
the Charge Balance Model section.

PHYSICS VS. MATERIALS REFERENCE ELECTRODE POTENTIAL

The Physics vs. Materials Reference Electrode Potential setting on the physics interface
node can be used to combine material library data for current densities and equilibrium
potentials with an arbitrary reference electrode scale in the physics. The setting affects
the electrode potentials used for model input into the materials node, as well as all
equilibrium potential values output from the materials node.

Note that the setting will only impact how potentials are interpreted in communication
between the physics and the Materials node. If the From material option is not in use
for equilibrium potentials or electrode kinetics, the setting has no impact.

This section is available when the Advanced Physics Options is selected in the Show More
Options dialog box shown when the Show More Options button ( ) is clicked.

234 | CHAPTER 5: BATTERY INTERFACES

CONSISTENT STABILIZATION AND INCONSISTENT STABILIZATION
To display these sections, click the Show More Options button ( ) and select
Stabilization from the Show More Options dialog box. These sections are applicable only
if Convection is selected in the Transport Mechanisms section. There are two consistent
stabilization methods available and selected by default — Streamline diffusion and
Crosswind diffusion. There is one inconsistent stabilization method, Isotropic diffusion,
which is not selected by default.

DEPENDENT VARIABLES
This physics interface defines the following dependent variables (fields): the electrolyte
potential, the electrolyte salt concentration , and the electric potential. The names
can be changed but the names of fields and dependent variables must be unique within
a model.

The electrolyte salt concentration variable is not solved for when using the Single-ion
conductor charge balance model (see previous section).

Certain nodes may add additional dependent variables to the model. For example the
intercalated solid lithium concentration in the Porous Electrode and Additional
Porous Electrode Material nodes.

In the COMSOL Multiphysics Reference Manual see Table 2-4 for links
to common sections and Table 2-5 to common feature nodes. You can
also search for information: press F1 to open the Help window or Ctrl+F1
to open the Documentation window.

• Introduction to Electrochemistry Modeling

• About the Domain, Boundary, Edge, Point, and Pair Nodes for the
Lithium-Ion Battery Interface
• Shared Nodes for Battery Interfaces
• Shared Physics Features in the Current Distribution Interfaces
• Theory for the Lithium-Ion Battery Interface

THE LITHIUM-ION BATTERY INTERFACE | 235

 • Tutorial of a Lithium-Ion Battery: Application Library path
Battery_Design_Module/Batteries,_Lithium-Ion/li_battery_tutorial_2d
• 1D Isothermal Lithium-Ion Battery: Application Library path
Battery_Design_Module/Batteries,_Lithium-Ion/li_battery_1d
• Capacity Fade of a Lithium-Ion Battery: Application Library path
Battery_Design_Module/Batteries,_Lithium-Ion/capacity_fade

About the Domain, Boundary, Edge, Point, and Pair Nodes for the
Lithium-Ion Battery Interface
The Initial Values node and Electrode Reaction are described below, the other nodes
for The Lithium-Ion Battery Interface are described in Shared Nodes for Battery
Interfaces.

Physics nodes are available from the Physics ribbon toolbar (Windows users), Physics
context menu (Mac or Linux users), or right-click to access the context menu (all
users).

Initial Values
The Initial Values node sets the initial values for the electrolyte potential, the electric
potential, and the electrolyte salt concentration.

For many electrochemical problems that use nonlinear electrode kinetics, such as
Butler-Volmer kinetics, providing reasonable initial values can significantly improve
solver convergence.

A good value for the Electric potential (SI unit: V) in electrode and porous electrode
domains can usually be derived from the boundary conditions. For instance, if a
boundary has been grounded or set to a cell potential, use that value as the initial value
also in the adjacent domain. For the Electrolyte potential (SI unit: V) a good initial
value is often the negative of the equilibrium potential of the grounded electrode.

The default initial Electrolyte salt concentration, 1·103 mol/m3, is a typical value for
common lithium-ion battery electrolytes. This input field is not available when using
the Single-ion conductor charge balance model.

236 | CHAPTER 5: BATTERY INTERFACES

Electrode Reaction
A default Electrode Reaction node is added to the Internal Electrode Surface or
Electrode Surface physics nodes. Use the Electrode Reaction feature to define the
electrode kinetics for the charge transfer reaction that occurs between the electrolyte
and a nonporous electrode. Additional subnodes are available from the context menu
(right-click the parent node) or from the Physics toolbar, Attributes menu.

See the Electrode Reaction node in Shared Physics Features in the Current
Distribution Interfaces for a general description of the Equilibrium Potential,
Electrode Kinetics and Stoichiometric Coefficients sections.

ELECTRODE KINETICS
In addition to the kinetics expression types described in the link above, two additional
kinetics expressions are available in the Lithium-Ion Battery interface.

The Lithium metal expression can be used to define a lithium metal deposition/
dissolution reaction.

The Insertion Reaction expression can be used for modeling a heterogeneous porous
electrode — that is, when the individual electrode particles are resolved in the model
and defined on the boundaries to the electrolyte domain.

THE LITHIUM-ION BATTERY INTERFACE | 237

 T he Ba t t e r y w i t h Bi n ary E l ec t rol yt e
Interface
The Battery with Binary Electrolyte (batbe) interface ( ), found under the
Electrochemistry>Battery Interfaces branch ( ) when adding a physics interface, is
used to compute the potential and current distributions in a generic battery. Multiple
intercalating electrode materials can be used, and voltage losses due to film formation
on the porous electrodes can also be included.

Use this physics interface for modeling batteries with alkaline binary (1:1) electrolytes,
such as NiMH or NiCd batteries.

Ohm’s law is used to describe the charge transport in the electrodes, whereas
concentrated electrolyte theory for an alkaline aqueous (1:1) electrolyte is used to
describe charge and mass transport in the electrolyte phase. An extra dimension can be
included in the porous electrode domains to describe transport of species in the solid
electrode phase using Fick’s law.

Dependent Variables and Extra Dimensions

Different combinations of four dependent variables are valid and solved in different
domains. The four dependent variables are:

• φ l, electrolyte potential
• φ s, electric potential in the electrodes
• cl, salt concentration in the electrolyte,
• cs, intercalation concentration in the electrode particles when using the Porous
Electrode and Additional Porous Electrode Material nodes.

The cs variable is solved for in an extra dimension, using an internal discretization in

the particle dimension, not visible in the ordinary model geometry. The cs variable can
be referred to as batbe.cs_surface, batbe.cs_center, or batbe.cs_average.
The concentration variation along the extra dimension can be plotted along the solid
electrode phase using the comp1.xdim1.atxd2 operator. See also Using Extra
Dimensions and Plotting Results in Extra Dimensions in the COMSOL Multiphysics
Reference Manual.

238 | CHAPTER 5: BATTERY INTERFACES

Default Nodes
When this physics interface is added, these default nodes are also added to the Model
Builder — Electrolyte, Insulation, No Flux, and Initial Values. Then, from the Physics
toolbar, add other nodes that implement, for example, Porous Electrodes and
nonporous Electrodes, and boundary conditions. You can also right-click Battery with
Binary Electrolyte to select physics features from the context menu.

Except for the Initial Values and Porous Matrix Adsorption/Desorption

Reaction nodes, the other nodes are described in Shared Nodes for
Battery Interfaces.

SETTINGS
The Label is the default physics interface name.

The Name is used primarily as a scope prefix for variables defined by the physics
interface. Refer to such physics interface variables in expressions using the pattern
<name>.<variable_name>. In order to distinguish between variables belonging to
different physics interfaces, the name string must be unique. Only letters, numbers, and
underscores (_) are permitted in the Name field. The first character must be a letter.

The default Name (for the first physics interface in the model) is batbe.

DOMAIN SELECTION

Exclude domains that do not conduct current.

OUT-OF-PLANE THICKNESS

For 2D components, the Thickness field (default value: 1 m) defines a

parameter for the thickness of the geometry perpendicular to the
two-dimensional cross-section. The value of this parameter is used, among
other things, to automatically calculate the total current from the current
density vector. The analogy is valid for other fluxes.

THE BATTERY WITH BINARY ELECTROLYTE INTERFACE | 239

 CROSS-SECTIONAL AREA

For 1D components, enter a Cross-sectional area Ac (SI unit: m2) to define

a parameter for the area of the geometry perpendicular to the 1D
component. The value of this parameter is used, among other things, to
automatically calculate the total current from the current density vector.
The analogy is valid for other fluxes. The default is 1 m2.

SPECIES
This section contains some global settings for the electrolyte which are used in the
Insertion Reaction type kinetics in the Porous Electrode Reaction node to calculate the
concentration of water in the electrolyte. The default values correspond to a KOH
electrolyte.

• Electrolyte anion molar mass MAn- (SI unit: kg/mol). The default is 0.017 kg/mol.
• Electrolyte cation molar mass MCat+ (SI unit: kg/mol). The default is 0.0391 kg/
mol.
• Solvent molar mass M0 (SI unit: kg/mol). The default is 0.018 kg/mol.

TRANSPORT MECHANISMS
Convection can be added as an additional transport mechanism. By default, the check
box Convection is not selected. Select the check box to enable convective transport.

PHYSICS VS. MATERIALS REFERENCE ELECTRODE POTENTIAL

The Physics vs. Materials Reference Electrode Potential setting on the physics interface
node can be used to combine material library data for current densities and equilibrium
potentials with an arbitrary reference electrode scale in the physics. The setting affects
the electrode potentials used for model input into the materials node, as well as all
equilibrium potential values output from the materials node.

Note that the setting will only impact how potentials are interpreted in communication
between the physics and the Materials node. If the From material option is not in use
for equilibrium potentials or electrode kinetics, the setting has no impact.

This section is available when the Advanced Physics Options is selected in the Show More
Options dialog box shown when the Show More Options button ( ) is clicked.

240 | CHAPTER 5: BATTERY INTERFACES

CONSISTENT STABILIZATION AND INCONSISTENT STABILIZATION
To display these sections, click the Show More Options button ( ) and select
Stabilization from the Show More Options dialog box. These sections are applicable only
if Convection is selected in the Transport Mechanisms section. There are two consistent
stabilization methods available and selected by default — Streamline diffusion and
Crosswind diffusion. There is one inconsistent stabilization method, Isotropic diffusion,
which is not selected by default.

DEPENDENT VARIABLES
This physics interface defines these dependent variables (fields), the Electrolyte
potential, the Electrolyte salt concentration and Electric potential. The name can be
changed but the names of fields and dependent variables must be unique within a
model. The Intercalating species concentration in the electrode particles is another,
hidden, dependent variable. This variable is solved for locally and with an independent
variable for the particle radius.

In the COMSOL Multiphysics Reference Manual see Table 2-4 for links
to common sections and Table 2-5 to common feature nodes. You can
also search for information: press F1 to open the Help window or Ctrl+F1
to open the Documentation window.

• Introduction to Electrochemistry Modeling

• Domain, Boundary, Edge, Point, and Pair Nodes for the Battery with
Binary Electrolyte Interface
• Shared Nodes for Battery Interfaces
• Shared Physics Features in the Current Distribution Interfaces
• Theory for the Battery with Binary Electrolyte Interface

1D Isothermal Nickel-Metal Hydride Battery: Application Library path

Battery_Design_Module/Batteries,_General/nimh_battery_1d

THE BATTERY WITH BINARY ELECTROLYTE INTERFACE | 241

 Domain, Boundary, Edge, Point, and Pair Nodes for the Battery with
Binary Electrolyte Interface
The Battery with Binary Electrolyte Interface shares most of its domain, boundary,
edge, point, and pair nodes with the other battery interfaces, except for Initial Values
and Porous Matrix Adsorption/Desorption Reaction, see Shared Nodes for Battery
Interfaces.

Physics nodes are available from the Physics ribbon toolbar (Windows users), Physics
context menu (Mac or Linux users), or right-click to access the context menu (all
users).

In general, to add a node, go to the Physics toolbar, no matter what

operating system you are using. Subnodes are available by clicking the
parent node and selecting it from the Attributes menu.

Initial Values
The Initial Values node sets the initial values for the electrolyte potential, the electric
potential, and the electrolyte salt concentration.

For many electrochemical problems that use nonlinear electrode kinetics, such as
Butler-Volmer kinetics, providing reasonable initial values can significantly improve
solver convergence.

A good value for the Electric potential (SI unit: V) in electrode and porous electrode
domains can usually be derived from the boundary conditions. For instance, if a
boundary has been grounded or set to a cell potential, use that value as the initial value
also in the adjacent domain. For the Electrolyte potential (SI unit: V) a good initial
value is often the negative of the equilibrium potential of the grounded electrode.

The default initial Electrolyte salt concentration, 1·103 mol/m3, is a typical order of
magnitude for common concentrated aqueous concentrated electrolytes.

Porous Matrix Adsorption/Desorption Reaction

Use this node to model non-faradaic reactions on the porous electrode particle surface,
for instance hydrogen adsorption/desorption in a NiMH battery.

The Porous Matrix Adsorption/Desorption Reaction can be added as a subnode to a

Porous Electrode parent node.

242 | CHAPTER 5: BATTERY INTERFACES

Enter values or expressions for the Rate expression k (SI unit: mol/(m2·s)) of the
surface reaction and the stoichiometric Coefficient vs (dimensionless) of the
intercalating species for this reaction. The Active specific surface area av (SI unit: 1/m)
will only have an impact on post precessing of the volumetric source variable (mol/
(m3·s)) of the intercalating species.

THE BATTERY WITH BINARY ELECTROLYTE INTERFACE | 243

 The Lead-Acid Battery Interface
The Lead-Acid Battery (leadbat) interface ( ), found under the
Electrochemistry>Battery Interfaces branch ( ) when adding a physics interface, is
used to compute the potential and current distributions in a lead-acid battery.

Ohm’s law is used to describe the charge transport in the electrodes, whereas
concentrated electrolyte theory is used to describe charge and mass transport in the
electrolyte phase. Mass balances for the porosities in the porous electrode domains
account for changes in state-of-charge.

Dependent Variables
Different combinations of four dependent variables are valid and solved in different
domains. The four dependent variables are:

• φ l, electrolyte potential
• φ s, electric potential in the electrodes
+ -
• cl, salt concentration in the electrolyte, here H / SO 4
• ε, porosity (volume fraction of liquid electrolyte) in the Negative Porous Electrode
and Positive Porous Electrode nodes.

A lead-acid cell typically consists of five parts: a positive porous electrode (PbO2), a
reservoir of electrolyte, a porous separator, a negative porous electrode (Pb), and two
electrodes in contact with the positive porous electrode and negative porous electrode,
respectively.

Default Nodes
When this physics interface is added, these default nodes are also added to the Model
Builder — Reservoir, Electric Insulation, No Flux, and Initial Values. Then, from the
Physics toolbar, add other nodes that implement, for example, Porous Electrodes and
nonporous Electrodes, and boundary conditions. You can also right-click Lead-Acid
Battery to select physics features from the context menu

SETTINGS
The Label is the default physics interface name.

The Name is used primarily as a scope prefix for variables defined by the physics
interface. Refer to such physics interface variables in expressions using the pattern
<name>.<variable_name>. In order to distinguish between variables belonging to

244 | CHAPTER 5: BATTERY INTERFACES

different physics interfaces, the name string must be unique. Only letters, numbers, and
underscores (_) are permitted in the Name field. The first character must be a letter.

The default Name (for the first physics interface in the model) is leadbat.

DOMAIN SELECTION

Exclude domains that do not conduct current.

OUT-OF-PLANE THICKNESS
See Out-of-Plane Thickness.

CROSS-SECTIONAL AREA
See Cross-Sectional Area.

MODEL SETTINGS
The settings for the Molar volume and Transport number determine how the electrolyte
velocity is calculated in the model. The default settings correspond to lead acid battery
using sulphuric acid as electrolyte.

PHYSICS VS. MATERIALS REFERENCE ELECTRODE POTENTIAL

The Physics vs. Materials Reference Electrode Potential setting on the physics interface
node can be used to combine material library data for current densities and equilibrium
potentials with an arbitrary reference electrode scale in the physics. The setting affects
the electrode potentials used for model input into the materials node, as well as all
equilibrium potential values output from the materials node.

Note that the setting will only impact how potentials are interpreted in communication
between the physics and the Materials node. If the From material option is not in use
for equilibrium potentials or electrode kinetics, the setting has no impact.

This section is available when the Advanced Physics Options is selected in the Show More
Options dialog box shown when the Show More Options button ( ) is clicked.

DEPENDENT VARIABLES
This physics interface defines the following dependent variables (fields): Electrolyte
potential, Electrolyte salt concentration, Electric potential, and Porosity. The names can

THE LEAD-ACID BATTERY INTERFACE | 245

 be changed but the names of fields and dependent variables must be unique within a
model.

• Introduction to Electrochemistry Modeling

• Domain, Boundary, Edge, Point, and Pair Nodes for the Lead-Acid
Battery Interface
• Shared Nodes for Battery Interfaces
• Theory for the Lead-Acid Battery Interface

Discharge and Self-Discharge of a Lead-Acid Battery: Application

Library path Battery_Design_Module/Batteries,_General/pb_acid_battery_1d

Domain, Boundary, Edge, Point, and Pair Nodes for the Lead-Acid
Battery Interface
Physics nodes are available from the Physics ribbon toolbar (Windows users), Physics
context menu (Mac or Linux users), or right-click to access the context menu (all
users).

The Lead-Acid Battery Interface shares all but a few of its domain, boundary, edge,
point, and pair nodes with the other battery interfaces as described in Shared Nodes
for Battery Interfaces.

These domain (and one boundary) nodes are unique for this physics interface and
described here:

• Initial Values • Reservoir

• Negative Porous Electrode • Separator
• Positive Porous Electrode

In the COMSOL Multiphysics Reference Manual, see Table 2-4 for links
to common sections and Table 2-5 to common feature nodes. You can
also search for information: press F1 to open the Help window or Ctrl+F1
to open the Documentation window.

246 | CHAPTER 5: BATTERY INTERFACES

 In general, to add a node, go to the Physics toolbar, no matter what
operating system you are using. Subnodes are available by clicking the
parent node and selecting it from the Attributes menu.

Reservoir
The Reservoir node defines a current balance and a material balance for the salt, here
+ -
H / SO 4 , in a free electrolyte domain.

Use this node for domains that do not contain electrode nor separator material.

The settings of the Electrolyte conductivity σl (SI unit: S/m) and the Electrolyte salt
diffusivity Dl (SI unit: m2/s) values defines the electrolyte salt transport due to
migration and diffusion.

Also convective transport can be of importance in lead acid cells. You may set the Mean
surface-averaged velocity expression to use analytical expressions for the velocity, based
on the volume changes and the electrolyte current for either the Negative electrode
main reaction or Positive electrode main reaction, or use User defined for an arbitrary
expression for the Velocity u (SI unit: m/s)

For the domain equations in the electrolyte, see the Theory for the
Lead-Acid Battery Interface.

Initial Values
The Initial Values node sets the initial values for the electrolyte potential, the electric
potential, and the electrolyte salt concentration. Use multiple Initial Values nodes to
specify different initial values in different domains.

For many electrochemical problems that use nonlinear electrode kinetics, such as
Butler-Volmer kinetics, providing reasonable initial values can significantly improve
solver convergence.

A good value for the Electric potential (SI unit: V) in electrode and porous electrode
domains can usually be derived from the boundary conditions. For instance, if a
boundary has been grounded or set to a cell potential, use that value as the initial value
also in the adjacent domain. For the Electrolyte potential (SI unit: V) a good initial
value is often the negative of the equilibrium potential of the grounded electrode.

THE LEAD-ACID BATTERY INTERFACE | 247

 The default initial Electrolyte salt concentration, 4900 mol/m3, is a typical value for a
standard lead-acid battery.

The initial value of the Porosity (dimensionless) will set the initial electrode
state-of-charge (SOC) in the Negative Porous Electrode and Positive Porous
Electrode nodes.

Negative Porous Electrode

Use the Negative Porous Electrode node to set up current balances for the electrode and
the pore electrolyte in the lead electrode, a material balance for the salt, and a mass
balance for lead, lead oxide, and lead sulfate, using the porosity variable. In addition,
the feature is also able to define the charge transfer reactions that take place in the lead
electrode.

By addition of Porous Electrode Reaction subnodes, the feature is also able to define
the charge transfer reactions that take place at the interface between the pore
electrolyte and the porous electrode matrix. A Porous Matrix Double Layer
Capacitance and a Porous Matrix Adsorption/Desorption Reaction (for the Battery
with Binary Electrolyte interface), can also be added to the node.

ELECTROLYTE PROPERTIES
See the Reservoir node for the settings of this section.

ELECTRODE PROPERTIES
The Porosity at zero charge ε0 and Porosity when fully charged εmax determines the
capacity of the electrode and defines the soc variable. The Exponent on porosity in
electrode exm defines how the effective transport parameters in the porous media
depends on the porosity.

See the Electrode for more information about the settings of this node.

For the domain equations in the electrolyte, see the Theory for the
Lead-Acid Battery Interface.

Positive Porous Electrode

Use the Positive Porous Electrode node to set up current balances for the electrode and
the pore electrolyte in the lead oxide electrode, a material balance for the salt, and a

248 | CHAPTER 5: BATTERY INTERFACES

mass balance for lead, lead oxide, and lead sulfate, using the porosity variable. In
addition, the feature is also able to define the charge transfer reactions that take place
in the lead oxide electrode.

See Negative Porous Electrode for all settings.

The difference between the Positive and Negative Porous Electrode nodes are the
default values for some of the parameters, for instance of the Equilibrium Potential of
the Porous Electrode subnode.

Separator
Use a Separator node to define a current balance in the electrolyte and a material
+ -
balance for the salt, here H / SO 4 . Both the material and current balances are
defined for porous media.

The Separator node can be added from the Electrolyte submenu.

The Porosity in separator εsep (dimensionless) and the Exponent on porosity in

electrolyte ex (dimensionless) parameters will define how the effective transport
parameters of the pore electrolyte are calculated.

See also the Reservoir node.

For the domain equations in the electrolyte, see the Theory for the
Lead-Acid Battery Interface.

THE LEAD-ACID BATTERY INTERFACE | 249

 The Single Particle Battery Interface
The Single Particle Battery (spb) interface ( ), found under the
Electrochemistry>Battery Interfaces branch ( ) offers a simplified (compared to, for
instance, the Lithium-Ion Battery interface) approach to battery modeling. The basic
assumptions used are valid when current distribution effects along the depth of the
porous electrodes are negligible, and when the salt concentration gradients in the
electrolyte do not cause significant changes of the local conductivity of the electrolyte.
The validity of the assumptions and the applicability of the single particle approach
depends on various battery parameters values such as electrode porosities and
thicknesses, and the electrode-electrolyte chemistry, in relation to the current load. As
a rule of thumb, the Single Particle Battery interface is typically applicable to battery
currents up to 1C (currents corresponding to a full charge or discharge in one hour).

Due to the lower computational load of the single particle model, the interface is
suitable for models including extended cycling for, for instance, life-time simulations
and thermal simulations of battery packs.

The Single Particle Battery interface models the charge distribution in a battery using
one separate single particle model each for the positive and negative electrodes of the
battery. The core simplification of the single particle model is to treat the large number
of individual electrode particles as a single particle, assuming that the reaction current
distribution across the porous electrodes is uniform. The single particle formulation
accounts for solid diffusion in the electrode particles and the intercalation reaction
kinetics. The ohmic potential drop in the separator is also included in the model, using
a lumped solution resistance term.

The single particle model is either solved in a global version, where all potential
dependent variables are solved globally, or in a local version (available in 1D, 2D and
3D), where the variables are solved for locally in the same spatial dimension as the
physics interface. The local version, which renders a significantly higher computational
load, is suitable for modeling non-homogeneous aging in cells where local differences
in the model parameters (such as temperature) induce localized differences in the
battery cell current density. It could also be used for modeling, for instance, cold start
of a battery pack, where local currents will cause local heating with a positive feedback
when the increased temperature raises the local electrolyte conductivity. Note that the
global and local approach both require fairly low currents for the single particle
approach to be valid, as described above. However, it is possible to set up the

250 | CHAPTER 5: BATTERY INTERFACES

electrolyte solution resistance as a function of the applied current in order to provide
a better representation even at higher values of current.

The local model contains both global and local variables. Conversion between local
and global variables are done by integrating over the total cell volume.

• Introduction to Electrochemistry Modeling

SETTINGS
The Label is the default physics interface name.

The Name is used primarily as a scope prefix for variables defined by the physics
interface. Refer to such physics interface variables in expressions using the pattern
<name>.<variable_name>. In order to distinguish between variables belonging to
different physics interfaces, the name string must be unique. Only letters, numbers, and
underscores (_) are permitted in the Name field. The first character must be a letter.

The default Name (for the first physics interface in the model) is spb.

DOMAIN SELECTION
This section is available in 1D, 2D, and 3D. The domain selection of the interface is
used to calculate the battery volume.

OPERATION MODE
Use the Operation mode setting to specify the load of the battery. Galvanostatic lets you
specify the Applied current (A). Charge-discharge cycling lets you specify the settings that
are required to apply a charge-discharge cycle, including constant current, constant
voltage and rest periods. Potentiostatic allows for specifying the Applied voltage (V) and
Circuit voltage source lets you connect to the Electrical Circuits interface.

BATTERY SETTINGS
You may define the host capacities of the two electrodes (which in term will set the
total capacity of the battery) either by the Cell capacity or the Volume fractions
alternative. The for the cell capacity case, the electrode volume fractions are derived by
setting explicit values for the Battery cell capacity in combination with the Fraction of
hosted capacity excess in negative electrode, which can be used to specify the relation in
size between the two electrodes. The fractional volumes correspond to the relative
thicknesses of the porous electrodes to the total thickness of the battery cell. (The

THE SINGLE PARTICLE BATTERY INTERFACE | 251

 volume fraction of the actual electrode materials within each electrode is defined in the
Positive Electrode and Negative Electrode nodes.)

Use the Model setting (available in 1D, 2D, and 3D) to switch between a Global or Local
definition of the dependent variables of the model. The difference between the global
and local model is described above.

INITIAL CHARGE DISTRIBUTION

The settings of this section are used to specify the target initial solid concentration
(state-of-charge) of the electrodes that will be solved for when the interface is solved
with a Current Distribution Initialization step in the Study sequence. The initial charge
distribution can then be used as initial conditions for a following Time Dependent
study step in the Study.

Cell state-of-charge sets the concentrations based on the cell capacity and the Initial cell
state of charge (1), Cell voltage sets the concentrations based on the cell capacity, and
the Electrode state-of-charges lets you specify the state-of-charge of each electrode
individually.

The Fraction of cyclable species loss after cell assembly can be used to reduce the amount
of cyclable species in relation to the capacity specified in the Battery settings section.
Use this setting to define irreversible losses of cyclable material, for instance due to
solid-electrolyte-interface (SEI) formation in a lithium-ion battery.

POROUS ELECTRODE REACTION KINETICS

This section is only visible if the Operation mode is set to Galvanostatic.

In certain cases the Butler-Volmer kinetics expression, used to define the electrode
reactions, can be inverted in order to define the electrode overpotential as an analytical
function of the current. The advantage of this is that the potential then does not have
to be solved for explicitly as a dependent variable in the model, and the nonlinearities
associated with the exponential Butler-Volmer expression can be avoided. This
improves computational efficiency significantly. The inverse expression can be used
only when

• the anodic and cathodic transfer coefficients are both equal to 0.5
• only one porous electrode reaction is present per electrode
• no double layer capacitance is present
• the battery is running in Galvanostatic mode

252 | CHAPTER 5: BATTERY INTERFACES

Enabling Use simplified lithium insertion reaction kinetics expression for either the
Positive electrode or Negative electrode will disable any Porous Electrode Reaction
subnodes to the corresponding electrode node and replace them with a single Lithium
Insertion Reaction subnode.

BATTERY VOLUME
This setting is available in 0D.

CROSS-SECTIONAL AREA
This setting is available in 1D. The setting is used to calculate the battery volume. See
Cross-Sectional Area.

OUT-OF-PLANE THICKNESS
This setting is available in 2D. The setting is used to calculate the battery volume. See
Out-of-Plane Thickness.

PHYSICS VS. MATERIALS REFERENCE ELECTRODE POTENTIAL

The Physics vs. Materials Reference Electrode Potential setting on the physics interface
node can be used to combine material library data for current densities and equilibrium
potentials with an arbitrary reference electrode scale in the physics. The setting affects
the electrode potentials used for model input into the materials node, as well as all
equilibrium potential values output from the materials node.

Note that the setting will only impact how potentials are interpreted in communication
between the physics and the Materials node. If the From material option is not in use
for equilibrium potentials or electrode kinetics, the setting has no impact.

This section is available when the Advanced Physics Options is selected in the Show More
Options dialog box shown when the Show More Options button ( ) is clicked.

ADVANCED SETTINGS
To display this section, click the Show More Options button ( ) and select Advanced
Physics Options in the Show More Options dialog box. In this section you can set the
Initial values of some of the dependent variables in the interface. The settings are
normally only needed if the model is solved without an initial Current Distribution
Initialization study step in the Study sequence. Also, you can set the check box Exclude
heat source variable from Jacobian. The check box is selected by default in 3D and is not
selected by default in other space dimensions. Note that this check box is relevant only
when coupling to heat transfer interfaces.

THE SINGLE PARTICLE BATTERY INTERFACE | 253

 DISCRETIZATION
The section is only available in 1D, 2D, and 3D. The chosen Element order will be used
by the dependent variables when the Model is set to Local.

Single Particle Model of a Lithium-Ion Battery: Application Library

path Battery_Design_Module/Batteries,_Lithium-Ion/
li_battery_single_particle

Model Tree Nodes for the Single Particle Battery Interface

When this physics interface is added, these default nodes are also added to the Model
Builder — Electrolyte and Separator, Positive Electrode, and Negative Electrode. Only
one instance each of these nodes can be present in the interface, so you cannot add
additional instances of these nodes, and they cannot be deleted. The selection of these
nodes are locked to the parent selection of the physics interface.

Electrolyte and Separator

The settings of this node are used to define the lumped electrolyte conductivity and
the cross-sectional area of the single particle model. For the conductivity, you may
either specify user-defined settings or make use of the Materials node and the Battery
Materials library.

The settings of the Model Inputs are used to specify the electrolyte salt concentration
when you use the Materials node to provide the electrolyte conductivity.

The Electrolyte solution resistance setting may either be Based on thickness and
conductivity or User defined. The first option will calculate the lumped electrolyte
resistance based on the Separator thickness (m) and the Electrolyte conductivity (S/m),
Effective conductivity correction (1) and the Electrolyte volume fraction in separator (1).
The Fraction of separator resistance value (1) is used to correct for the fact that the
lumped effective electrolyte thickness is thicker than the separator due to distribution
effects in the porous electrodes. It is typically a value larger than 1.

The Separator thickness setting can also be used in combination with the parameters
below to calculate the cross-sectional area of the separator in the battery, and it may
also be used to compute to lumped solution resistance.

254 | CHAPTER 5: BATTERY INTERFACES

The Separator cross-sectional area setting may either be Based on thickness and volume
fraction of User defined. The first option will calculate the area based on the Separator
thickness and the Separator volume fraction in battery (1).

Positive Electrode
The settings of this node are used to define the properties of the positive electrode
material.

Subnodes (one Porous Electrode Reaction is added by default) are used to define the
properties of the electrochemical reactions in the electrode. You may also add
additional Porous Electrode Reaction and Porous Matrix Double Layer Capacitance
subnodes. These subnodes are available by clicking the parent node and selecting it
from the Attributes menu, or by right-clicking the parent node.

If the Use simplified reaction kinetics expression for check-boxes for the Positive
electrode has been enabled in the Porous Electrode Reaction Kinetics section on the
top-node, only one single Lithium Insertion Reaction is present, and it cannot be
deleted.

ELECTRODE SETTINGS
The Solid volume fraction (1) is used to calculate the electrode surface area of the
electrode. If the battery capacity is defined by Volume fractions on the parent interface
node, this setting will also have an impact on the resulting electrode host capacity.

PARTICLE INTERCALATION
This section handles the settings for the intercalating species in the electrode particles.

For the remaining settings of this section see the Porous Electrode node in the
Lithium-Ion Battery and Battery with Binary Electrolyte interfaces.

Negative Electrode
The settings of this node are used to define the properties of the negative electrode
material. The settings are identical to the Positive Electrode.

Lithium Insertion Reaction

This node is available as a subnode to the Positive Electrode and Negative Electrode
nodes.

THE SINGLE PARTICLE BATTERY INTERFACE | 255

 The node is only present when the Use simplified lithium insertion reaction kinetics
expression for check-boxes for either the Positive electrode or Negative electrode has
been enabled in the Porous Electrode Reaction Kinetics section on the top node.

For the rest of the settings of this node, see the Insertion Reaction.

256 | CHAPTER 5: BATTERY INTERFACES

The Lumped Battery Interface
The Lumped Battery (lb) interface ( ), found under the Electrochemistry>Battery
Interfaces branch ( ) offers a simplified (compared to, for instance, the Lithium-Ion
Battery or the Single Particle Battery interface) approach to battery modeling.

Instead of differentiating between the various processes in the negative and positive
electrodes, and the electrolyte, the Lumped Battery interface makes use of a small set
of lumped parameters for adding contributions for the sum of all voltage losses in the
battery, stemming from ohmic resistances and (optionally) charge transfer and/or
diffusion processes. The applicability of the lumped approach depends on various
internal battery parameters such as the combination of electrode and electrolyte
materials, porosities and layer thicknesses, and the electrode-electrolyte chemistry, in
relation to the current load.

Due to the limited set of parameters needed, the interface is suitable when only little
information is available about the internal structure, or chemistry, of a battery. Heat
sources are calculated automatically by the physics interface and can be used together
with a Heat Transfer interface for thermal simulations.

The Lumped Battery interface is based on a similar set of equations as The Single
Particle Battery Interface, with additional simplifications based on the assumption that
the activation and concentration overpotentials can be attributed to one electrode only.

The interface solves for the battery state-of-charge as a dependent variable. If

concentration overpotentials are included in the model and calculated based on
diffusion in an idealized particle, the state-of-charge variable is solved for in an extra
dimension, representing a generalized electrode particle (or electrolyte diffusion layer)
wherein concentration overpotentials occur due to limited mass transport of a reacting
species to the electrode-electrolyte interface, where the charge transfer reaction takes
place.

The lumped model is either solved in a global version, where the soc dependent
variable and diffusion extra dimension are defined globally, or in a local version
(available in 1D, 2D, and 3D), where the variables are solved for locally in the same
spatial dimension as the physics interface. The local version, which renders a
significantly higher computational load, is suitable for modeling inhomogeneous cells
where local differences in the model parameters (such as temperature dependent
resistances) induce localized differences in the battery cell current density. One
example could be cold start of a battery pack, where local currents will cause local

THE LUMPED BATTERY INTERFACE | 257

 heating with a positive feedback when the increased temperature raises the local
electrolyte conductivity.

The local model contains both global and local variables. Conversion between local
and global variables are done by integrating over the total cell volume.

• Introduction to Electrochemistry Modeling

SETTINGS
The Label is the default physics interface name.

The Name is used primarily as a scope prefix for variables defined by the physics
interface. Refer to such physics interface variables in expressions using the pattern
<name>.<variable_name>. In order to distinguish between variables belonging to
different physics interfaces, the name string must be unique. Only letters, numbers, and
underscores (_) are permitted in the Name field. The first character must be a letter.

The default Name (for the first physics interface in the model) is lb

DOMAIN SELECTION
This section is available in 1D, 2D and 3D. The domain selection of the interface is
used to calculate the battery volume.

OPERATION MODE
Use the Operation mode setting to specify the load of the battery.

Galvanostatic lets you specify the Applied current (A). This can be used to specify the
battery current load. (The expression may be time-dependent using the character t for
time.). Charge-discharge cycling mode lets you specify the settings that are required to
apply a charge-discharge cycle, including constant current, constant voltage and rest
periods. Potentiostatic allows for specifying the Applied voltage (V) and Power allows
for specifying the Applied power (W). Circuit voltage source lets you connect to the
Electrical Circuits interface.

BATTERY SETTINGS
The Battery Cell Capacity (C) specifies the battery capacity.

The Initial cell state-of-charge (1) specifies the state-of-charge of the battery when the
simulation starts.

258 | CHAPTER 5: BATTERY INTERFACES

Use the Model setting (available in 1D, 2D and 3D) to switch between a Global or Local
definition of the dependent variables of the model. The difference between the global
and local model is described above.

HARMONIC PERTURBATION
To display this section, click the Show More Options button ( ) and select Advanced
Physics Options.

Use Perturbation amplitude (A) to specify the perturbation on the applied battery
current. This section is applicable only for frequency domain, perturbation studies
using the Galvanostatic operation mode.

BATTERY VOLUME
A battery volume variable is used in order to calculate a battery heat source variable
([Link], SI-unit: W/m3) from the lumped model. The heat source may typically be
used for thermal simulations in combination with a Heat Transfer interface.

A Battery Volume (m3) setting is available in 0D.

In 1D, the selected domain length, in combination with the Cross-Sectional Area is
used for calculating the volume.

In 2D, the selected domain area, in combination with the Out-of-Plane Thickness is
used for calculating the volume.

In 3D, the battery volume equals the volume of the selected domain.

ADVANCED SETTINGS
To display this section, click the Show More Options button ( ) and select Advanced
Physics Options.

In this section you can set the check box Exclude heat source variable from Jacobian. The
check box is selected by default in 3D and is not selected by default in other space
dimensions. Note that this check box is relevant only when coupling to heat transfer
interfaces. Excluding the heat source from the Jacobian may decrease the computation
time..

Model Tree Nodes for the Lumped Battery Interface

When this physics interface is added, these default nodes are also added to the Model
Builder — Cell Equilibrium Potential and Voltage Losses. Only one instance each of
these nodes can be present in the interface, so you cannot add additional instances of

THE LUMPED BATTERY INTERFACE | 259

 these nodes, and they cannot be deleted. The selection of these nodes are locked to the
parent selection of the physics interface.

Cell Equilibrium Potential

The settings of this node define the thermodynamics of the battery.

Specify the Open circuit voltage at reference temperature (V) and Temperature derivative
of open circuit voltage (V/K) as a function of state-of-charge, in the corresponding
tables. Linear interpolation between the provided values, as well as linear extrapolation
outside the range of values will be used. Note, the temperature derivative of open
circuit voltage data is used to calculate the temperature dependence of the open circuit
voltage and in the calculation of the reversible (entropic) contribution and heat of
mixing contribution to the total heat source.

Also, set the Reference temperature in this node.

Voltage Losses
The settings of this node define the voltage losses that occur in the battery when a
current is applied.

OHMIC OVERPOTENTIAL
The Ohmic Overpotential varies linearly with the battery current. The value of the Ohmic
overpotential at 1C (V) specifies the value of ohmic voltage loss for a battery current of
1C. The 1C current equals the battery capacity value, set a the interface top node,
divided by 1 h.

ACTIVATION OVERPOTENTIAL
Enable Include activation overpotential to add a voltage loss related to the charge
transfer processes in the battery. A Dimensionless charge exchange current value of 1
corresponds to an activation overpotential of approximately 25 mV for a battery
current of 1C. For higher currents the activation overpotential varies approximately
logarithmically with the current magnitude.

Enable Include double layer capacitance to include capacitative charging of the double
layer over which the charge transfer processes occur. These effects typically occur on a
time scale of tens of microseconds, or less.

260 | CHAPTER 5: BATTERY INTERFACES

CONCENTRATION OVERPOTENTIAL
Enable Include concentration overpotential to add a voltage loss related to mass
transport (diffusion) processes in the battery. Two different concentration
overpotential models are available: Particle diffusion and Resistor-Capacitor pair.

For Particle diffusion, the magnitude of the concentration overpotential will depend
both on the Open circuit voltage, specified on the Cell Equilibrium Potential node, and
the cycling history of the battery. The value of the Diffusion time constant is related to
the relaxation time of the battery for reaching steady state at open circuit. Increasing
the value of the diffusion time constant will generally increase the concentration
overpotential.

For the Resistor-Capacitor pair option, the concentration overpotential will depend
both on the RC time constant and the RC potential at 1C parameters. The latter
parameter equals the steady-state overpotential that the RC component will approach
for a 1C constant load. (Note that the Particle diffusion overpotential will never reach
a steady state value for a constant load.)

PARTICLE DISCRETIZATION
This section is only available when Include concentration overpotential is enabled, using
a Particle diffusion model. The section handles the settings for how the extra dimension
used for solving the diffusion equation is defined. For the settings of this section, see
the Particle Intercalation node in the Lithium-Ion Battery and Battery with Binary
Electrolyte interfaces.

Capacity Loss
The settings of this node define the capacity loss that occurs in the battery due to
parasitic reactions.

CAPACITY LOSS
The Loss kinetics can be specified by either using a Built in expression or an User defined
expression. The Built in option calculates a loss current based on a Calendar aging time
constant that defines the rate of the parasitic reactions, and dimensionless aging factors
dependent on Voltage, Current, Aging history and Temperature, respectively. The loss
current is used to calculate the accumulated capacity loss corresponding to the parasitic
reactions.

All aging factors having the value of 1 would result in a constant capacity fade, starting
from initial time, reaching 0 remaining cell capacity when the time is equal to the

THE LUMPED BATTERY INTERFACE | 261

 Calendar aging time constant, independent of battery SOC, capacity throughput, aging
history and temperature.

Enable Voltage to specify the Offset potential and Transfer coefficient parameters, that
relate how the rate of the parasitic reactions changes when the battery voltage deviates
from the average open circuit voltage. In many battery systems, it is seen that high
state-of-charge values (typically resulting in high battery voltage) accelerate capacity
loss.

Battery lifetime is closely related to the amount of cycled equivalent full cycles. Enable
Current to specify the Cycling capacity loss factor parameter, that defines the additional
capacity loss induced by cycling. For example, a value of 2·10−4 (with all other aging
factors set to 1) would result in an additional capacity fade of 20% for a cycled amount
corresponding to 1000 cycles of the initial capacity.

Enable Aging history to define a decelerating aging rate. Specify the Decelerating aging
factor that defines how many times the capacity loss rate will have been reduced when
all capacity has been lost.

Enable Temperature to specify the Activation energy and Reference temperature

parameters, in order to calculate a temperature dependent aging factor defined using
an Arrhenius expression.

The User defined option of Loss kinetics can be used to explicitly specify the Loss
current.

Short Circuit
Use this setting to define the short circuit scenario inside a lumped battery. Define the
Short Circuit Conductance in S to evaluate short circuit currents and corresponding heat
source. This node can be used to model self discharge in a lumped battery, along with
other short circuit scenarios.

262 | CHAPTER 5: BATTERY INTERFACES

T he B a t t e r y E q u i v al en t Ci rc u i t Mod el
Wizard Entry
The Battery Equivalent Circuit model wizard entry can be used to define a battery
model based on an arbitrary number of electrical circuit elements. Models created with
the Battery Equivalent Circuit can typically be used to monitor the state-of-charge and
the voltage response of a battery during a load cycle.

When selecting the Battery Equivalent Circuit in the Model Wizard, this adds an
Electrical Circuit interface to the model, including a number of predefined circuit
elements that are used to define the open circuit voltage, the load current and an
internal resistance. Additional circuit elements such as resistors, capacitors and
inductors may be added by the user.

See also The Electrical Circuit Interface.

Figure 5-1: Circuit elements and corresponding node numbers in the Electrical Circuit
interface added by the Battery Equivalent Circuit entry in the Model Wizard.

THE BATTERY EQUIVALENT CIRCUIT MODEL WIZARD ENTRY | 263

 Shared Nodes for Battery Interfaces
The Battery with Binary Electrolyte Interface, The Lithium-Ion Battery Interface, and
The Lead-Acid Battery Interface share many domain, boundary, edge, point, and pair
nodes.

The following domain and boundary nodes are described in this section and available
for the interfaces as noted (listed in alphabetical order):

• Additional Porous Electrode • No Flux

Material • Porous Electrode
• Concentration • Porous Electrode Reaction
• Electrolyte • Positive Electrode Selection
• Flux • Reaction Source
• Initial Cell Charge Distribution • Separator
• Negative Electrode Selection

264 | CHAPTER 5: BATTERY INTERFACES

These shared nodes are described for the Current Distribution interfaces (listed in
alphabetical order).

• Double Layer Capacitance • Electrode Power

• Electric Ground • Electrolyte Potential
• Electric Potential • Electrolyte Current Source
• Electric Reference Potential • Electrolyte Current Density
• Electrode • Electrode Current
• Electrode Current • Harmonic Perturbation
• Electrode Current Density • Insulation
• Electrode Current Source • Internal Electrode Surface
• Electrode Surface • Porous Matrix Double Layer
• Electrode Reaction Capacitance

• Electrode-Electrolyte Boundary • Reference Electrode

Interface • Symmetry
• Electrode Potential

In the COMSOL Multiphysics Reference Manual see Table 2-4 for links
to common sections and Table 2-5 to common feature nodes. You can
also search for information: press F1 to open the Help window or Ctrl+F1
to open the Documentation window.

Electrolyte
Use the Electrolyte node to define an electrolyte domain that only conducts current in
the ion conducting phase. The combined charge and mass transfer in the electrolyte is
defined by the node.

The Convection section is available when the Convection check box is selected on the
interface top node. The Velocity field u (SI unit: m/s) of the solvent is specified as a
feature input. Select the source of velocity field from the velocity field list.

The Electrolyte conductivity, σl (SI unit: S/m), parameter will define how the current
in the domain depends on the gradient of the potential and the concentration variable,
the Diffusion coefficient (SI unit: m2/s), defines how the flux of ions relates to
concentration gradients, and the Transport number t+ (also called transference

SHARED NODES FOR BATTERY INTERFACES | 265

 number), which by default is set to 0.363 (a typical value for li-ion batteries), specifies
how much of the charge is carried by the positive ions.

Use the Activity dependence on concentration parameter to modify the ion activity. The
default is 1(dimensionless).

For the Battery with Binary Electrolyte interface, also enter the Solution density ρ
(SI unit: kg/m3) (the electrolyte density). The default is 1.293e3 kg/m3 (A typical
value for a KOH electrolyte).

Note that the electrolyte in this case does not refer to the pore electrolyte in porous
electrodes (which should be defined by a Porous Electrode node instead). For porous
separators, use the Separator instead.

For the domain equations in the electrolyte, see the Theory for the
Battery with Binary Electrolyte Interface and Theory for the Lithium-Ion
Battery Interface sections.

Separator
Use a Separator node to model electrolyte charge and mass transport in an
electronically isolating porous matrix. Use correction factors to account for the
lowered diffusion coefficients in the electrolyte and the lowered conductivities of the
electrode, due to the lower volume fractions of each phase and the tortuosity of the
porous matrix.

See also the Electrolyte node for more information about some of the settings of this
node.

DISSOLVING-DEPOSITING SPECIES
See the Porous Electrode node for more information about some of the settings of this
node.

Porous Electrode
The Porous Electrode node sets up current balances for a porous electrode matrix and
a pore electrolyte, as well as the mass balance for the pore electrolyte in a domain. The
node may also set up a mass balance of an intercalating species in the electrode
particles. By addition of Porous Electrode Reaction subnodes, the feature is also able
to define the charge transfer reactions that take place at the interface between the pore

266 | CHAPTER 5: BATTERY INTERFACES

electrolyte and the porous electrode matrix. A Porous Matrix Double Layer
Capacitance and a Porous Matrix Adsorption/Desorption Reaction (for the Battery
with Binary Electrolyte interface), can also be added to the node.

Use correction factors to account for the lowered diffusion coefficients in the
electrolyte and the lowered conductivities of the electrode, due to the lower volume
fractions of each phase and the tortuosity of the porous matrix.

See also the Electrolyte and Electrode nodes for more information about the settings
of this node.

ELECTROLYTE PROPERTIES
See the Electrolyte node for more information about the settings of this section.

ELECTRODE PROPERTIES
See the Electrode node for more information about the settings of this section

PARTICLE PROPERTIES
By selecting Intercalating particles, the node adds a mass balance and the corresponding
dependent variables for solving for an intercalating concentration. The settings related
to the intercalation are set on the Particle Intercalation child node.

POROUS MATRIX PROPERTIES

The Electrode volume fraction εs and Electrolyte volume fraction ε1 parameters are used
in the mass balance equations to account for the available volume of each phase, and
also in the Porous Electrode Reaction to calculate the surface area. These parameter
values may also be used by the Effective Transport Parameter Correction (next section).
Similarly, the Electrode tortuosity τs and Electrolyte tortuosity τ1 parameters may also
be used by the Effective Transport Parameter Correction (next section).

EFFECTIVE TRANSPORT PARAMETER CORRECTION

Use the settings of this section to calculate effective transport parameters for the
electrode and the electrolyte if your corresponding parameter values refer to
nonporous media.

DISSOLVING-DEPOSITING SPECIES
Use the settings of this section to define species that participate in
dissolution-deposition electrode reactions within the porous electrode, for instance,
metal deposition/dissolution or oxide formation.

SHARED NODES FOR BATTERY INTERFACES | 267

 Use the Add ( ) and Delete ( ) buttons as needed in the tables to control the
number of species.

Dependent variables for the volumetric molar concentration are added for each
dissolving-depositing species. These variables can be used to keep track of the amount
of reacted material in the porous electrode. The total molar dissolution/deposition
rate depends on the reaction rates and stoichiometry, defined in the Porous Electrode
Reaction subnodes.

The Density and Molar mass determine the electrode growth velocity and the resulting
dissolved/deposited layer thickness. By multiplying by the electrode surface area (in
the case of multiple electrode reaction the average surface area is used), the change in
electrode and electrolyte volume fractions can be also be calculated. By use of the Add
volume change to electrode volume fraction (not available for Separator node) and
Subtract volume change from electrolyte volume fraction check boxes you may define
how these volume changes should be included in the model.

Thickness variables, based on the surface area, are also defined that you for instance
can use to couple to the Film Resistance (see below).

FILM RESISTANCE
A film resistance is typically used for modeling the build-up of a SEI (solid electrolyte
interface) layer in lithium-ion battery graphite electrodes. See also the Electrode
Surface node.

Particle Intercalation
This node is available as a subnode to the Porous Electrode and Additional Porous
Electrode Material nodes in The Lithium-Ion Battery Interface and The Battery with
Binary Electrolyte Interface interfaces. The node is only visible if Intercalating Particles
has been selected on the parent node.

SPECIES SETTINGS
The Initial species concentration cs,init (SI unit: mol/m3) is used by the solver and can
be used to specify the initial state-of-charge of the electrode.

The Maximum species concentration cs,max (SI unit: mol/m3) defines the maximum
possible concentration of the intercalated concentration. The value is used by Porous
Electrode Reaction when the Kinetic expression type has been set to Lithium Insertion.

268 | CHAPTER 5: BATTERY INTERFACES

PARTICLE TRANSPORT PROPERTIES
The Species concentration transport model specifies the diffusion model for the
intercalating species in the electrode particles.

Fick’s law and Baker-Verbrugge both add an extra dimension, defined on the porous
electrode domain, within which a diffusion equation is applied in order to solve for the
concentration distribution along the depth within a single particle of the electrode.
The transport in the extra dimension is defined by the Intercalation diffusivity Ds (SI
unit: m2/s).

Fick’s law defines the molecular flux of the intercalated species as the product of the
diffusion coefficient and the concentration gradient. The Baker-Verbrugge models adds
a correction to the diffusion coefficient based on the Equilibrium potential, Eeq, of the
intercalation reaction. This potential is defined in the Equilibrium Potential section
below. Generally, the Baker-Verbrugge model is better at capturing state-of-charge
dependent transport rates and staging phenomena, whereas Fick’s law may be
numerically more stable. Note that the parameter values of the diffusivity from the
material library generally have been estimated assuming Fick’s law and may have to be
reduced when switching to Baker-Verbrugge.

Use No spatial gradients to assume a constant concentration along the depth of the
particle. No spatial gradients significantly reduces the computational load of the model.

The geometry in the extra dimension is one-dimensional and is defined by the Particle
type (Spheres (the default), Cylinders, or Flakes) together with the Particle mean
center-surface distance rp.

Use the Minimum and the Maximum electrode state-of-charge, SOCmin (dimensionless)
and SOCmax (dimensionless) to specify a nominal state-of-charge window for the
electrode. These values are used together with the Initial Cell Charge Distribution
node to define an initial cell state of charge.

PARTICLE DISCRETIZATION
This section is not available if No spatial gradients is selected under Particle Transport
Settings.

Use these settings to control the Distribution of the mesh and the Element order of the
extra particle dimension.

The predefined distributions Square or Cubic root sequence create mesh distributions
with a denser mesh toward the particle surface.

SHARED NODES FOR BATTERY INTERFACES | 269

 The Use fast assembly in particle dimension option enables an alternative method for
assembling of the diffusion equation in the particle dimension that may decrease
computation time when the number of mesh elements in the battery cell dimension is
of the same order of magnitude as the number of elements in the particle dimension
(this is typically the case for 1D problems). When the fast assembly option is enabled,
it is not possible to postprocess the solid particle concentration along the particle
dimension, and the diffusion coefficient in the particle cannot vary along the particle
depth. The same equations are solved for regardless of assembly method.

The fast assembly option is not available if Baker-Verbrugge species concentration

transport model is enabled.

HEAT OF MIXING
This section is not available if No spatial gradients is selected under Particle Transport
Settings, or if Use fast assembly in particle dimension is enabled under Particle
Discretization.

Include heat of mixing defines a heat source defined as the gradient of the molar
enthalpy times the molar flux of the intercalating species, integrates it over the particle,
and adds it to the total heat source variable in the domain. The molar enthalpy is based
on the Equilibrium potential of the insertion reaction, defined below.

The heat source is typically used when coupling the battery interface to a heat transfer
interface using the Electrochemical Heating node.

The heat of mixing is usually small in relation the other heat sources in the battery, such
as Joule heating in the electrolyte, or the heat of reactions.

EQUILIBRIUM POTENTIAL
This section defines the Equilibrium potential of the intercalation reaction, Eeq
(SI unit: V), used by the Particle Transport Properties and Heat of Mixing sections, when
applicable.

STRESS AND STRAIN

This section is not available if No spatial gradients or the particle type Flakes is selected
under Particle Transport Settings, or if Use fast assembly in particle dimension is enabled
under Particle Discretization.

When modeling diffusion in the particle you may enable the Calculate stress and strain
check box to compute a number stress and strain related variables in the particle. The
variables are based on the Young’s modulus, the Poisson’s ration and the relative

270 | CHAPTER 5: BATTERY INTERFACES

volume change of the particle. The relative volume change is typically dependent on
the concentration in the particle.

See also Stress and strain in intercalating particles in the theory chapter below.

Diffusion-Induced Stress in a Lithium-Ion Battery: Application Library

path Battery_Design_Module/Batteries,_Lithium-Ion/
diffusion_induced_stress

Porous Electrode Reaction

The Porous Electrode Reaction node defines the electrode kinetics for a charge transfer
reaction that occurs at the interface between the pore electrolyte and the electrode
matrix a porous electrode. The node can be added as subnode to a Porous Electrode
node. Add multiple nodes to the same Porous Electrode node to model multiple
reactions, for instance in self discharge or capacity fade problems.

See the Electrode Reaction node in Shared Physics Features in the Current
Distribution Interfaces for a general description of the Equilibrium Potential,
Electrode Kinetics and Stoichiometric Coefficients sections.

ELECTRODE KINETICS
The battery interfaces have some tailor-made kinetic expressions types (see also
Electrode Reaction).

Lithium Insertion
The charge transfer reaction can be described by the reaction at the surface of the
electrode particles with subsequent lithium intercalation. This solves the charge
transfer current density in the particles in combination with the diffusion of the
intercalating species (see the theory section).

The Lithium insertion option is available for the Lithium-Ion Battery interface. The
expression is suitable for any positive or negative intercalation reaction. The Reference
exchange current density io,ref(T) (SI unit: A/m2) depends on the electrode material in
use and the temperature.

Insertion Reaction
The Insertion reaction option is available for the Battery with Binary Electrolyte
interface. It can be used for both the positive and the negative electrode main reactions

SHARED NODES FOR BATTERY INTERFACES | 271

 of a NiMH battery. The Reference exchange current density io,ref(T) (SI unit: A/m2)
depends on the electrode material in use and the temperature.

Lead-Acid Battery Charge and Lead-Acid Battery Discharge

These options are available for the Lead-Acid Battery interface. The kinetic section is
equal between the Lead-acid battery charge or Lead-acid battery discharge, but the Active
specific surface area equations differ.

ADVANCED INSERTION KINETICS SETTINGS

To display this section, click the Show More Options button ( ) and select Advanced
Physics Options.

By enabling Extrapolate insertion kinetics using first order kinetics for high and low socs
numerical stability can be improved for solid concentration values close to 0 or the
maximum concentration. The feature is enabled by default. Use the Extrapolation soc
window width to specify how close to 0 or the maximum soc the extrapolated kinetics
expression should be used.

The option is available both for the Lithium Insertion and the Insertion Reaction
kinetics.

ACTIVE SPECIFIC SURFACE AREA

The Active specific surface area av (SI unit: m2/m3) specifies the area of the
electrode-electrolyte interface that is catalytically active for this porous electrode
reaction. av is multiplied by iloc (defined in the Electrode Kinetics section) to produce
a current source in the domain.

When using a Particle-based area the particle radius is taken from the parent node if
using Intercalating particles (Lithium-ion and Battery with Binary Electrolyte
interfaces).

For the Lead-Acid Battery interface the active surface area can also be calculated as a
function of the porosity of the electrodes, which changes during discharge and
recharge as defined by the Maximum active surface area, amax (dimensions L2/L3; that
is, the SI unit is 1/m) and the Morphology number (dimensionless).

Reaction Source
Use the Reaction Source node to define sources or sinks in the mass balance of the salt
in the electrolyte. To display this option, click the Show More Options button ( ) and

272 | CHAPTER 5: BATTERY INTERFACES

select Advanced Physics Options then select Reaction Source from the Additional Sources
submenu.

Additional Porous Electrode Material

Use the Additional Porous Electrode Material node to define an additional porous
electrode material in a porous electrode, for instance to solve for an additional
intercalation concentration in the solid phase of the electrode particles. The feature can
only be applied to domains that contain an active Porous Electrode node. A Porous
Electrode Reaction node is added by default.

You specify the reactions occurring on the additional material, giving rise to fluxes in
and out from the electrode particles, using Porous Electrode Reaction subnodes,
which is available from the context menu (right-click the parent node) or from the
Physics toolbar, Attributes menu. Also add a Porous Matrix Double Layer Capacitance
and, for the Battery with Binary Electrolyte interface, a Porous Matrix Adsorption/
Desorption Reaction subnode.

The current sources and sinks defined in the Additional Porous Electrode Material
subnodes are also used in the Porous Electrode node domain equations that describe
the electrolyte and electrode current balances, and the mass balance for the electrolyte
salt.

This physics node is available for the Lithium-Ion Battery and Battery with Binary
Electrolyte interfaces.

See the Porous Electrode for more information about the settings of this node.

Concentration
Add the Concentration boundary condition from the Electrolyte submenu to set the
Concentration on boundary of the salt to a given value or expression.

No Flux
A No Flux boundary condition is added by default for all external boundaries to an
electrolyte domain.

Select additional nodes from the Electrolyte submenu overwrite this boundary
condition.

SHARED NODES FOR BATTERY INTERFACES | 273

 Flux
Add the Flux boundary condition from the Electrolyte submenu to set the Salt
electrolyte inward flux.

The flux of ions will be set in the normal direction to the boundary.

Initial Cell Charge Distribution

Use the Initial Cell Charge Distribution global node to define the initial cell voltage or
cell state-of-charge (SOC) of a battery cell. When used together with a Current
Distribution Initialization study step, the node will solve for the intercalated
concentrations in the Porous Electrode and the Additional Porous Electrode Material
nodes in order to comply with the given initial conditions.

The node also offers the possibility to balance the electrodes by calculating the
electrode phase volume fractions.

The node only has an effect on the actual equations solved for when used in a Current
Distribution Initialization study step. SOC and porosity variables will however be
defined for all study steps. For more information on the functionality of this feature,
see Initial Charge Distribution in the Battery Cell.

Use the Negative Electrode Selection and Positive Electrode Selection subnodes to
select what domains of the battery model that correspond to the negative and positive
electrodes, respectively. The node is only available in the Lithium-Ion Battery and
Battery with Binary Electrolyte interfaces.

BATTERY CELL PARAMETERS

Select an Initial battery cell setting — Initial cell voltage (the default) or Initial cell
state-of-charge.

The entered Initial cell voltage Ecell,0 (SI unit: V) needs to be a valid value that can be
physically achieved for the combination of state-of-charge windows and equilibrium
potentials of the active materials of the two electrodes (as defined in the Porous
Electrode and Porous Electrode Reaction node). The default is 3 V.

The Initial cell state-of-charge SOCcell,0 (dimensionless) should range between 0 and
1; 0 representing a fully discharged and 1 a completely charged cell. The default is 0.5.

The Battery cell capacity Qcell,0 (SI unit: C) is physically limited by the maximum
amount of cyclable species in the selected electrode materials (as defined in the Porous
Electrode node), and the model geometry (as defined in the Geometry node). A too

274 | CHAPTER 5: BATTERY INTERFACES

high value in combination with a too small electrodes may result in intercalation
concentrations higher that the maximum concentrations, or electrode porosities
higher than one when defining the cell balancing in the next section.

BATTERY CELL ELECTRODE BALANCING

Electrode balancing optimizes the amount of electrode material in each electrode with
regards to the total capacity of the battery cell, and to ensure that the concentration of
intercalated species in electrode material is maintained within the specified
state-of-charge window during cycling.

The feature computes the electrode volume fraction variable for each of the electrodes,
which may be used when defining the electrode volume fractions in the Porous
Electrode nodes. The electrode balancing does not support models using Additional
Porous Electrode Material nodes.

A geometrically larger electrode domain results in a lower electrode volume fraction,

and an electrode with an active material with a relatively narrow SOC window and a
low maximum concentration results in a high electrode volume fraction, and vice versa.

The Fraction of cyclable species loss after cell assembly fcycl,loss (dimensionless) and
Fraction of hosted capacity excess in the negative electrode fhost,neg,ex (dimensionless)
are properties that strongly impact the charge distribution in many battery cell
chemistries. The default values are 0.08 and 0.20, respectively, and represent a typical
case of a fresh lithium-battery cell with a 20% excess of carbon-based negative
electrode, and where 8% of the cyclable lithium is lost due to irreversible process at cell
assembly and initial “formation” cycling.

To balance the electrodes, enter in the Porous Matrix properties section of the Positive
Porous Electrode nodes either <physics interface name>.epss_neg or
physics interface name>.epss_pos (for example, batbe.epss_neg or
liion.epss_pos) in the Electrode Volume Fraction text field, depending on the porous
electrode being a negative or a positive electrode.

Negative Electrode Selection

Use the Negative Electrode Selection subnode with the Initial Cell Charge Distribution
node to select the Porous Electrode domain that is the negative electrode in the
battery model.

The node is only available in the Lithium-Ion Battery and Battery with Binary
Electrolyte interfaces.

SHARED NODES FOR BATTERY INTERFACES | 275

 Positive Electrode Selection
Use the Positive Electrode Selection subnode with the Initial Cell Charge Distribution
node to select the Porous Electrode domain that is the positive electrode in the battery
model.

The node is only available in the Lithium-Ion Battery and Battery with Binary
Electrolyte interfaces.

276 | CHAPTER 5: BATTERY INTERFACES

Theory for the Lithium-Ion Battery
Interface
The Lithium-Ion Battery Interface defines the current balance in the electrolyte, the
current balances in the electrodes, the mass balance for the lithium salt, and the mass
balance of lithium in lithium-ion batteries.

The electrolyte in the modeled batteries has to be a quiescent binary 1:1 electrolyte,
containing lithium cations (Li+) and anions (An-).

The physics interface solves for five dependent variables:

• φ s, the electric potential,

• φ l, the electrolyte potential,
• Δ φ s,film, the potential losses due to a resistive film on the electrode particles in the
porous electrodes, also called solid-electrolyte interface (SEI),
• cs, the concentration of lithium (LiΘs) in the electrode particles, and
• cl, the electrolyte salt concentration.

In the electrolyte and pore electrolyte, two variables are defined, φ l and cl. Assuming
electroneutrality, cl denotes both the Li+ concentration and the An- concentration.

The domain equations in the electrolyte are the conservation of current and the mass
balance for the salt according to the following:

2σ l RT ∂ ln f
∇ ⋅  – σ l ∇φ l + ------------------  1 + -------------- ( 1 – t + )∇ ln c l = i tot + Q l
 F  ∂ ln c l 
∂c l i tot + Q l
ε l ------- + ∇ ⋅ ( – ε l D l ∇c l ) = R l –  --------------------- t +
∂t F

where σl denotes the electrolyte conductivity, f the activity coefficient for the salt, t+
the transport number for Li+ (also called transference number), itot the sum of all
electrochemical current sources, and Ql denotes an arbitrary electrolyte current source.
In the mass balance for the salt, εl denotes the electrolyte volume fraction, Dl the
electrolyte salt diffusivity, and Rl the total Li+ source term in the electrolyte.

In the electrode, the current density, is, is defined as

THEORY FOR THE LITHIUM-ION BATTERY INTERFACE | 277

 i s = – σ s ∇φ s

where σs is the electrical conductivity.

The domain equation for the electrode is the conservation of current expressed as

∇ ⋅ i s = – i tot + Q s

where Qs is an arbitrary current source term.

The electrochemical reactions in the physics interface are assumed to be insertion

reactions occurring at the surface of small solid spherical particles of radius rp in the
electrodes. The insertion reaction is described as

+ -
Li + e + Θ s ⇔ LiΘ s

where Θs denotes a free reaction site and LiΘs an occupied reaction site at the solid
particle surface.

The concentration of Θs does not have to be solved for since the total concentration
of reaction sites, cs,max, is assumed to be constant, implying that

c Θ s = c s, max – c s

An important parameter for lithium insertion electrodes is the state-of-charge variable

for the solid particles, denoted soc. This is defined as

cs
soc = ----------------
c s, max

The equilibrium potentials E0 of lithium insertion electrode reactions are typically

functions of soc.

The electrode reaction occurs on the particle surface and lithium diffuses to and from
the surface in the particles. The mass balance of Li in the particles is described as

∂c s
-------- = – ∇ ⋅ ( – D s ∇c s )
∂t

where cs is the concentration of Li in the solid phase. This equation is solved locally by
this physics interface in a 1D pseudo dimension, with the solid phase concentrations at
the nodal points for the element discretization of the particle as the independent
variables. The gradient is calculated in Cartesian, cylindrical, or spherical coordinates,

278 | CHAPTER 5: BATTERY INTERFACES

depending on if the particles are assumed to be best described as flakes, rods or spheres,
respectively.

The boundary conditions are as follows:

∂c
-------s- = 0
∂r r=0
∂c s
– D s -------- = – R LiΘ
∂r r = rp

where RLiΘ denotes the molar flux of lithium at the particle surface, caused by the
electrochemical insertion reactions.

The stoichiometric notations used in the physics interface are according to the general
electrochemical reaction as expressed below:

 νox Sox + ne  νred Sred

-
⇔
ox red

where the stoichiometric coefficients, νi, is positive (νox) for products and negative
(νred) for reactants in a reduction reaction. From this definition, the number of
electrons, n, in the electrode reaction can be calculated according to

n = –  zi νi
i

where zi denotes the charge of species i. According to these relations, the lithium
insertion reaction has the following stoichiometric coefficients:

ν Li+ = – 1
ν An - = 0
ν LiΘs = 1

with a resulting n = 1. These are the default settings for the reactions in this physics
interface. When modeling other reactions, such as irreversible anion oxidation or
noninsertion solid lithium metal deposition, other coefficients have to be used.

In the porous electrodes, itot, denotes the sum of all charge transfer current density
contributions according to:

THEORY FOR THE LITHIUM-ION BATTERY INTERFACE | 279

 i tot =  Av,m iloc, m
where, Av denotes the specific surface. The source term in the mass balance is
calculated from:

ν Li+, m i loc, m
R l, p = –  Av,m -------------------------------
nm F
m

It is also possible to specify additional reaction sources, Rl, src, that contribute to the
total species source according to:

R l = R l, p + R l, src

At the surface of the solid particles the following equation applies:

ν LiΘ, m i loc, m A v,m

R LiΘ = –  ---------------------------------
nm F
-------------------------------------
( N shape ε s ) ⁄ r p
m

where the last factor (normally equal to 1) is a scaling factor accounting for differences
between the surface area (Av,m) used to calculate the volumetric current density, and
the surface area of the particles in the solid lithium diffusion model. Nshape is 1 for
Cartesian, 2 for cylindrical, and 3 for spherical coordinates.

If the solid phase diffusion coefficient is very large or if the spatial concentration
gradients in the particle can be neglected, the solid phase concentration evolution in
time can be calculated from

∂ε s c
------------s- = R vΘ
∂t

The molar source RvΘ at the positive and negative electrodes is given as follows:

ν LiΘ, m A v,m i loc, m

R vΘ = –  -----------------------------------------------
nm F
-
m

A resistive film (also called solid-electrolyte interface, SEI) might form on the solid
particles resulting in additional potential losses in the electrodes. To model a film
resistance, an extra solution variable for the potential variation over the film, Δ φ s, film,
is introduced in the physics interface. The governing equation is then according to

Δφ s, film = i tot R film

280 | CHAPTER 5: BATTERY INTERFACES

where Rfilm (SI unit: Ω·m2) denotes a generalized film resistance. The activation
overpotentials, ηm, for all electrode reactions in the electrode then receives an extra
potential contribution, which yields

η m = φ s – Δφ s, film – φ l – E eq, m

INITIAL CHARGE DISTRIBUTION IN THE BATTERY CELL

The number of parameters in battery models are many, but especially setting the
charge distribution in the cell (that is, the intercalating species concentration in each
electrode material) is not always straightforward because it often requires more
detailed information than just cell voltage and capacity.

It is, however, possible to compute the initial charge distribution taking into account
that initially, when no current is applied on a battery cell and no sources of polarization
apply, it is only the difference between the positive and negative electrode material
equilibrium potentials that dictates the cell voltage. Two constraints can be set up with
the battery cell capacity and voltage as inputs for this computation:

• The battery cell capacity, Qcell,0 (SI unit: C), is equal to the sum of the charge of
cyclable species, Qcycl, in the positive and negative electrodes (and additional porous
electrode materials if present in the model):
Q cell,0 = Q cycl,pos + Q cycl,neg + Q cycl,addm

The cyclable species charge in an electrode, or an additional electrode material, is

defined as:

Q cycl,electrode = c s,avg,cycl,electrode  Fε s dΩ
Ω electrode

where εs denotes the electrode volume fraction and cs,avg,cycl,electrode is the local
average cyclable species concentration defined as:
c s,avg,cycl,electrode = c s,avg,electrode – soc min c s, max

cs,avg is the average species concentration, which initially, when no concentration

gradients are present within the electrode particles, is equal to the concentration at
the surface of the electrode particles, cs,surf. socmin is the minimum allowed
state-of-charge in the electrode material. The amount of cyclable species charge of
additional electrode materials is calculated similarly.
• The electrode potential is constant in each electrode and the difference between the
positive and negative electrode potentials is equal to cell voltage:

THEORY FOR THE LITHIUM-ION BATTERY INTERFACE | 281

  φ s dΩ  φ s dΩ
Ω pos Ω neg
E cell,0 = ---------------------- – ----------------------
dΩ  dΩ
Ω pos Ω neg

Initially, when no polarization is present in the cell, the expression is equal to

difference in the open-circuit potential of the electrode materials, Eeq:
E cell, 0 = E eq,pos ( soc pos, 0 ) – E eq,neg ( soc neg, 0 )

The cell voltage is restricted to the open-circuit potential of the electrode materials
and the cell voltage should be set within the following range:
E eq,pos ( soc max ) – E eq,neg ( soc min ) ≤ E cell,0 ≤ E eq,pos ( soc min ) – E eq,neg ( soc max )

where the subscripts max and min of the electrode state-of-charge indicate the
maximum and minimum allowed amount of intercalated species in terms of
state-of-charge in the electrode materials.
For any additional electrode material, the intercalated concentration is constrained
to fulfill
E eq,addm ( soc addm, 0 ) = φ s – φ l

Alternatively, the potential constraints can be replaced to instead constrain the initial
cell state-of-charge:

• The cell state-of-charge, soccell,0 (dimensionless), relates the battery cell capacity to
the charge of cyclable species in each electrode:
Q cycl,neg + Q cycl,addm,neg = Q cell,0 soc cell,0

Q cycl,pos + Q cycl,addm,pos = Q cell,0 ( 1 – soc cell,0 )

The cell state-of-charge ranges between 0 and 1. A state-of-charge of 0 indicates

that the cell is completely discharged and if it is 1 the cell is fully charged.

BALANCING THE ELECTRODES

The balancing of the electrodes in the cell means that the amount of electrode active
material in each electrode is designed after the battery cell capacity. In other words, the
cyclable species capacity can be fully hosted either in the positive or negative electrode
without having too much unused excess material and to keep the concentration of
intercalating species within the specified state-of-charge window. For batteries this is

282 | CHAPTER 5: BATTERY INTERFACES

of paramount importance to maximize energy density and life-time, and sometimes
also for safety reasons.

The battery interface can supply electrode volume fractions that balance the electrodes.
These are calculated by connecting the amount of active host material — that is, the
maximum amount of cyclable species in the electrode — to the cell capacity initial.
Here, the active host material in the positive electrode is set equal to the cell capacity.
In some battery chemistries, for instance lithium-ion batteries, the host material
amount in both electrodes deviate. Especially, negative carbon-based electrodes are
often set in excess compared to the positive electrode to account for irreversible losses
in the cell during operation. Cyclable species can in some cases be lost directly after cell
assembly. The following relations therefore apply:

Q cell,0
Q host,pos,0 = -----------------------------
1 – f cycl,loss

Q host,neg,0 = ( 1 + f host,neg,ex )Q host,pos,0

where Qhost (SI unit: C) is the amount of active host material, fcycl,loss the fractional
loss of cyclable species, and fhost,neg,ex the fractional excess of negative active host
material.

To calculate the electrode volume fraction, the fact that the amount of active host
material can be computed from the following equation needs to be considered:

Q host =  Δsocc s, max Fε s dΩ

Ω electrode

where Δsoc is the allowed state-of-charge window of the electrode material.

The expression for the electrode volume fraction in each electrode is therefore:

Q host,electrode,0
ε s = ----------------------------------------------------------
 Δsocc s, max FdΩ
Ω electrode

From the electrode volume fraction it is shown that the battery cell capacity should be
selected carefully, because the capacity is limited by the electrode material and size. The
capacity should never be set so that the electrode volume fraction is larger than 1.

Note that electrode balancing described as above does not take into account additional
electrode materials.

THEORY FOR THE LITHIUM-ION BATTERY INTERFACE | 283

 STRESS AND STRAIN IN INTERCALATING PARTICLES
The electrode host material can undergo significant volume changes during charging
and discharging. If concentration gradients are present in the electrode particles,
resulting in inhomogeneous elastic deformation, this will give rise to stresses.

Since atomic diffusion in solids is a much slower process than elastic deformation,
mechanical equilibrium is established much faster than that of diffusion. Hence,
mechanical equilibrium can be treated as a static equilibrium problem. In the analysis
below, the electrode particles (spheres or cylinders) are assumed to be isotropic linear
elastic solids.

The relative change in volume δV/V0 is typically dependent on the solid phase
concentration cs (or the state-of-charge variable soc). Note that cs is solved for in a 1D
extra dimension using spherical or cylindrical coordinate systems (for spheres or
cylinders, respectively), as described above. In the equations presented below, the
relative volume change is considered to be a generic function of the concentration ΔV/
V0 = fvol(cs(r)).

Particle Type: Spheres

The relationships between stress, σ(r) (SI unit: Pa), and strain, ε(r) (SI unit: 1),
expressed in the spherical coordinate system for the radial and tangential components
(considering that σ θ ( r ) = σ φ ( r ) ) are

1 1
ε r ( r ) = ---- [ σ r ( r ) – 2νσ θ ( r ) ] + --- f vol ( c s ( r ) )
E 3

1 1
ε θ ( r ) = ---- [ σ θ ( r ) – ν ( σ θ ( r ) + σ r ( r ) ) ] + --- f vol ( c s ( r ) )
E 3

where E (SI unit: Pa) is Young’s modulus and ν (SI unit:1) is Poisson’s ratio. It is
assumed that these elastic properties are independent of concentration.

The expressions for radial and tangential stresses in a spherical particle of radius rp that
satisfy the boundary condition σr(rp) = 0 and remain finite at r = 0, can be obtained as
follows, by solving the equation for static mechanical equilibrium in the absence of any
body force:
r r
 p 
σ r ( r ) = --------------------- ----3- f vol ( c s ( r′ ) )r′ dr′ – ----3- f vol ( c s ( r′ ) )r′ dr′

2E 1 1
 
2 2
3(1 – υ) r r

 p0 0 

284 | CHAPTER 5: BATTERY INTERFACES

 r r
 p 
σ θ ( r ) = ---------------------  ----3- f vol ( c s ( r′ ) )r′ dr′ + ----3- f vol ( c s ( r′ ) )r′ dr′ – f vol ( c s ( r ) )

E 2 1
 
2 2
3(1 – υ) r r
 p0 0 

where the two integrals represent contributions, respectively, one given by an integral
over the entire volume of the spherical particle and another given by an integral over
a spherical volume of radius r within the particle. Note, that the tangential component
additionally contains a local term as given by the last term in the expression.

The hydrostatic stress σh(r) (SI unit: Pa) (or the mean stress) is given by

σ r ( r ) + 2σ θ ( r )
σ h ( r ) = --------------------------------------
3

The von Mises stress σv(r) (SI unit: Pa) given by

σv ( r ) = σr ( r ) – σθ ( r )

Because of spherical symmetry, one principal shear stress is zero and the other two are
both equal to ( σ r ( r ) – σ θ ( r ) ) ⁄ 2 .

The strain energy density Ws(r) (SI unit: J/m3) accumulated as a result of the elastic
deformation for the isotropically deformed sphere is given as

2 2
σ r ( r ) + 2σ θ ( r ) – 2νσ θ ( r ) ( 2σ r ( r ) + σ θ ( r ) )
W s ( r ) = -------------------------------------------------------------------------------------------------------------
2E

The total elastic strain energy density stored in the host electrode material Ws,tot(r) (SI
unit: J/m3), which provides the driving force for fracture, is obtained as,
rp
3ε s
W s,tot ( r ) = -------
rp
3 
- W s ( r′ )r′ 2 dr′
0

where εs is the electrode volume fraction in the host material.

Particle Type: Cylinders

The relationships between stress, σ(r), and strain, ε(r), expressed in the cylindrical
coordinate system for the radial, tangential and axial components are as follows:

1 1
ε r ( r ) = ---- [ σ r ( r ) – ν ( σ θ ( r ) + σ z ( r ) ) ] + --- f vol ( c s ( r ) )
E 3

THEORY FOR THE LITHIUM-ION BATTERY INTERFACE | 285

 1 1
ε θ ( r ) = ---- [ σ θ ( r ) – ν ( σ z ( r ) + σ r ( r ) ) ] + --- f vol ( c s ( r ) )
E 3

1 1
ε z ( r ) = ---- [ σ z ( r ) – ν ( σ r ( r ) + σ θ ( r ) ) ] + --- f vol ( c s ( r ) )
E 3

The expressions for radial, tangential and axial diffusion-induced stresses for a
transversely isotropic cylindrical particle of radius rp are,
r r
 p 
E -  ---- 1- 1- 
σr ( r ) = --------------------
3 ( 1 – υ )  r2
f vol ( c s ( r′) )r′dr′ – ----
r
2
f vol ( c s ( r′ ) )r′dr′ 
 p0 0 

r r
 p 
σ θ ( r ) = --------------------- ----2- f vol ( c s ( r′ ) )r′dr′ + ----2- f vol ( c s ( r′ ) )r′dr′ – f vol ( c s ( r ) )

E 1 1
3(1 – υ)  r  r
 
 p0 0 

r
 p 
σ z ( r ) = ---------------------  ----2- f vol ( c s ( r′ ) )r′dr′ – f vol ( c s ( r ) )
E 2
3(1 – υ) r  
 p0 

The hydrostatic stress σh(r) is given by,

σr ( r ) + σθ ( r ) + σz ( r )
σ h ( r ) = ------------------------------------------------------
3

The von Mises stress σv(r) is given by

2 2 2
( σr ( r ) – σθ ( r ) ) + ( σθ ( r ) – σz ( r ) ) + ( σz ( r ) – σr ( r ) )
σv ( r ) = -----------------------------------------------------------------------------------------------------------------------------------------
2

The strain energy density Ws(r) accumulated as a result of the elastic deformation for
the isotropically deformed cylinder is given as

2 2 2
σ r ( r ) + σ θ ( r ) + σ z ( r ) – 2ν ( σ r ( r )σ θ ( r ) + σ θ ( r )σ z ( r ) + σ z ( r )σ r ( r ) )
W s ( r ) = ---------------------------------------------------------------------------------------------------------------------------------------------------------------------------
2E

The total elastic strain energy density stored in the host electrode material Ws,tot(r) is
given as
rp
2ε s
W s,tot ( r ) = -------
rp
2
- W s ( r′ )r′dr′

0

286 | CHAPTER 5: BATTERY INTERFACES

References
1. K.E. Thomas, J. Newman, and M. Darling, Mathematical Modeling of Lithium
Batteries, Chapter 12 in Advances in Lithium-Ion Batteries, edited by W.A. van
Schalkwijk and B Scrosati, 2002, Kluwer Academic/Plenum Publishers.

2. M. Doyle and others, J. Electrochem. Soc., vol. 143, p. 1890, 1996.

3. D Baker and M Verbrugge, [Link] Sources, 185 (2008) 1398–1407,

Thermodynamic model development for lithium intercalation electrodes

THEORY FOR THE LITHIUM-ION BATTERY INTERFACE | 287

 Theory for the Battery with Binary
Electrolyte Interface
The Battery with Binary Electrolyte Interface defines the current balance in the
electrolyte, the current balances in the electrodes, the mass balance for a salt, and the
mass balance of an intercalating species such as hydrogen in a nickel-metal hydride
battery.

The electrolyte in the modeled batteries has to be a quiescent alkaline binary 1:1
electrolyte, containing a cation (Cat+) and an anion (An-).

The physics interface solves for five dependent variables:

• φ s, the electric potential,

• φ l, the electrolyte potential
• Δ φ s, film, the potential drop due to a resistive film on the electrode particles in the
porous electrodes
• cs, the concentration of an intercalating species in the electrode particles
• cl, the electrolyte salt concentration

In the electrolyte and pore electrolyte, two variables are defined: φ l and cl. Assuming
electroneutrality, cl denotes both the Cat+ concentration and the An- concentration.

The domain equations in the electrolyte are the conservation of current and the mass
balance for the salt according to the following:

∇ ⋅ i l = i tot + Q l
2σ l RT ∂ ln f cl
i l = – σ l ∇ϕ l – ------------------  1 + --------------  t + + ----- ∇ ln c l
F ∂ ln c l c0
∂ε l c l
- + ∇ ⋅ Nl = Rl
-----------
∂t
il t+
N l = – D l ∇c l + ---------
F

where il denotes the electrolyte current density, σl the electrolyte conductivity, f the
activity coefficient for the salt, t+ the transport number for Cat+ (also called
transference number), itot the sum of all electrochemical current sources, c0 the solvent

288 | CHAPTER 5: BATTERY INTERFACES

concentration, and Ql denotes an arbitrary electrolyte current source. In the mass
balance for the salt, Nl denotes the flux of the cation, εl the electrolyte volume fraction,
Dl the electrolyte salt diffusivity, and Rl the total Cat+ source term in the electrolyte.

In the electrode, the current density, is, is defined as

i s = – σ s ∇φ s

where σs is the electrical conductivity.

The domain equation for the electrode is the conservation of current expressed as

∇ ⋅ i s = – i tot + Q s

where Qs is an arbitrary current source term.

Reactions occur on the surface of small solid spherical host particles of radius rp. The
reactions can either be electrochemical or chemical adsorption/desorption reactions
not involving electrons.

The electrochemical reactions involve cations or anions and are written generally as

+ - -
ν Cat+ Cat + ν An- An + ne + ν s Θ s ⇔ ν s SΘ s + X+…

where Θs is a free reaction site and SΘs is an occupied reaction site at the solid particle
surface. Additional product species (X, …) are not handled by this physics interface.

The absorption/desorption chemical reactions that do not involve charged species and
are written generally as:

ν s SΘ s ⇔ ν s Θ s + X+…

with a reaction rate k (SI unit: mol/(s·m2)). The signs νs is here positive, and the
reaction rate is defined as positive for reactions going from left to right.

The concentration of Θs does not have to be solved for because the total concentration
of reaction sites, cs, max, is assumed to be constant, implying that

c Θs = c s, max – c s

An important parameter for intercalation electrodes is the state-of-charge variable soc

for the solid particles, defined as

THEORY FOR THE BATTERY WITH BINARY ELECTROLYTE INTERFACE | 289

 cs
soc = -----------------
c s, max

The equilibrium potentials Eeq of intercalation electrodes reactions are typically

functions of the soc.

The reactions occur on the particle surface only, but the intercalant species can be
transported within the particles by diffusion. Within the particles the mass balance can
be written as

∂c s
-------- = – ∇ ⋅ ( – D s ∇c s )
∂t

where cs is the concentration of the intercalating species. This equation is solved locally
by this physics interface in a 1D extra (pseudo) dimension, using a finite element
discretization with the solid phase concentration as dependent variable. The
divergence and gradient operator in the above equation are be applied using either
spherical, cylindrical or Cartesian coordinates, depending on the particle type (spheres,
cylinders, or flakes).

The boundary conditions are as follows:

∂c
-------s- = 0
∂r r=0
∂c s
– D s -------- = R s, tot
∂r r = rp

where Rs, tot is the total surface molar flux of the intercalating species due to the
electrochemical and chemical reactions.

The stoichiometric notations used in the physics interface are according to the general
electrochemical reaction as expressed below:

 νox Sox + ne  νred Sred

-
⇔
ox red

where the stoichiometric coefficients, νi, are positive (νox) for products and negative
(νred) for reactants in a reduction reaction. From this definition, the number of
electrons, n, in the electrode reaction can be calculated according to

290 | CHAPTER 5: BATTERY INTERFACES

 n = –  zi νi
i

where zi denotes the charge of species i.

In the porous electrodes, itot denotes the sum of all charge transfer current density
contributions according to:

i tot =  Av,m iloc, m

where Av denotes the specific surface. The source term in the mass balance is calculated
from:

ν Cat +, m i loc, m
R l, p = –  A v,m -----------------------------------
nm F
m

It is also possible to specify additional reaction sources, Rl, src, that contribute to the
total species source according to:

R l = R l, p + R l, src

At the surface of the solid particles you have that

ν sΘ, m i loc, m A v,m

R s, electrochem = –  ------------------------------
nm F
- -------------------------------------
( N shape ε s ) ⁄ r p
m

where the last factor (normally equal to 1) is a scaling factor accounting for differences
between the surface area (Av,m) used to calculate the volumetric current density, and
the surface area of the particles in the solid lithium diffusion model. Nshape is 1 for
Cartesian, 2 for cylindrical, and 3 for spherical coordinates.

The surface area is commonly derived from the electrode volume fraction, particle size
and shape according to

N shape ε s
A v, m = -----------------------
rp

If the solid phase diffusion coefficient is very large and/or if the spatial concentration
gradients in the particle can be neglected, the solid phase concentration evolution in
time can be calculated from

THEORY FOR THE BATTERY WITH BINARY ELECTROLYTE INTERFACE | 291

 ∂ε s c
------------s- = R v, tot
∂t

The molar source, Rv, tot, due to the electrochemical and chemical reactions at the
positive and negative electrodes is given as follows:

ν sΘ, m A v,m i loc, m

R v, tot = –  ---------------------------------------------
nm F
–  ν s, m A v,m k m
m m

A resistive film (also called solid-electrolyte interface, SEI) might form on the solid
particles resulting in additional potential losses in the electrodes. To model a film
resistance, an extra solution variable for the potential variation over the film, Δ φ s,film,
is introduced in the physics interface. The governing equation is then according to

Δφ s, film = i tot R film

where Rfilm (SI unit: Ω·m2) denotes a generalized film resistance. The activation
overpotentials, ηm, for all electrode reactions in the electrode then receives an extra
potential contribution, which yields

η m = φ s – Δφ s, film – φ l – E eq, m

It is also possible to model an electrode reaction at the interface between an electrolyte

and a solid conductor. Typically a reaction of interest could be

+ -
Cat + e ⇔ Y ( s )

where Y could be some metal deposited on the electrode surface. Because this is not
an insertion reaction, cs is of no relevance at this boundary. The stoichiometric
coefficients for the above reaction are:

ν Cat+ = – 1
ν An- = 0

This results in the following boundary condition for the species flux at the electrode -
electrolyte interface

ν Cat+, m i m
n ⋅ Nl = –  --------------------------
nm F
-
m

and the following condition for the currents:

292 | CHAPTER 5: BATTERY INTERFACES

 i tot =  im
i l ⋅ n = i tot
i s ⋅ n = – i tot

where the normal vector n points into the electrolyte domain.

Initial Charge Distribution in the Battery Cell

The number of parameters in battery models are many, but especially setting the
charge distribution in the cell (that is, the intercalating species concentration in each
electrode material) is not always straightforward because it often requires more
detailed information than just cell voltage and capacity.

It is, however, possible to compute the initial charge distribution taking into account
that initially, when no current is applied on a battery cell and no sources of polarization
apply, it is only the difference between the positive and negative electrode material
equilibrium potentials that dictates the cell voltage. Two constraints can be set up with
the battery cell capacity and voltage as inputs for this computation:

• The battery cell capacity, Qcell,0 (SI unit: C), is equal to the sum of the charge of
cyclable species, Qcycl, in the positive and negative electrodes:
Q cell,0 = Q cycl,pos + Q cycl,neg

The cyclable species charge in an electrode is defined as:

Q cycl,electrode = c s,avg,cycl,electrode  Fε s dΩ
Ω electrode

where εs denotes the electrode volume fraction and cs,avg,cycl,electrode is the local
average cyclable species concentration defined as:
c s,avg,cycl,electrode = c s,avg,electrode – soc min c s, max

cs,avg is the average species concentration, which initially, when no concentration

gradients are present within the electrode particles, is equal to the concentration at
the surface of the electrode particles, cs,surf. socmin is the minimum allowed
state-of-charge in the electrode material.
• The electrode potential is constant in each electrode and the difference between the
positive and negative electrode potentials is equal to cell voltage.

THEORY FOR THE BATTERY WITH BINARY ELECTROLYTE INTERFACE | 293

  φ s dΩ  φ s dΩ
Ω pos Ω neg
E cell,0 = ---------------------- – ----------------------
dΩ  dΩ
Ω pos Ω neg

Initially, when no polarization is present in the cell, the expression is equal to

difference in the open-circuit potential of the electrode materials, Eeq:
E cell, 0 = E eq,pos ( soc pos, 0 ) – E eq,neg ( soc neg, 0 )

The cell voltage is restricted to the open-circuit potential of the electrode materials
and the cell voltage should be set within the following range:
E eq,pos ( soc max ) – E eq,neg ( soc min ) ≤ E cell,0 ≤ E eq,pos ( soc min ) – E eq,neg ( soc max )

where the subscripts max and min of the electrode state-of-charge indicate the
maximum and minimum allowed amount of intercalated species in terms of
state-of-charge in the electrode materials.

Alternatively, the second constraint can be replaced with another to allow the initial
cell voltage input to be replaced with initial cell state-of-charge:

• The cell state-of-charge, soccell,0 (dimensionless), relates the battery cell capacity to
the charge of cyclable species in each electrode.
Q cycl,neg = Q cell,0 soc cell,0

Q cycl,pos = Q cell,0 ( 1 – soc cell,0 )

The cell state-of-charge ranges between 0 and 1. A state-of-charge of 0 indicates

that the cell is completely discharged and if it is 1 the cell is fully charged.

Balancing the Electrodes

The balancing of the electrodes in the cell means that the amount of electrode active
material in each electrode is designed after the battery cell capacity. In other words, the
cyclable species capacity can be fully hosted either in the positive or negative electrode
without having too much unused excess material and to keep the concentration of
intercalating species within the specified state-of-charge window. For batteries this is
of paramount importance to maximize energy density and life-time, and sometimes
also for safety reasons.

The battery interface can supply electrode volume fractions that balance the electrodes.
These are calculated by connecting the amount of active host material — that is, the

294 | CHAPTER 5: BATTERY INTERFACES

maximum amount of cyclable species in the electrode — to the cell capacity initial.
Here, the active host material in the positive electrode is set equal to the cell capacity.
In some battery chemistries, for instance lithium-ion batteries, the host material
amount in both electrodes deviate. Especially, negative carbon-based electrodes are
often set in excess compared to the positive electrode to account for irreversible losses
in the cell during operation. Cyclable species can in some cases be lost directly after cell
assembly. The following relations therefore apply:

Q cell,0
Q host,pos,0 = -----------------------------
1 – f cycl,loss

Q host,neg,0 = ( 1 + f host,neg,ex )Q host,pos,0

where Qhost (SI unit: C) is the amount of active host material, fcycl,loss the fractional
loss of cyclable species, and fhost,neg,ex the fractional excess of negative active host
material.

To calculate the electrode volume fraction, the fact that the amount of active host
material can be computed from the following equation needs to be considered:

Q host =  Δsocc s, max Fε s dΩ

Ω electrode

where Δsoc is the allowed state-of-charge window of the electrode material.

The expression for the electrode volume fraction in each electrode is therefore:

Q host,electrode,0
ε s = ----------------------------------------------------------
 Δsocc s, max FdΩ
Ω electrode

From the electrode volume fraction it is shown that the battery cell capacity should be
selected carefully, because the capacity is limited by the electrode material and size. The
capacity should never be set so that the electrode volume fraction is larger than 1.

THEORY FOR THE BATTERY WITH BINARY ELECTROLYTE INTERFACE | 295

 Theory for the Lead-Acid Battery
Interface
The Lead-Acid Battery Interface uses concentrated electrolyte theory to model
electrolyte transport and electrodes of changing porosity in a lead-acid battery. The
physics interface solves for the electrolyte salt concentration, electrode porosities,
electrolyte potential, and electrode potential. The notations for these dependent
variables are the following:

• cl, dissociated salt concentration of electrolyte, here H+/HSO4-,

• ε, porosity (volume fraction of liquid electrolyte) of the porous electrodes,
• φ l, electrolyte potential, and
• φ s, electric potential in the electrodes.

A lead-acid cell typically consists of five parts: a positive porous electrode (PbO2), a
reservoir of electrolyte, a porous separator, a negative porous electrode (Pb), and two
current collectors/feeders in contact with the positive porous electrode and negative
porous electrode, respectively.

In this section:

• The Electrode Reactions Equations

• Electrode Kinetics and Active Available Surface Areas
• Electrode Charge Transport Equations
• Electrolyte Transport Equations

The Electrode Reactions Equations

The main electrode reaction in the positive (PbO2) electrode is

- + -
PbO 2 ( s ) + HSO 4 ( aq ) + 3H ( aq ) + 2e ⇔ PbSO 4 ( s ) + 2H 2 O ( l )

and in the negative (Pb) electrode

- + -
Pb ( s ) + HSO 4 ( aq ) ⇔ PbSO 4 ( s ) + H ( aq ) + 2e

During discharge of the battery the direction of the reactions are from left to right.

296 | CHAPTER 5: BATTERY INTERFACES

Electrode Kinetics and Active Available Surface Areas
The electrode kinetics, described using the Butler-Volmer expression, depends on the
electrolyte concentration according to the following:

cl γ α a Fη – α c Fη
i loc = i 0  -------------  exp  --------------- – exp  ----------------- 
 c l, ref   RT   RT  

where i0 denotes the exchange current density (SI unit: A/ m2), γ the reaction order
(dimensionless), αa the anodic charge transfer coefficient (dimensionless), αc the
cathodic charge transfer coefficient (dimensionless). The overpotential, η, is according
to the following equation:

η = φ s – φ l – E eq

During a discharge, the active surface area, av (SI unit: m2/ m3), is calculated using
the equation below:

ε – ε0 ξ
a v = a v, max  -----------------------
 ε max – ε 0

where ζ is a morphology correction parameter (dimensionless). This surface area can

also be used for side-reactions such as oxygen evolution and oxygen reduction and the
non-faradaic double layer currents.

In the charging reactions, PbSO4 is a reactant but also an insulator, reducing the
available active surface area. To account for this effect, the following expression can be
used for the active surface area for the charging reactions:

ε – ε 0 ξ ε max – ε
a v, charge = a v, max  -----------------------  -----------------------
ε max – ε 0 ε max – ε 0

Electrode Charge Transport Equations

Ohm’s law describes the transport of charge in the electrode’s current collectors and
feeders:

i s = – σ s ∇φ s

In the porous electrode domains the following expression is used:

exm
is = –ε σ s ∇φ s

THEORY FOR THE LEAD-ACID BATTERY INTERFACE | 297

 where ε denote the porosity of the electrode and exm is an empirical parameter that
describes the correction factor for the effective transport properties.

Current conservation is described by ∇ ⋅ i s = Q s . Here Qs is the sum of all current

contributions.

Electrolyte Transport Equations

A modified version of Ohm’s law describes the charge transport in the electrolyte. In
the reservoir, the current density expression is defined as

σ l RT
i l = – σ l ∇φ l +  -------------- ( 1 – 2t + )∇ ln c l
F

where σl denotes the electrolyte conductivity, R the molar gas constant, T the
temperature, F Faraday’s constant, and t+ the transport number.

In the porous domains (the separator and the porous electrodes), it is defined as

ex σ l RT
i l = ε ( – σ l ∇φ l ) + ε  -------------- ( 1 – 2t + )∇ ln c l
ex
 F 

Current conservation is described by ∇ ⋅ i l = Q l . Here Ql denotes the sum of all

current contributions.

The dissociated salt ions can be transported due to convection, migration and
diffusion. The molar flux vector, Nl, (SI unit: mol/m2 s), is written as:

N l = – D∇c l + uc l

Where D (SI unit: mol/(s /m2)) is the binary diffusion coefficient into which the
migration effects are incorporated, and u (SI unit: m/s) is the volume averaged
velocity.

In the reservoir, the material balance equation is

∂
c = ∇ ⋅ ( D∇c l ) – u ⋅ ∇c l
∂t l

In the porous electrodes the electrochemical reactions give rise to sources in the
material balance equation, resulting in

∂ ex
ε c = ∇ ⋅ ( ε D∇c l ) – u ⋅ ∇c l + R l
∂t l

298 | CHAPTER 5: BATTERY INTERFACES

where Rl is the a source term (SI unit: mol/s /m3) resulting from the electrochemical
reactions. This source term is according to the equation below:

a v, m i m
Rl = –  ------------------
nm F
- ( ( 1 – c l V e ) ( ( 1 – t + )ν
+
H ,m
+ t + ν HSO , m ) – c l V 0 ν H2O, m )
-
4

where nm denotes the number of electrons involved in reaction (dimensionless), V 0

the partial molar volume of the solvent (H2O) (SI unit: m3/mol), V e the partial molar
volume of the electrolyte (SI unit: m3/mol),

ν H +, m

the stoichiometric coefficients for the proton,

ν HSO - , m
4

the stoichiometric coefficient for the bisulfate ion, and

ν H2O, m

the stoichiometric coefficient for water in reaction m.

In the separator, the corresponding transport equation is used for the electrolyte, but
where the source term, Rl, is zero.

For a boundary, the flux of electrolyte species due to the electrochemical reactions is
calculated according to

im
n ⋅ Nl = –  -----------
nm F
- ( ( 1 – t + )ν
H ,m
+ + t + ν HSO , m )
-
4

As the solid material in the electrodes react, the porosity changes due to volume
changes. This is described by the equation below:

∂ε a v, m i m
∂t
=  ------------------
nm F
- ( ν Pb, m V Pb + ν PbO2, m V PbO2 + ν PbSO4, m V PbSO4 )
m

where V i denotes the molar volumes (SI unit: m3/mol) for the solid materials in the
electrodes,

ν Pb, m

the stoichiometric coefficient of lead,

THEORY FOR THE LEAD-ACID BATTERY INTERFACE | 299

 ν PbO2, m

the stoichiometric coefficient of lead oxide, and

ν PbSO4, m

the stoichiometric coefficient for lead sulfate in reaction m. For a species with a known
density, ρi (SI unit: kg/m3), and molar mass Mi it can be calculated as

Mi
V i = -------
ρi

In the separator the porosity is constant.

For results and analysis purposes the following state-of-charge expression, soc, for the
electrodes, is also defined

ε – ε0
soc =  -----------------------
 ε max – ε 0

Assuming that the main Pb and PbO2 reactions are the main contributions to the
currents in each electrode, the average superficial velocity in each electrode
compartment can be calculated as

il
u PbO2 = – ------- ( ( V PbSO4 – V PbO2 – ( 3 – 2t + )V e + 2V 0 ) ) )
2F

and

il
u Pb = – ------- ( V Pb – V PbSO4 – ( 1 – 2t + )V e )
2F

Because the reservoir is normally adjacent to the positive PbO2 electrode,

u ≈ u PbO2

is usually a good approximation in the reservoir and

u ≈ u Pb

can be used in the separator.

These assumptions result in a noncontinuous velocity, and hence a noncontinuous

convection contribution to the electrolyte transport, at the interface between the

300 | CHAPTER 5: BATTERY INTERFACES

separator and reservoir domains. The physical background to this is that as water is
either consumed or created at the positive electrode during charge or discharge, the
liquid level in the reservoir either rises or falls. However, the combination of low
velocities and moderate concentration gradients at the separator/reservoir interface
makes these velocity approximations acceptable in most cases.

THEORY FOR THE LEAD-ACID BATTERY INTERFACE | 301

 Theory for the Single Particle
Battery Interface
The Single Particle Battery Interface models the charge distribution in a battery by
accounting for solid diffusion in the electrode particles and the intercalation reaction
kinetics. The ohmic potential drop in the electrolyte is included in the model using a
lumped solution resistance term.

The cell potential Ecell (SI unit: V) is defined as

E cell = φ s, pos – φ s, neg = E pos – E neg + Δφ l

where φ s, pos and φ s, neg are the potentials of the electron conducting phase (one for
each electrode), Epos and Eneg are the electrode potentials, and Δφ l is the potential
drop over the electrolyte phase separating the electrodes.

The battery cell current density, icell (SI unit: A·m−2), is defined as

Δφ l
i cell = ----------
R sol

where Rsol (SI unit: Ω·m2) is the solution resistance.

For the global formulation, the potential drop in the electrolyte solution phase is
obtained by the relation

A sep i cell = I cell

where Asep (SI unit: m2) is the separator cross-sectional area and Icell (SI unit: A) is
the battery cell current.

For the local formulation, the following relation is used

 icell dvol dΩ
Ω
A sep --------------------------------
- = I cell
V cell

where Vcell is the cell volume and Ω is the selected domain where the single particle
interface is active. Note that dvol is the cell cross-sectional area in 1D, the
out