Sensors in Neural Engineering – Electrode Polarisation

Henry Lancashire

February 2024

Contact details:
Implanted Devices Group
Malet Place Engineering Building, room 8.03
Phone: 020 3108 1611
Email: [email protected]

Introduction
• The interface between the electron conductor and the ion conductor is a phase boundary (very narrow).
• How to characterise this interface?
We have already considered RA .
What are CH , VEE , and RL ?
Content
– Electrochemical cells and half-cell potentials (considered known).
– Types of reference electrodes
– Faradaic and non-faradaic processes
– Electrode polarisation

Figure 1: Equivalent circuit of the electrode-electrolyte interface (of a single electrode).

Naming Conventions
• Cations and Anions are charged particles in solution.
– Cations are positively charged (e.g. H+ ).
– Anions are negatively charged (e.g. Cl− ).
• Cathodes and Anodes are electrodes.
– Cations are attracted to the Cathode, the cathode donates electrons.
– Anions are attracted to the Anode, the anode accepts electrons.
– Conventional current leaves the electrolyte at the cathode.
• We are concerned with electrolytic cells (we apply electrical energy) so Cathodes are negative (for the purpose of
this course, but not universally).
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Potential at the interface

• VEE is the electrode potential.

• VEE occurs spontaneously, no external voltage source is needed.
→ VEE , the electrode potential
• Well characterised for several metals in 1 molar aqueous solution of their salts.

• Half-cell potential: measured against a reference electrode.

• We call this a half cell because a typical electrochemical cell consists of two electrode-electrolyte interfaces. Two
electrodes are needed to complete a circuit and for current to flow. Two electrodes are also needed to observe the
potential of an electrode, we need a comparison point: a reference electrode.

Equilibrium Potentials
• VEE is the electrode potential when no current is flowing, and no external potential difference is applied.

• In some cases VEE called the Equilibrium Potential, this is true when a defined redox couple is present and no
current is flowing. Not all electrodes have defined redox couples.
• We must also consider two other terms:
– E 0 , the standard potential, is the potential observed for a redox couple where the ratio of ionic activity 1.
′
– E 0 , the formal potential, is measured in a known solution where the concentration ratio is 1 (O:R = 1),
this accounts for varying activity as ionic strength in solution changes.
• We can bring these ideas together in Nernst’s Equation:
′
E = E0 + RT
F ln( [O]
[R] )

Equilibrium Potentials

• For an equilibrium we require a defined redox couple.

• Redox means Reduction-Oxidation.
• An example redox couple is Silver - Silver Chloride (Ag|AgCl).
AgCl + e ⇌ Ag + Cl− , E 0 = +0.222 V vs. NHE at 25◦ C.

• Consider a cell with one platinum electrode and one Ag|AgCl electrode in 1M KCl.
Pt|KCl(1M)|AgCl|Ag
• We cannot identify a redox couple for the platinum electrode for Pt|K+ Cl− , (no H2 is present in the cell): the
platinum electrode is not at equilibrium.

• The platinum electrode may have any potential between the K+ reduction and Cl− oxidation points:
K+ + e → K(s)
2Cl− → Cl2 + 2e

Equilibrium Potentials
• Platinum in salt solutions (without dissolved H2 and O2 gas) has this property where the electrode potential is
poorly defined, and can vary widely even if little or no current is flowing.

• We are first interested in the opposite condition, where the electrode has a stable, predictable potential, even if
(some) current is flowing.

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Figure 2: Ideal electrodes. An ideally polarisable electrode changes potential easily with little change in current, while
an ideally non polarisable electrode passes current easily with little change in potential. Easily is not necessarily a good
term here, there may still be kinetic barriers.

1 Reference Electrodes
Reference electrode
We will start by considering the Standard Hydrogen Electrode (SHE).
• Reference electrodes have stable half-cell potentials.
• The SHE is the recognised 0 V for all half-cell potentials.
• Pt in acid solution, with known pH and proton activity.

• H2 bubbled near Pt.

• Pt-H interface continuously refreshed: does not change.
• Low impedance.
• Not very practical (idealised).

• The SHE is an idealised electrode, the H + activity is 1, achieved with a 1 N (1 normal), in practice a 1 M
concentration of [H + ].
• The cell is described as:

• Pt | H2 (a = 1) | H + (a = 1)
• This form of notation uses | to define an interface between phases.

Figure 3: The Standard Hydrogen Electrode.

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Which Hydrogen Electrode?

SHE Saturated Hydrogen Electrode: Potentials are related to a specific ion activity (aH+ = 1) of the acid solution, with
1 N [H + ], in which the electrode is immersed and to a specific partial pressure (1 bar, 100 kPa) the hydrogen.
This is idealised.
NHE Normal Hydrogen Electrode: A synonym for SHE, except: 1 M [H + ], and 1 atm (101 kPa) H2 . Also idealised.

RHE Reversible Hydrogen Electrode: A more practical reference than the SHE. It operates with H2 at one atmosphere
pressure in H2 SO4 electrolyte with no additional ions. The RHE potential depends on pH (and aH+ ) according
to ERHE = −0.059V · pH (vs. SHE, 25 ◦ C). The electrode potential varies with pH, you should be able to see
that at pH=0 then ERHE = ESHE = 0V . Much more practical.
DHE Dynamic hydrogen electrode: A pseudo-reference electrode assembly, simulating a reversible hydrogen electrode
with an approximately 20 mV to 40 mV more negative potential (from http://www.corrosion-doctors.org/
Dictionary/Dictionary-D.htm). No hydrogen gas supply is required: hydrogen gas is evolved at the electrode
surface through application of direct current.
Mostly we do not use an SHE, NHE, RHE, or even DHE. There are limited uses. They require Hydrogen gas
(dangerous) and very carefully controlled conditions (SHE, NHE), or they require a knowledge of your system which
is not always possible (RHE, DHE). Instead we use alternative reference electrodes which achieve controlled interface
conditions by a method other than bubbling a highly flammable gas. Two such examples are the Saturated Calomel
Electrode and the Ag|AgCl electrode. Both have stable electrode potentials.

Saturated Calomel Electrode

• Calomel is a toxic mineral of Mercury Chloride (Hg2 Cl2 ).
Electrode
• Many reference electrodes are manufactured in the way described here, this is a double junction electrode

• Pt conductor in Hg with paste of Hg2 Cl2

• In KCl, potassium chloride, solution saturated with undissolved Cl− to keep the activity constant (> 4 M usually).
This is why such an electrode is called saturated, in practice recrystalised KCl can be seen in the electrolyte
demonstrating saturation. Even if some Cl− leaks out the solution will remain saturated due to replenishment
from this crystalline KCl.
• E=+0.268 V at 25◦ C vs. SCE in saturated KCl
• Closed by porous glass plugs
→ Limited flow of charges

→ High impedance

Ag/AgCl Electrode
• Chlorided Silver wire, solid AgCl (Silver Chloride).
• KCl electrolyte with known Cl− concentration. This may be saturated, but is usually not saturated. The
electrolyte in most commercial Ag/AgCl Electrodes is saturated with silver ions to reduce dissolution of the
electrode. Silver has very low solubility in water, so this is a minor contribution to the solution.
• Closed by porous glass plug. This is a single junction electrode, contrast with the double junction SCE. Both SCEs
and Ag/AgCl Electrodes can be made as single or double junctions.
• The potential to the SHE reference is tabulated. You can see that the potential depends upon concentration (like
the RHE) and upon temperature, think about Nernst’s equation.

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Figure 4: The Saturated Calomel Electrode (SCE). Many reference electrodes are manufactured in the way shown here,
this is a double junction electrode, there are two porous glass plugs. Double junctions are more stable than single
junctions; however, double junctions are more expensive and more complex to maintain, and have a higher impedance.

Other reference electrodes

• Copper - copper(II) sulfate electrode (CSE) (E = + 314 mV)
• Palladium-hydrogen electrode (E = + 50 mV)
• Mercury - mercurous sulfate electrode (MSE) (E = +0.64 V in saturated K2 SO4 , E = + 0.68 V in 0.5 M H2 SO4 )
• There are also non-aqueous electrodes. Non-aqueous electrodes are used for different chemistries, in solvents other
than water. They are not relevant to this course.

1.1 Reference electrodes in practice

Practical uses
• Why use such electrodes in biomedical applications?
– Consider a biopotential recording situation, with two electrodes.
– How precise can you be if the naturally occurring half-cell potentials that exist across your electrodes are
fluctuating?
– The electrodes previously described have known, stable, half-cell potentials.
• Most of the electrodes considered up to now are toxic.
• Silver is toxic, but with the Ag-AgCl electrode the AgCl is not very soluble (∼ 2 mg.dm−3 at 20◦ C in water).
• The KCl electrolyte can be made as a gel.

Electro-oculography (EOG)
EOG is an application where knowing electrode potential really matters, see figure below. When trying to detect
gaze there is a potential difference in the eyeball. As the eyeball moves the potential difference across the orbit changes.
Electrode potential must be constant so that small (mV) changes due to eye movement are measurable. If the electrodes
drift this would be registered as a change in gaze! Also note this application can measure near-DC changes in potential,
so low drift is crucial.

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Figure 5: The Ag/AgCl Electrode. This is a single junction electrode, contrast with the double junction SCE. Both
SCEs and Ag/AgCl Electrodes can be made as single or double junctions.

Figure 6: The electrode potentials for Ag/AgCl Electrodes at different temperatures and activities of Cl− . You can see
that the potential depends upon concentration (like the RHE) and upon temperature, think about Nernst’s equation.

Figure 7: Ag/AgCl Electrodes used for body sensing, with KCl electrolyte gel and self-adhesive backing.

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Figure 8: Electro-oculography (EOG). Slide from Nick Donaldson.

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2 Electrode Polarisation
Charge Transfer at Electrodes
• We have considered cases where no current is flowing. Or at least, cases where if current is flowing the potential
of the electrode is dominated by VEE . When current flows processes take place at electrodes.
• When current flows charge transfer processes occur.
• Processes at electrodes are:
– Faradaic, or
– Non-Faradaic.
• Faradaic reactions are where electrons cross the electrode-electrolyte phase boundary.
→ Current flows across the interface.
• Non-Faradaic reactions are where no electrons cross the interface.
→ Current can still flow (transiently) external to the electrode interface.

Non-Faradaic Processes
• Where no charge crosses the interface, we can represent this as a capacitor.
• CH is the double layer capacitance.
• CH occurs spontaneously, no external voltage source is needed.
• In the vicinity of the electrode there is reorganisation of charges across the interface
– No direct current flow → CH , sometimes Cdl , this is a capacitance due to the:
– Helmholtz Double Layer.
– Imagine the electrode and electrolyte as two plates of a capacitor, charge can build up across this interface
through reorganisation of charges. The Double Layer exists in solution, the inner layer is ions adsorbed to
the electrode surface, the outer layer is ions which are not adsorbed (remain in solution) and is at the closest
distance these ions can approach the electrode. Remember in aqueous liquids there is limited long-range
organisation past 1 to 2 molecule-molecule distances.
– Typical units: µF.cm−2 .

Faradaic Reactions
• Faradaic reactions are where electrons cross the electrode-electrolyte phase boundary.
• Oxidation or Reduction occurs.
• Faradaic reactions follow Faraday’s Law(s) of Electrolysis.

Faradaic Reactions
• Faradaic reactions follow Faraday’s Law(s) of Electrolysis.
• The amount of chemical reaction is proportional to the amount of electrical charge passed.
• Mass of product (m) ∝ Charge (Q) , Q = it.
→ m
Q = Z, Z = electrochemical equivalent of a substance.

• Chemical Equivalent Weight (E) = M

υ , M = molar mass, υ (upsilon) = valence.

• m= xM
υNA , x = number of electrons.

• m= QM
eυNA , Q = xe, e = charge on an electron.

• m= QM
Fυ , F = Faraday’s Constant, the charge on one mole of electrons.
• F = 96500 C.mol−1 .

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Figure 9: The Helmholtz double layer acts like a capacitor, and consists of an Inner Helmholtz Plane (IHP), where ions
are specifically adsorbed to the electrode surface, and Outer Helmholtz Plane (OHP), of the closest ions still in solution.
Charges are balanced across the interface (above), with positive or negative charge on the electrode causing a equal and
opposite charge in solution by electrostatics. There is a potential gradient across the double layer (below), non-adsorbed
ions do not experience lower potentials which may affect reaction rates. From Bard and Faulkner, Electrochemical
Methods, 2001.

Electrode Polarisation
• Half-cell potentials of most conductor/electrolyte pairs are unknown.
• Half-cell potentials exist when no external voltage is applied.
• What happens when a current flows?
• Charge transfer, various redox reactions.
→ Electrode polarisation.
The potential across the interface varies with the current flow.

Polarisation types
• There are 3 types of polarisation:
– Activation: the potential difference that drives reactions at the interface, depending on the activation energy.
– Concentration: a change in ion concentration due to charge transfer changes the equilibrium potential for
the reaction (usually depletes the reactants).
– Ohmic: IR drop in the electrolyte due to its volume resistance
• Sometimes, polarisation is described as an over-voltage
– η = E − Eequilibrium
– η is polarisation related to a specific reaction and that reaction’s equilibrium.

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Figure 10: Capacitance at a metal-solution interface. The charge on the metal, q M may be positive or negative, but at
all times q M = q S (charge in the solution). From Bard and Faulkner, Electrochemical Methods, 2001.

Activation polarisation
• Current flowing across the phase boundary (metal-solution) at an electrode is similar to an electron crossing a pn
junction.
• The current depends on the over-voltage (η, eta).
• Butler-Volmer equation i = i0 (e−αzf η − e(1−α)zf η )
– i0 is the exchange current
– α is the transfer coefficient (0 ≤ α ≤ 1)
– z is the charge per ion
F
– f = RT
∗ F = Faraday constant,
∗ R = Gas Constant,
∗ T = Absolute temperature

Figure 11: Butler-Volmer response: (a) i0 = 10−3 A/cm2 ; (b) i0 = 10−6 A/cm2 ; (c) i0 = 10−9 A/cm2 . In all cases,
z=1, T=298K, α=0.5. Here (a) is “non-polarisable” and (c) is “polarisable”.

Usage?
• Generally, platinum has low over-voltages (more reversible) and mercury has high over-voltages (more polarisable).
• Reducing over-voltages for hydrogen evolution has long been of great technological importance. Consider the need
for Hydrogen gas for fuel cells, we can reduce over-voltages with catalysts or electrode materials (note different axis
orientation).

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Figure 12: Reducing reaction over-potential using a catalyst. Note the unusual axis orientation, which is sometimes used
in the USA or when i is varied, ↔ = i, ↕ = E.

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Concentration Polarisation
• The potentials in the electrochemical series are for metals in solutions of defined concentration (1 M, mol.dm−3 ).
• Concentration will generally not be molar and will change with the dominant reaction.
h i
• Nernst equation E = E0 + RT nF ln CO
CR

• Ions also have a drift velocity in the electric field.

– Ions cannot move infinitely fast, so reactions become diffusion limited due to reactant depletion.

Figure 13: Concentration polarisation develops from a change in the concentrations of reactants. Where no current
is flowing the reactants are at their bulk concentrations. When Faradaic current flows reactants are depleted near the
electrode and products increased. At an anode reduced species are oxidised, at a cathode oxidised species are reduced.
The bulk concentration remains constant and reactants diffuse towards the electrode to maintain the current flow.

Figure 14: Diffusion limited current. As the current increases the rate of reactant-to-product conversion increases, and
more reactant must diffuse to the electrode. Ions in solution cannot diffuse infinitely fast, therefore a diffusion layer
develops at the electrode with a thickness dependent upon time and current. The current becomes limited to the rate
at which reactant from the bulk can diffuse to the electrode. Physical solution stirring and electric field migration are
also considered and this is sometimes refered to as mass transport limited. As the diffusion layer thickness grows with
time a linear sweep in voltage (η) will reach a peak and then decline (not shown) as the availability of reactant limits
the current.

Ohmic Polarisation
• There is resistance in wires, which can generally be neglected in biomedical situations (it is small), and resistance
in volume conductors which generally cannot be neglected.
RA Remember the access resistance?
• The volume resistance also changes the recorded potential as the current increases. In this case, of course, the
increase is linear (according to Ohm’s Law).
This is not electrode polarisation as such, as the ohmic drop occurs throughout the electrolyte, not at the
electrode-electrolyte interface.

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