Unit 1

Battery Technology

• Battery Technology

Introduction to batteries: Redox reactions and electron transfer, the basic

principles behind battery operation. Electrochemical cells: anode, cathode,
electrolyte, and their roles in energy conversion. Key battery performance metrics.
Emerging Battery Technologies, Lead-acid batteries (working principles and
applications), Nickel-metal hydride batteries (improved efficiency, environmental
advantages, and limitations), Lithium-ion batteries (chemistry variations and
performance characteristics), exploring alternative chemistries (sodium-ion,
solid-state, and organic batteries). Limitations and Sustainability Concerns:
Charge and discharge cycles: battery degradation, Safety concerns with lithium-ion
batteries: thermal runaway, fire hazards, Environmental impact of battery
production (resource extraction, mining, and pollution).

INTRODUCTION

Can you imagine a world without batteries? The clock on your wall requires a battery for it to
work. The watch on your wrist goes on a battery. The motor vehicle needs a battery for it to start
and take you to your destination. Battery is the backbone of UPS to run your computer without
interruption. After a day’s work, if you pick-up the remote control of the television, it is again the
battery that helps you to change channels of the T.V. Cameras, laptop computers, cellular
phones, key chain laser, heart pacemaker and children’s toys – they all require batteries.
Batteries are used for so many different purposes and different applications require batteries
with different properties. The battery required to start a car must be capable of delivering a large
electrical current for a short period of time. The battery that powers a cardiac pacemaker must
be small, rugged, leak proof, compact and capable of delivering a steady current for an extended
period of time. In UPS systems, longer and consistent backup is needed. Batteries for hearing
aids must be above all tiny. Batteries for torpedoes and submarines must be stable during
storage and give high power for short times & certainly rechargeable. For a lap-top computer, a

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battery in the form of a flexible sheet distributed around the case is much preferred. Batteries
remain an enormous industry with a turnover of billions of pounds worldwide.
Primary batteries: They are galvanic cells which produce electricity from chemicals that are
sealed into it when it is made. This type of cells cannot be recharged as the cell reaction cannot
be reversed efficiently by recharging. Once the cell reaction has reached equilibrium the cell
must be discarded. No more electricity is generated, and we say the battery is ‘dead’. These are
also known as ‘throw – away’ batteries or irreversible batteries.
Eg: Dry cell, Lithium copper sulfide cell.
Secondary batteries: A secondary cell is rechargeable by passing current through it. In the
charging process, an external source of electricity reverses the spontaneous cell reaction and
restores a non- equilibrium mixture of reactants. After charging, the cell can be used for
supplying current when required, as the reaction sinks toward equilibrium again. Thus, as the
secondary cell can be used through a large number of cycles of discharging and charging. Such
cells are also known as rechargeable cells, storage cells, or accumulators.
Eg. Lead-acid batteries, Nickel-cadmium cell, Lithium- ion battery.
Requirements of Primary Battery:
• Compact, lightweight and must be fabricated from easily available raw materials.
• Economic and have benign environmental properties
• Should have a high energy density, longer shelf life
• Provide constant voltage and should have a long discharge period
Requirements of Secondary Battery
• Long shelf-life in both charged & discharged conditions
• Longer cycle life and design life
• High power to weight ratio
• Short time for a recharge.
• High voltage & high energy density

BASIC PRINCIPLE BEHIND BATTERY OPERATION

The basis for a battery operation is the exchange of electrons between two chemical reactions,
an oxidation reaction and a reduction reaction. The key aspect of a battery which differentiates
it from other oxidation/reduction reactions (such as rusting processes, etc) is that the oxidation

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and reduction reaction are physically separated. When the reactions are physically separated,
a load can be inserted between the two reactions. The electrochemical potential difference
between the two batteries corresponds to the voltage of the battery which drives the load, and
the exchange of electrons between the two reactions corresponds to the current that passes
through the load. The components of a battery, which are shown in the figure below, and consist
of an electrode and electrolyte for both the reduction and oxidation reaction, a means to
transfer electrons between the reduction and oxidation reaction (usually this is accomplished
by a wire connected to each electrode) and a means to exchange charged ions between the two
reactions.

The key components which determine many of the basic properties of the battery are the
materials used for the electrode and electrolyte for both the oxidation and reduction reactions.
The electrode is the physical location where the core of the redox reaction – the transfer of
electrons – takes place. In many battery systems, including lead acid and alkaline batteries, the
electrode is not only where the electron transfer takes places but is also a component in the
chemical reaction that either uses or produces the electron. However, in other battery systems
(such as fuel cells) the electrode material is itself inert and is only the site for the electron
transfer from one reactant to another. For a discharging battery, the electrode at which the
oxidation reaction occurs is called the anode and has a positive voltage, and the electrode at
which the reduction reaction occurs is the cathode and is at a negative voltage.

Battery

Batteries are devices that store energy in the form of chemical energy and convert it when
required to electrical energy. Through the electrochemical reactions that occur in a battery,
electrons are released and flow from one conductor (electrode) to another through external
electric circuit providing an electric current that is used to do tasks. At the same time, charged
ions are transported through an electrically conducting solution (electrolyte), which is in
contact with the electrodes to bring the reactants to the electrode/electrolyte interface.
The electrodes and electrolyte can be made from various materials. Variations in the
composition of the electrolyte and electrodes result in different electrochemical reactions and
charged ions. These influence the extent to which energy can be stored, as well as the operating
voltage and performance of the battery.

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A battery can be comprised of one or more electrochemical cells. An electrochemical cell
consists of two electrodes or metallic conductors, in contact with an electrolyte, an ionic
conductor. An electrode and its electrolyte comprise an electrode compartment. The two
electrodes may share the same compartment. If the electrolytes are different, the two
compartments may be joined by a salt bridge, which is a tube containing a concentrated
electrolyte solution in agar jelly that completes the electrical circuits and enables the cell to
function. So an electrochemical cell can be defined as a single arrangement of two electrodes
in one or two electrolytes which converts chemical energy into electrical energy or electrical
energy into chemical energy. Electrochemical cells can be classified into two types:
• Galvanic Cells
• Electrolytic Cells

external circuit

internal circuit

Figure 1 A schematic diagram of Electrochemical Cell

Galvanic Cells
A galvanic cell is an electrochemical cell that produces electricity as a result of the
spontaneous redox reaction occurring inside it. Galvanic cell generally consists of two
electrodes dipped in two electrolyte solutions which are separated by a porous diaphragm or
connected through a salt bridge. It is a single arrangement of two electrodes in one or two
electrolytes which converts stored up chemical energy in the form of electroactive materials
(anode & cathode active materials) directly into electrical energy. The negatively charged

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electrons flow from anode to cathode and are attracted to the positive cathode through the
external circuit.

Anode vs. Cathode:

Anode ;
• the electrode at which oxidation occurs
• is where electrons are produced
• is what anions migrate towards
• has a –ve sign.
Cathode ;
• the electrode at which reduction occurs
• is where electrons are consumed
• is what cations migrate towards
• has a +ve sign
A typical galvanic cell can be illustrated by Daniel cell (Fig. 1.1.1)

-
e
v

Oxidation at Zn reduction at Cu

Half cell I (Anode compartment) Half cell II (Cathode compartment)

Figure 2 A schematic diagram of Daniel cell

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 A Daniel cell consists of two compartments, one of which contains zinc rod dipped in
zinc sulphate solution and the other with a copper rod dipped in a copper sulphate solution. The
two electrolytes are connected by a salt bridge. When the zinc and copper rod electrodes are
connected externally through a voltmeter by using a wire, the following oxidation-reduction
reactions taking place at the electrodes. At the zinc electrode, zinc goes into the solution as Zn2+
ions, liberating two electrons. In the process zinc undergoes oxidation liberating two electrons.
The positive ion flows from the salt bridge to the cathode and the zinc electrode becomes
lighter.
⚫ Zn (s) → Zn2+ (aq) + 2e- ---------------------------(1).
At the copper electrode reduction of Cu2+ ions takes place with the deposition of metallic
copper on the copper rod, by consuming two electrons. The negative ions flow from salt bridge
to anode and copper electrode becomes heavier. The ionic conduction in the solution is
coupled to the electronic conduction in the electrodes.
⚫ Cu2+ (aq) + 2e- → Cu(s) --------------------------- (2)
Each of these reactions is known as half cell reaction. The reaction (1) in which loss of electrons
takes place is called oxidation half reaction; while the reaction 2, in which gain of electrons
takes place, is called reduction half reaction. The net reaction is obtained by adding reactions 1
and 2. i.e. Zn(s)+ Cu2+ (aq) → Zn2+ (aq) + Cu(s) is called redox or oxidation – reduction reaction.
When the circuit is closed, the electrons flow from zinc to copper through the external wire to
feed the Cu2+ ions in the process of discharging copper and thus electrical energy or current is
produced which may be used for the purpose of external work.
As in the case of Daniel cell, by the combination of any two different electrodes materials one
can construct a galvanic cell. The electrode with a greater tendency to go into the solution by
liberating electrons acts as an anode, & the other one with more tendency to undergo reduction
acts as a cathode. In a galvanic cell anode is negative and the cathode is positive. The reason to
this nomenclature is that oxidation is accompanied by the liberation of electrons which are
given up to that electrode which thereby acquires a negative charge. Reduction on the other
hand, is accompanied by absorption of electrons by reactant in solution from the electrode,
which thereby acquires a positive charge. Hence the flow of electrons is from the negative
electrode to positive electrode and the direction of flow of positive electricity, which is known
as conventional current, is from the cathode to anode.

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Electrolytic cells
An electrolytic cell is an electro –chemical cell in which a non- spontaneous reaction is driven
by an external source of current although the cathode is still the site of reduction, it is now the
negative electrode whereas the anode, the site of oxidation is positive.
The electrolytic cell (Fig.1.1.2) find wide applications in the purification of metals & also in
electro deposition of a metal on to the surface of another metal, alloy or any conductor in
general, by the process of electrolysis.

Electrolyte-MgCl2

MgCl2

Figure 3 Schematic diagram of an electrolytic cell

Electrolysis involves the conversion of electrical energy into chemical energy i.e. chemical
changes are brought about by the expense of electrical energy. Since electrolysis is a non
spontaneous process, the minimum energy required to carry out such a process is equal to the
free energy increase accompanying the change, & this is equal but opposite in sign to the free
energy decrease accompanying the reverse spontaneous process. This is true when
electrolysis is carried out reversibly. However, in irreversible conditions, the potential to be
applied for electrolysis is higher than the reversible emf of the cell.
Representation of a galvanic cell
According to the present convention, a galvanic cell is represented by keeping in view the
following points:

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 1. The anode is written on the left hand side and the cathode is written on the right hand
side of cell representation.
2. The anode is written by writing the metal (or solid phase) first and then the electrolyte
along with the concentration in the bracket. The two are separated by a vertical line or a
semicolon. The electrolyte may be represented by the formula of the whole compound
or by ionic species.
Anode representation
Metal/ Metal ion (concentration) i.e. M/Mn+ (c)
Zn│Zn2+ or Zn; Zn2+ or Zn │ ZnSO4 (1M) or Zn; ZnSO4 (1M)
3. The cathode of the cell is represented by metal ion first and then the metal (or solid
phase) thereafter. The two are separated by a vertical line or a semicolon.
Cathode representation:
Mn+ (c) / M i.e. Metal ion (concentration) / Metal
e.g. Cu2+│Cu or Cu2+; Cu or Cu2+ (1M); Cu or CuSO4 (1M)/Cu
4. A salt bridge is indicated by two vertical lines, separating the two half-cells. Thus the
Daniel cell, may be represented as:
Zn │ ZnSO4 (1M)║ CuSO4(1M)/Cu
Cu(s) / Cu2+ (aq) ║Ag+(aq) / Ag (s)

Comparisons of Galvanic and Electrolytic cells

Galvanic Cell Electrolytic Cell

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1. Cell reaction is spontaneous 1. Cell reaction is non-spontaneous
2. Converts chemical energy to electrical
2. Converts electrical energy into chemical
energy energy
Anode is negative and cathode is positive 3. Anode is positive and cathode is negative
3. Usually have two electrodes and two
4. Single electrolyte and two electrodes
electrolytes
4. 5.
5. Used as a potable source of electrical Used for electrolysis apparatus like
energy in cars, flashlights and calculators electroplating and electrorefining

Example. Daniel cell Example. Electroplating of nickel

Typically, the anode and cathode are made of different types of chemical compounds or metals.
The electrolyte is a medium that allows the charged ions to be transported toward the
electrodes. In fact, the flow of positive charged ions through the electrolyte balances the
movement of negative electrons which makes the battery cell electrically neutral during its
operation. Also, a porous and electronically insulating separator is often used between the
anode and cathode to improve the mechanical strength of the electrolyte and reduce the risk of
an internal short circuit. Typically, separators have a high ionic conductivity and provide
electronic insulation. The current collectors can also provide efficient transfer of electrons and
remove heat from the electrodes. Thin foils of aluminium or copper are typically used as current
collectors.

Electromotive force
Electricity cannot flow from one electrode to another unless there is a potential difference
between the two points. The difference of potential, which causes a current to flow from the
electrode at higher potential to an electrode at lower potential is called the “electromotive
force”(e.m.f.) of the cell “or the “cell potential” and is expressed in volts V. The emf of a cell is
denoted by E cell .Mathematically,
Ecell = Ecathode- Eanode

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The driving force that pushes the negatively charged electrons away from the anode and pulls
them towards the cathode is known as emf. The E Cell depends on the nature of the electrodes
composition, (combination of electrodes, strong tendency to lose or gain electrons produces
large cell potential) temperature (E∞T) and concentration of the electrolyte solutions. To
facilitate comparison of different galvanic cells, their standard emf, denoted by E0 cell is used.
Standard emf of a cell is defined as the emf of a cell when the reactants & products of the cell
reaction are at a unit concentration or unit activity, at 298 K and at 1 atmospheric pressure
including pure solids and liquids.
The emf of a cell represents the driving force of a cell reaction. As represented by the
thermodynamic relation,
∆G = -nFE
Where ∆G is the free energy change accompanying a cell reaction, n is the number of electron
transfer during the cell reaction, and F is the Faraday constant, F = eN A, the magnitude of the
charge per mole of electrons. Hence the above equation is the key connection between the
electrical measurements on the one hand and thermodynamic properties on the other.
The cell reaction is spontaneous or feasible when ∆G is negative. ∆G can be negative only if the
emf of the cell is positive, because, the other two factors, n & F are always positive. Thus emf of
a galvanic cell is always positive. The positive emf value indicates the spontaneity of cell
reaction in the given direction. When the cell potential is large, a given number of electrons
traveling between the electrodes can do a large amount of electrical work. When the cell
potential is small, the same number of electrons can do only a small amount of work. A cell in
which the overall reaction is at equilibrium can do no work, and then the cell potential is zero.

The greater the difference, the greater is the cell potential, and the higher is the voltage. A
practical way to measure the electrical potential of an electrode (cathode or anode) is to assign
zero for the electrical potential of the reaction that occurs at the electrode and then use it as a
reference electrode.
Standard electrode potential:
Standard electrode potential is the electrode potential when the electrode is in contact with a
solution of unit concentration at 298 K involving pure solids and liquids. If the electrode involves
a gas, then the gas is at 1 atmospheric pressure. It is denoted by Eo. When elements are
arranged in increasing order (downwards) of their standard electrode potential, a series called

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electrochemical series is obtained. In a cell, the electrode with lower electrode potential has
less tendency to undergo reduction and it acts as anode similarly electrode with higher
electrode potential has higher tendency to undergo reduction and acts as cathode.
Reducing agents Stable ions Electrode half reaction E0 volts
Lithium Li+ -3.03
Potassium K+ -2.92
Aluminium Al3+ -1.66
Zinc Zn2+ -0.76
Iron Fe3+ -0.44
Lead Pb2+ -0.13
H2 2H+ 0
Copper Cu2+ 0.34
Silver Ag+ 0.80
Gold Au3+ 1.52

Figure 4 Selected standard electrode potentials

Nernst equation

Nernst equation is an expression of a quantitative relationship between electrode

potential/cell potential and concentration of the electrolyte species in an electro-chemical
reaction. i.e. mathematical expression that relates the potential of an electrode to the
concentrations of those species in solution that are responsible for the potential. Consider a
general redox reaction: Mn+(aq) + ne- M(s)

E = Eo + 2.303RT/nF log [Mn+]

E= Electrode potential at some moment in time

E0= Standard electrode potential

R= Universal gas constant (joules per mol per K)

T= Temperature in Kelvin scale F= Faraday constant (96,500 Coulumbs)

n = Number of electrons transferred in the half reaction/ cell reactions

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[Mn+]= Concentration of metal ion at that moment in time (moles per litre).

At 298 K, when the values of R.T and F are substituted, the equation reduces to,

E = Eo + (0.0592/n) log [Mn+]

This expression is known as the Nernst equation for electrode potential at 298 K. From these
equations, it is clear that,

i) If the concentration of the solution (Mn+) is increased, the electrode potential

increases and vice versa.
ii) If the temperature is increased, the electrode potential increases and vice versa.

The Nernst equation can also be applied for the calculation of emf of a cell. Consider the cell
reaction aA+ bB cC +dD

The Nernst equation for the emf of the cell is

Ecell = Eocell – 2.303RT/nF log [C]c [D]d /[A]a [B]b

At 298 K,

Ecell = Eocell – (0.0591/n) log [C]c [D]d /[A]a [B]b

Where n is the number of electrons transferred during the cell reaction and Eocell is the standard
emf of the cell.

Significance of the Nernst equation:

• To calculate the potential of a cell that operates under non-standard conditions.

• To measure the equilibrium constant for a reaction, when the overall cell potential for
the reaction is zero

E=E° - (RT/nF)lnKc where E=0

• It also helps to compute the Gibbs free energy and predict the spontaneity of an
electrochemical reaction.

ΔG = -nFE Joules

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Numericals

1. Using the electrochemical series, calculate the emf of the cell Fe(s) /Fe 2+(0.1 M) ││
Cd2+(0.2 M) / Cd at 298 K. Write the cell reactions.

From the series we have;

Eo Cd2+/Cd = − 0.40 V ; Eo Fe2+/Fe = − 0.44 V

At anode Fe →Fe2+ + 2 e−

At Cathode Cd2+ + 2 e− → Cd

Net reaction: Fe + Cd2+→ Fe2+ + Cd

EMF of the cell at 298 K is given by

Eocell = Eocathode − Eo anode

= − 0.40 − (− 0.44)

= 0.04 V

Ecell = Eocell − (0.0591 / n) log [ Fe2+ ] / [Cd2+]

= 0.04 −( 0.0591/ 2 ) log [0.1] / [0.2]

= 0.0488 V

2. Calculate E.M.F. of the zinc – silver cell at 25˚C when [Zn2+] = 1.0 M and [Ag+] = 10
M (E0cell = 1.56V at 25˚C). Write the cell representation and cell reactions
Cell representation
Zn│Zn2+(1M) ║ Ag+(10M)│Ag
Cell reaction:
Zn + 2Ag+ ↔ Zn2+ + 2Ag

0.0592
0 [Zn 2+ ]
Ecell = Ecell − 2 log [Ag + ]2

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 0.0592
Ecell = − -2
1.56 log 10
2

E cell
= 1.6192 V
0.0592 1
Ecell = 1.56 − 2 log 102
KEY BATTERY PERFORMANCE METRICS

The characteristic performance of a battery determines its suitability for the desired
application. Some of them are –

a. Current:
Current is a measure of the rate of flow of electrons during discharge. It is the amount of
charge flowing per unit time and is expressed in ampere (coulomb per second). For uniform
current, electrolyte of high conductance is desirable. Batteries provide direct current.
b. Capacity:
Capacity is the charge in ampere hours (A h) that could be obtained from the battery.
This depends on the size of the battery and is determined by the Faraday relation,
𝑚 ×𝑛 ×𝐹
𝐶=
𝑀
Where C is the capacity in A h, m is the mass of active material and M is the molar mass.

Figure 5 Battery voltage during discharging

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 The amount of active materials consumed during discharge determines the capacity of the
battery. The capacity also depends on the discharge conditions. It is measured by finding the
time ‘t’ taken for the battery to reach a minimum voltage, Ecellmin for a fixed current discharge (i
amperes). (The cell is said to be dead at minimum voltage). A plot of time against voltage at a
fixed current discharge is shown in Fig. 5 and 6 The length of the flat portion of the curve is a
measure of the capacity of the battery, the longer the flat portion better the capacity.
c. Energy Efficiency:
Energy efficiency for a storage battery is given by -
% Energy efficiency
= (Energy released on discharge / Energy required for charging) × 100
Energy efficiency depends on the current efficiency of the electrode processes, the
overpotentials during discharge and charge, and internal resistance. A battery should have high
energy efficiency.
d. Cycle Life:
The cycle life of a battery is the number of charge-discharge cycles that can be achieved
before failure occurs. (Note that cycle life applies to secondary batteries). It is necessary that
during charging the active material is regenerated in a suitable state for discharge. The
discharge-charge cycle depends on chemical composition, morphological changes, and
distribution of active materials in the cell.
The cycle life of a battery is affected by corrosion at contact points, shedding of the active
material from the plates, and shorting between the electrodes due to irregular crystal growth
and changes in morphology.
e. Shelf Life
Shelf life is the period of storage under specified conditions during which a battery retains its
performance level. Shelf life is affected by self-discharge. Self-discharge occurs when there is
a reaction between the anode and the cathode active materials or corrosion of current
collectors.
In addition, a commercial battery should have tolerance to service conditions such as variation
in temperature, vibration and shock, and should have reliable output.
f. Energy Density:
Energy density is the ratio of the energy available from a battery to its mass (or volume) (Wh/Kg)
or Wh/L.

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Energy density is determined by measuring the capacity and recording the average voltage
(voltage averaged during the discharge) and the total mass (or volume) of the battery. A battery
should have continuous energy density above a certain value or a very high energy density for a
short period.

g. Power Density:
Power density is the ratio of the power available from a battery to its mass (W/kg) or volume
(W/L). A battery should have continuous power density above a certain value or a high value for
a short period

ELECTROLYTES

The electrolyte can be a liquid, solid, polymer, or composite (hybrid) depending on the type of
battery. The electrolyte should have a high ionic conductivity, no electric conductivity,
nonreactivity with the electrode materials and a wide operating temperature range. The
traditional liquid electrolyte generally has a low viscosity, high energy density, high
charge/discharge rate capability, a relatively low operational temperature (between – 40 °C and
60 °C) and low flammability. The polymeric electrolyte can be either a gel or a solid. The solid
polymeric electrolyte has the advantageous of high flexibility, high energy density,
multifunctional applications, good safety and mechanical properties and thermal/chemical
stability. But solid polymeric electrolytes typically have low ionic conductivities at room
temperature (10−5 – 10−1 mS cm−1). Gel polymeric electrolytes, on the other hand, have
relatively high ionic conductivities (1 mS cm−1), high flexibility, multifunctional applications, and
chemically stability, but they have poor mechanical strength and poor interfacial properties.
The main advantages of a solid polymeric electrolyte are no electrolyte leakage, high safety
(nonflammability), nonvolatility, thermal and mechanical stability, ease of fabrication, and high
achievable power density and cyclability.

Lead Acid Battery/Storage Battery (Lead Accumulator or Car Battery or the acid battery)
Construction: The electrodes are lead grids. Grids are used to maximize the surface area. The
anode grid is filled with finely divided spongy lead (Pb) and the cathode grid is packed with lead
dioxide (PbO2). Both electrodes are submerged in a sulfuric acid solution (H2SO4) having a

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specific gravity of about 1.25 that acts as the electrolyte. The anode and cathode grids are
separated by insulators like strips of wood, rubber, or glass fiber. The battery is encased in a
plastic container or hard vulcanized rubber vessel. The cell doesn’t need separate anode and
cathode compartments because the oxidizing and reducing agents are both solids (PbO 2 & Pb)
that are kept from coming into contact by insulating spacers between the grids. Both anode and
cathode are immersed in a common electrolyte (i.e. cell without liquid junction). This is an
example of a wet cell because the electrolyte is an aqueous sulphuric acid solution.

Figure 6 Construction of Lead acid Battery

Discharging reactions

At the anode

Pb (s) → Pb2+ (aq) + 2e-

Pb2+(aq) + SO42-(aq) → PbSO4(s)

Pb(s)+ SO42-(aq) → PbSO4(s) + 2e-

At the cathode:

PbO2(s) + 4H+(aq) + 2e− → Pb2+(aq) + 2H2O(l)

Pb2+(aq) + SO42−(aq) → PbSO4(s)

PbO2(s) + 4H+(aq) + SO42−(aq) + 2e− → PbSO4(s) + 2H2O(l)

Overall: Pb(s) + PbO2(s) +4H+(aq) + 2SO42−(aq) → 2PbSO4(s) + 2H2O(l)

Explanation:

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At the anode, lead atoms lose two electrons (e-) and become positively charged lead ions (Pb2+).
The lead ions combine with the sulfate ions (SO42-) in the sulfuric acid solution to produce lead
sulfate (PbSO4).
At the cathode, lead dioxide gains electrons, releasing oxygen, which attaches to hydrogen ions
(H+) to produce water (H2O (l) and lead ions. The lead ions react with sulfate ions to produce
lead sulfate. As this reaction progresses, the flow of electrons creates an electric current. Lead
sulfate adheres to each electrode and water increases. The concentration of sulfuric acid
decreases and the amount of lead and lead dioxide decreases. When the reactants are
depleted, the battery stops producing electricity. The reaction can be reversed by recharging the
battery & the PbSO4 formed during discharge remains adhered to each electrode and is
available at the site during recharging. The nominal voltage of each cell is about 2.1 V. The lead
storage battery is designed to operate reversibly so that it can be used for storing electrical
energy. They are called storage batteries because their essential function is to store electrical
energy. It is used to store energy in chemical form.
Reactions during Charging:
Cathodic Reaction: PbSO4(s) + 2e- → Pb(s)+ SO42-(aq)
Anodic Reaction: PbSO4(s) + 2H2O(l) → PbO2(s) + SO42-(aq) + 4H +(aq) +2e-
Net reaction: 2PbSO4(s) + 2H2O(l) → Pb(s) + PbO2(s) +2H2SO4
Recharging is possible because PbSO4 formed during discharge adheres to the electrodes. By
attaching an external power source to a battery ( >2 volts), a current runs through the poles in
the opposite direction from normal discharge. This changes the lead sulfate and water back into
the original reactants, lead dioxide and sulfuric acid, i.e. the electrodes return to their former
composition and the sulfuric acid is regenerated. Charging, therefore, produces a gradual
increase in sulfuric acid concentration. Since the level of charge on a storage battery is related
to sulfuric acid concentration, the specific gravity of the (H2SO4) solution is a measure of the
operational condition of a battery. A charged battery at room temperature with its electrolyte at
normal concentration supplies a potential difference of 2.1 to 2.2 V. The complete reaction
cycle of a lead acid storage battery is as follows.

Discharge
Pb(s) + PbO2 + 2 H2SO4(aq) 2 PbSO4(s) + 2 H2O(l)
Charge

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In an automobile, the energy necessary for recharging the battery is provided by the generator
driven by the engine. As the external source forces electrons from one electrode to another, the
PbSO4 is converted to Pb at one electrode and PbO2 at the other.

Overcharging:
Electrolysis of water: The net reaction can be summarized by the equation.
2H2O (l) + electrical energy → 2H2(g) + O2(g)
No gases will be liberated during charging if lead ions are present in the solution. If the
electrolysis is permitted to proceed further, hydrogen gas is formed at the cathode, and oxygen
gas is evolved at the anode. The hydrogen ions are discharged at the cathode through the
reaction.
2H+(aq) + 2e-→ H2(g)
Sulphate ions are resistant to oxidation and are not discharged at the cathode. Water is oxidized
at the anode in preference to SO42-
2H2O(l) →O2(g) + 4H+(aq) + 4e-
Consequences: (i) Excessive charging may reduce the acid level and may damage the exposed
electrode grids (ii) In extreme cases, there will be dangerous high-pressure build-up that can
lead to a serious risk of explosion. In more normal circumstances, the older version of the
battery needs to be ‘topped up’ from time to time.
Recent years have seen the introduction of “maintenance–free batteries” without a gas–release
vent. Here the gassing is controlled by careful choice of the composition of the lead alloys used
i.e. by using a Pb-Ca (0.1 %) as the anode which inhibits the electrolysis of water.
Alternatively, some modern batteries contain a catalyst (e.g. a mixture of 98% ceria (cerium
oxide) & 2% platinum) that combines the hydrogen and oxygen produced during discharge back
into the water. Thus, the battery retains its potency and requires no maintenance. Such
batteries are sealed as there is no need to add water and this sealing prevents leakage of cell
materials.
Applications: Many battery designs are available for a wide variety of uses that can be classified
into three main categories. (a) Automotive (b) Industrial & (c) Consumer batteries.
The automotive type is used in cars and trucks, to provide a short burst of power for starting the
engine. It is incorporated as an essential accessory into the starting circuit of internal
combustion engines for starting, lighting & ignition (SLI). The industrial batteries are used for

19
heavy-duty applications such as motive and standby power. This class of batteries is used to
operate electric trucks, submarines, and mine locomotives. They also provide power for the air
conditioning and lighting systems. It is used in stationary backup power applications such as
telecommunication systems, to ensure that, for example, the telephone network will continue
to operate even in the event of a mains power failure. Such batteries are kept in hospital
operating theaters, railway signal centers, and other places where a power failure might be
disastrous and is used to supply electrical power during emergencies. The consumer batteries
are used in emergency lighting systems, security and alarm systems, public address systems,
power tools, UPS in computers, and vehicles.
Advantages:
• A lead storage battery is highly efficient. The voltage efficiency of the cell is defined as
follows.
• Voltage efficiency = average voltage during discharge
average voltage during charge
• The voltage efficiency of the lead–acid cell is about 80 %.
• The near reversibility is a consequence of the faster rate of chemical reactions in the
cell, i.e. anode oxidizes easily, and the cathode reduces easily leading to an overall
reaction with a high negative free energy change.
• A lead – acid battery provides a good service for several years. The number of recharges
possible ranges from 300 to 1500, depending on the battery’s design and conditions.
The sealed lead-acid batteries can withstand up to 2000 – recharging. The time
required for recharging is relatively low i.e about 2-8 hours.
• The battery has low internal self–discharge.
• A typical car battery provides a voltage of 12 V. This is not a large voltage, but the battery
can provide a large current. E.g. over 10 A, without being destroyed.
Disadvantages:
• If left unused in partially charged condition, it can be ruined in a short time by nucleation
and the growth of relatively large PbSO4 crystals, which are not easily reduced or
oxidized by the charging current. This disaster is known as ‘sulfation’.
• The lead acid battery has low energy storage to weight ratio i.e. its chief disadvantage is
its great weight. (energy density ~ 35 wh / kg)

20
 • The cell potential decreases with a decrease in concentration of sulfuric acid. During
the discharge process sulfuric acid is consumed and water is produced. So, the solution
of sulfuric acid in the cell becomes less concentrated. The state of charge of the cell can
be judged by the concentration of sulfuric acid in the liquid and this is usually done with
a simple device to measure the density of the liquid. The density of a healthy, fully
charged battery is ≥ 1.25 g/mL.
• The battery is not efficient at a lower temperature. For a battery to function properly, the
electrolyte must be fully conducting. There will be an increase in the viscosity of the
electrolyte due to a decrease in the temperature. This leads to a decrease in cell
potential.
• Overcharging may damage the exposed electrodes and may also lead to an explosion in
extreme cases. Sulfuric acid is a highly corrosive liquid. In the event of an explosion, the
electrolyte is sprayed on to the individual who is working on the battery. Therefore,
safety goggles must be worn when working with these batteries.
• Lead is toxic and hence environmental & health problems arise due to careless disposal
by consumers.
• The corrosion of the lead grid at the lead dioxide electrode is one of the primary causes
of lead acid battery failure.

Nickel-Metal Hydride (NiMH) battery:

As electronic products have come to feature more sophisticated functions, more compact
sizes, and lighter weights, the sources of power that operate these products have been required
to deliver increasingly higher levels of energy. To meet this requirement, nickel-metal hydride
batteries have been developed and manufactured with nickel hydroxide for the positive
electrode and hydrogen absorbing alloys, capable of absorbing and releasing hydrogen at high-
density levels, for the negative electrode. Because NiMH batteries have about twice the energy
density of Ni-Cd batteries and a similar operating voltage as that of Ni-Cd batteries, they have
become a mainstay in rechargeable batteries.

Construction

21
Nickel-metal hydride batteries consist of a cathode containing nickel hydroxide as its principal
active material, a anode mainly composed of hydrogen-absorbing alloys, a separator made of
fine fibers, an alkaline electrolyte, a metal case, and a sealing plate provided with a self-
resealing safety vent. Their basic structure is identical to that of Ni-Cd batteries. With
cylindrical nickel-metal hydride batteries, the electrodes are separated by the separator, wound
into a coil, inserted into the case, and sealed by the sealing plate through an electrically
insulated gasket.

Structure of Nickel-Metal Hydride Batteries

Figure 7 Construction of Nickel-Metal Hydride Battery

Hydrogen-absorbing alloys have a comparatively short history which dates back about 20 years
to the discovery of NiFe, MgNi and LaNi5 alloys. They are capable of absorbing hydrogen
equivalent to about a thousand times of their own volume, generating metal hydrides and also
of releasing the hydrogen that they absorbed. These hydrogen-absorbing alloys combine metal
(A) whose hydrides generate heat exothermically with metal (B) whose hydrides generate heat

22
endothermically to produce the suitable binding energy so that hydrogen can be absorbed and
released at or around normal temperature and pressure levels. Depending on how metals A and
B are combined, the alloys are classified into the following types: AB (TiFe, etc.), AB2 (ZnMn2,
etc.), AB5 (LaNi5, etc.) and A2B (Mg2Ni, etc.). From the perspective of charge and discharge
efficiency and durability, the field of candidate metals suited for use as electrodes in storage
batteries is now being narrowed down to AB5 type alloys in which rare-earth metals, especially
metals in the lanthanum group, and nickel serve as the host metals; and to AB 2 type alloys in
which the titanium and nickel serve as the host metals.

Nickel-metal hydride batteries employ nickel hydroxide for the positive electrode like Ni-Cd
batteries. Hydrogen is stored in a hydrogen-absorbing alloy for the negative electrode, and an
aqueous solution consisting mainly of potassium hydroxide for the electrolyte. Their charge
and discharge reactions are shown below.

As can be seen by the overall reaction given above, the chief characteristics of the principle
behind a nickel-metal hydride battery is that hydrogen moves from the positive to negative
electrode during charge and reverse during discharge, with the electrolyte taking no part in the
reaction, which means that there is no accompanying increase or decrease in the electrolyte. A
model of this battery’s charge and discharge mechanism is shown in the figure below.

23
 Figure 8 Working of Ni-MH Battery

The hydrogen-absorbing alloy negative electrode successfully reduces the gaseous oxygen
given off from the positive electrode during overcharge by sufficiently increasing the capacity of
the negative electrode which is the same method employed by NiCd batteries. By keeping the
battery’s internal pressure constant in this manner, it is possible to seal the battery.

Advantages of nickel metal hydride batteries

1. Energy density and capacity

NiMH batteries boast commendable energy density, surpassing traditional nickel-cadmium

batteries. Their capacity ranges from approximately 1000mAh to 3000mAh or higher, providing
reliable and sustained power for various devices.

2. Rechargeability and cycle life

These batteries excel in longevity, enduring hundreds to thousands of charge-discharge

cycles. Their rechargeability and ability to retain capacity over multiple cycles make them a
cost-effective and sustainable option for numerous consumer electronics and portable
gadgets.

3. Environmental friendliness

Comprising fewer harmful materials compared to certain battery types, NiMH batteries
present an environmentally friendly choice. The absence of toxic cadmium reduces
environmental impact during disposal or recycling, aligning with eco-conscious practices.

4. Enhanced safety features

24
Relative to some battery chemistries, NiMH batteries possess a safer profile, exhibiting
stability and lower risk of thermal runaway or fire hazards. This safety factor contributes to
their suitability in various applications where reliability is crucial.

5. Cost-effectiveness

NiMH batteries are known for their cost efficiency. With the capability to be recharged
hundreds to thousands of times before significant capacity loss, they offer a long-term
economic power solution, reducing the need for frequent replacements.

Disadvantages of nickel metal hydride batteries

1. High self-discharge rate

A notable drawback of NiMH batteries is their relatively high self-discharge rate. They can lose
around 1-5% of their charge per day when idle, affecting their shelf life and necessitating
regular recharging.

2. Memory effect and voltage sag

While less prone than nickel-cadmium batteries, NiMH cells can still suffer from memory
effect issues if not fully discharged before recharging. Moreover, they might exhibit voltage sag
under heavy loads, impacting performance in devices requiring consistent power output.

3. Sensitivity to temperature extremes

Extreme temperatures adversely affect NiMH battery performance. High temperatures

accelerate self-discharge and degrade the battery, while low temperatures reduce efficiency
and capacity, limiting functionality in extreme environmental conditions.

4. Limited fast charging capability

NiMH batteries have slower charging rates compared to newer technologies. Their limited
ability for rapid charging requires longer charging times, affecting convenience in fast-paced
scenarios.

5. Reduced voltage output

25
Compared to some newer battery chemistries, NiMH batteries exhibit lower voltage outputs,
affecting their compatibility with devices requiring higher voltage levels for optimal
performance.

Applications of NiMH batteries

NiMH batteries have found applications across various industries and consumer devices,
catering to diverse power needs.

Some of the typical applications include Consumer electronics, Power tools, medical devices,
Hybrid vehicles, Emergency lighting and backup power, Renewable energy storage, Flashlights
and portable devices, and Electric bicycles and scooters.

Li-Ion batteries
Li-ion batteries have revolutionized the world of portable electronics and are making
significant strides in electric vehicles and grid storage.
Construction:
The anode is a lithium-carbide intercalate (LixC6). The cathode is a transition metal oxide MO2
of variable oxidation state (MnO2, CoO2, NiO2) which can intercalate lithium usually cobalt
dioxide, CoO2 is used. The electrolyte is usually inert polar dry ether or carbonate (diethyl
carbonate or propylene carbonate), in which a conductivity salt such as LiPF6 or LiBF4 is
dissolved.

Figure 9 Schematic diagram of Rechargeable lithium ion battery

26
Working: Graphite has a layered structure and its electrochemically reduced in an aprotic
organic electrolyte containing lithium salts and lithium in interclated (or doped) between the
layers of graphite to form Lithium-Graphite interclated compound (GIC). Li-GIC undergoes
oxidation leaving an electron.
At anode:
Li ( C ) Li+ + e- + C ………………………….(1)
When a negative electrode is discharged, lithium is deinterclated (undoped) from lithiated
graphite and lithium ions dissolve into the elctrolyte. The lithium content in the LiCoO 2 electrode
reversibly changes during charge and discharge as indicated in the following equation:
At cathode:
Li+ + e- +CoO2 LiCoO2 ……………….(2)

Net cell reaction:

CoO2 + Li ( C ) Discharge LiCoO2 + C ………………….(3)
Charge
Explanations: It is called as a lithium ion battery to emphasise that it contains no lithium metal.
Both the electrodes are intercalation compounds. The electrode on the left serves as the anode
when the cell discharges. It is a special intercalation compound consisting of a graphite host
into which lithium ions have been electrochemically inserted between the carbon atom layers.
The lithiated graphite is written as LixC6. During the discharge, the lithium ions are extracted by
the half-reaction (1). The electrode that serves as cathode during discharge is normally cobalt
dioxide. The reduction half reaction is cathode during discharge is normally cobalt dioxide. The
reduction half reaction shown in eq.(2), where cobalt undergoes reduction from IV to III
oxidation state. The overall reaction is shown in eq.(3). During discharge, the Li+ ions
spontaneously migrate from the lithium graphite anode to the CoO2 cathode, enabling the
current to flow through the external circuit. When charged, cobalt ions are oxidized and lithium
ions migrate into the graphite, when discharging the battery delivers energy to the external load
and when charging it receives energy from a D.C. power source. The electrode that acts as an
anode, during discharging becomes a cathode when its charging.
Advantages
• Designed to overcome the safety problems associated with the highly reactive
properties of Lithium metal.

27
 • Long cycle life (400-1200 cycles).
• Smaller, lighter and provide greater energy density than either nickel-cadmium or
nickel-metal-hydride batteries
• Can be operated in a wide temperature range and can be recharged before they are
fully charged.
• Typically designed to be recharged in the device rather than in an external charger.
• The average voltage of a Li-ion battery is equivalent to three Ni-Cd cells.
• A typical Li-ion battery can store 150 watt-hours of electricity in 1 kilogram of battery
as compared to lead acid batteries can sore only 25 watt-hours of electricity in one
kilogram.

Limitations
• Poor charge retention
• Self discharge rate is about 10% per month
• High cost
• Traditional Li-ion batteries rely on liquid electrolytes, which are flammable and can
pose a fire risk if the battery ruptures or overheats. This is where solid-state
electrolytes emerge as a potential game-changer.
o The liquid electrolytes in Li-ion batteries have the following limitations.
a. Flammability: In case of a battery malfunction, like overheating due to external
factors or internal short circuits, these flammable organic solvents can readily ignite,
leading to thermal runaway – a potentially catastrophic chain reaction.
b. Volatility: Liquid electrolytes are prone to evaporation at high temperatures,
particularly during charging, leading to a loss of electrolyte and reduced battery
performance over time.
c. Limited Temperature Range: The performance of liquid electrolytes deteriorates
at extreme temperatures. They freeze at low temperatures, hindering ion movement
and compromising battery performance. Conversely, high temperatures can accelerate
solvent decomposition, impacting battery life and safety.
SAFETY CONCERNS WITH LITHIUM-ION BATTERIES

28
Lithium-ion batteries are widely used in current electronics because they have a high energy
density and can be recharged. Nevertheless, they also pose safety risks, mainly associated
with the possibility of thermal runaway, which can result in fires and explosions. Below are
many critical safety considerations related to lithium-ion batteries.:
a. Internal Shorts and Thermal Runaway: When a lithium-ion battery cell is damaged or
malfunctioning, it can experience internal shorts, resulting in fast heating and a chain
reaction called thermal runaway. Thermal runaway can cause the electrolyte in the
battery to deteriorate and emit flammable gasses, resulting in an accumulation of
pressure within the cell. In severe instances, this can result in the battery releasing gas,
igniting, or detonating.
b. Overcharging and Overheating: Excessive charging of a lithium-ion battery can result
in the accumulation of excessive heat, which can then lead to thermal runaway. The
majority of lithium-ion batteries are equipped with integrated protective circuits to
safeguard against overcharging. However, these circuits can malfunction under
specific circumstances. In addition, being exposed to elevated temperatures, such as
leaving a gadget inside a hot vehicle, can potentially lead to overheating and thermal
runaway.
c. Physical Damage: Mishandling a lithium-ion battery by dropping or crushing it can
cause harm to the internal components, resulting in short circuits and thermal
runaway. It is imperative to use caution while handling lithium-ion batteries and refrain
from exposing them to physical impact.
d. Manufacturing Defects: Inadequate manufacturing processes or flaws in battery cells
might heighten the probability of thermal runaway. Implementing quality control
procedures is essential for guaranteeing the safety and dependability of lithium-ion
batteries.
e. Puncture or Penetration: Intentionally or accidentally puncturing or piercing a lithium-
ion battery can result in internal shorts and initiate thermal runaway. Therefore, it is
imperative to exercise great care while dealing with defective batteries and ensure
their correct disposal.
f. Age and Degradation: Over a period of time, lithium-ion batteries undergo
degradation, resulting in a decrease in their capacity and performance. As batteries
deteriorate over time, they may become increasingly susceptible to overheating and

29
 thermal runaway. Adhering to proper maintenance practices, such as preventing
severe discharges and exposure to harsh temperatures, may significantly extend the
lifespan of lithium-ion batteries.
To reduce the safety hazards linked to lithium-ion batteries, manufacturers incorporate a range
of safety measures and practices, including as:
a. Battery Management Systems (BMS): The Battery Management System (BMS)
oversees and regulates the process of charging and discharging lithium-ion batteries in
order to avoid excessive charging, excessive discharging, and overheating.
b. Thermal Management Systems: Thermal management devices, such as heat sinks
and cooling fans, are used to disperse the heat produced during the process of
charging and discharging to prevent thermal runaway.
c. Quality Control and Testing: Manufacturers do thorough testing and quality control
inspections to detect and rectify possible flaws in battery cells before their release
into the market.
d. Safety Standards and Regulations: Governments and standards organizations set
safety rules and regulations for lithium-ion batteries to guarantee their secure design,
production, and utilization.

Exploring alternative batteries

Sodium-ion batteries (SIBs)
Sodium-ion (Na-ion) batteries emerge as a compelling contender, offering immense potential
due to the abundant and readily available element sodium (Na).

1. Sodium:
Lithium, the heart of Li-ion batteries, is a relatively rare element found in specific geological
formations. Extracting and processing lithium can be energy-intensive and geographically
limited, contributing to cost fluctuations. In contrast, sodium (Na) is the sixth most abundant
element in the Earth's crust, readily available in seawater and salt deposits.
Extracting sodium is a simpler and less energy-intensive process compared to lithium. This
translates to a more stable and potentially lower cost for the raw material used in Na-ion
batteries. This cost advantage positions sodium-ion as a potentially game-changing
technology for large-scale energy storage applications.

30
2. Similarities and Differences:
Similarities: Lithium (Li) and sodium (Na) belong to the same group (Group 1, Alkali Metals) in
the periodic table. They share similar chemical properties, readily losing their single valence
electron and transforming into positively charged ions (Li+ and Na+). This ability to lose
electrons makes them ideal candidates for battery applications.

Ionic Radius: A crucial difference exists in their ionic radii. Lithium ions (Li+) are smaller
(around 0.76 Å) compared to sodium ions (Na+) (around 1.00 Å). This difference in ionic size
has implications for how these ions interact with electrode materials in batteries.

The Flow of Ions: Li-ion and Na-ion batteries function based on the movement of ions
between electrodes during charge and discharge cycles. However, the larger size of Na+ ions
can pose a challenge for some electrode materials traditionally used in Li-ion batteries. These
materials might not offer enough space for efficient Na+ ion movement, hindering
performance.
Challenges and Advancements in Na-ion Technology:
Electrode Material Design: The key challenge lies in creating electrode materials with
structures that can efficiently accommodate the larger sodium ions. Researchers are actively
exploring novel materials like Prussian blue analogues and layered sodium vanadates that
show promise for improved Na+ ion mobility.

Performance Optimization: While advancements are being made, Na-ion batteries generally
exhibit lower energy and power densities than Li-ion batteries. Ongoing research focuses on
optimising electrode materials and electrolytes to enhance these performance metrics.
EMERGING BATTERY TECHNOLOGIES
Emerging battery technologies are constantly developing to fulfil the increasing requirements
of many industries, such as consumer electronics, electric vehicles (EVs), renewable energy
storage, and grid stability. Presented below are many noteworthy developing battery
technologies:
a. Solid-State Batteries: These batteries substitute the liquid or gel electrolyte present
in conventional lithium-ion batteries with a solid electrolyte, resulting in increased

31
 energy density, enhanced safety, and perhaps extended longevity. The improved energy
density and lower fire danger of solid-state batteries are expected to bring about a
revolution in electric vehicles (EVs) and portable gadgets.
b. Lithium-Sulfur Batteries: Lithium-sulfur batteries possess the capacity to provide
greater energy density in comparison to lithium-ion batteries. They employ sulfur as
the cathode material, which is abundant and affordable, resulting in the possibility of
reduced production expenses. Nevertheless, there are still unresolved issues that
need to be tackled, such as the low electrical conductivity of sulfur and the dissolution
of polysulfides.
c. Lithium-air batteries: Lithium-air batteries have an exceedingly elevated theoretical
energy density, with the potential to surpass even that of gasoline. The anode is
composed of lithium metal, while the cathode is made up of oxygen obtained from the
air. Nevertheless, it is necessary to address practical obstacles such as the restricted
number of cycles that lithium metal anodes may undergo and concerns over their
stability.
d. Metal-Air Batteries: Metal-air batteries, such as zinc-air and aluminum-air batteries,
employ a metal anode and oxygen derived from the atmosphere as the cathode. These
materials have large theoretical energy densities and may be inexpensive since their
component materials are abundant. Nevertheless, the issues concerning reversibility,
efficiency, and cycle life must be resolved to achieve commercial feasibility.
• Flow Batteries: Flow batteries are a type of rechargeable battery where energy is stored
in liquid electrolytes and can be charged or discharged by circulating these liquids
through an electrochemical cell. Flow batteries use two liquid electrolytes (one for each
electrode), typically stored in separate external tanks. These electrolytes contain active
materials that undergo oxidation and reduction reactions during charge and discharge
cycles. Vanadium redox flow batteries (VRFBs) are now the most prominent form. They
use vanadium ions in both the positive and negative electrolytes. This is one of the most
common flow battery types due to its stability and long lifespan. However, continuing
research aims to investigate other chemistries that can provide better energy density
and cheaper prices.

32
 These nascent battery technologies are at different phases of advancement,
spanning from initial investigation to commercial implementation. Ongoing research
and innovation in battery technology are essential for tackling difficulties and fully
harnessing their capacity to fuel the future.

Alternative energy devices

Fuel Cells

A fuel cell is a galvanic cell of a special type in which chemical energy contained in a fuel –
oxidant system is converted directly into electrical energy in a continuous electrochemical
process. It is an energy conversion device or electricity producer. The fuel cell has two
electrodes and an electrolyte like a primary cell. The reactants (i.e. fuel + oxidant) are
constantly supplied from outside and the products are removed at the same rate as they are
formed.
Cell: Fuel/ electrode/electrolyte/electrode/oxidant.
Anode: Fuel + oxygen ----------->Oxidation products+ ne-
Cathode: Oxidant + ne- ---------->Reduction products
A fuel cell consists of fuel, electrodes, electrolyte, & oxidant. Fuel undergoes oxidation at the
anode and oxidant gets reduced at the cathode. The cell can produce current as long as the
reactants are supplied. Most fuel cells produce low voltages, commonly less than one volt, so
a number of them are connected in series in “fuel batteries.”

Figure 10
Construction of Fuel cell

Eg:- H2-O2 fuel cell, CH3OH-O2 fuel cell, Solid-oxide fuel cell, Molten carbonate fuel cell

33
Advantages of fuel cells
• High fuel to electricity conversion efficiency of 70-75 % while a thermal power plant
converts 35-40% chemical energy of coal into electrical energy.
• Fuel cell products do not cause pollution problems such as noise pollution, chemical
pollution and thermal pollution normally associated with conversional power plants.
• Fuel cell power plants can be located near the point of use electricity such as on an
urban location, rather than at a remote place. So transmission and distribution lose
(~30%) could be avoided.
• A fuel cell will produce a steady electric current as long as fresh reactants are available.

1. Methanol Fuel Cells

Construction and Working
Electrolyte:- Sulphuric acid
Electrodes:- Typical gas diffusion electrodes, made up of porous C coated with Pt
catalyst.
Fuel:- Methanol
Oxidant:- Air
Catalyst:- Platinum
Operating temperature:- 30 – 80oC.
Charge-carrier:- H+

Mechanism for Methanol Oxidation

• Electrosorption (forming Pt-CH2OH, Pt2-CHOH species) of methanol onto Platinum layer
deposited on membrane electrode assembly (MEA)
• Addition of oxygen to adsorbed carbon-containing intermediates generating CO2

34
 Figure 11 Schematic Diagram of a Methanol Fuel Cell

2. Proton exchange membrane fuel cell (PEMFC)

Polymer electrolyte membrane fuel cells – also called proton exchange membrane fuel cells –
deliver high power density and offer the advantages of low weight and volume, compared to
other fuel cells. PEM fuel cells use a solid polymer as an electrolyte and porous carbon
electrodes containing a platinum catalyst. They need only hydrogen, oxygen from the air, and
water to operate and do not require corrosive fluids like some fuel cells. Polymer electrolyte
membrane fuel cells operate at relatively low temperatures, around 80 oC (176 oF).
Low temperature operation allows them to start quickly (less warm-up time) and results in less
wear on system components, resulting in better durability. However, it requires that a noble-
metal catalyst (typically platinum) be used to separate the hydrogen’s electrons and protons,
adding to system cost. The platinum catalyst is also extremely sensitive to CO poisoning,
making it necessary to employ an additional reaction to reduce CO in the fuel gas if the hydrogen
is derived from an alcohol or hydrocarbon fuel. This also adds cost. Developers are currently
exploring Pt/Ru catalysts that are more resistant to CO.
Role of Proton conducting membranes:
35
• The membrane function in two ways: It acts as the electrolyte which provides ionic
communication between the anode and the cathode and also it serves as the separator for
the two-reactant gases.
• Optimized proton and water transport properties of the membrane and proper water
management are crucial for efficient fuel cell operation.
• Dehydration of the membrane reduces the proton conductivity and excess of water can
lead to the flooding of the electrolyte. Both conditions result in poor performance.
• The absence of solution-phase electrolyte in PEF fuel cells, compared to alkaline and
phosphoric acid fuel cells greatly reduces the complexity of the fuel and oxidant flow
controls.
• Polymeric electrolyte is carbon dioxide tolerant.
• The most important breakthrough came with the development of perflourinated membrane
by DuPont. From 1966, the membrane requirements were best met by nafion family of
perfluorinated ionomer membranes. Lifetimes over 60,000 hrs have been achieved at 353
K. Their general formula is

F F F F F F F F F

C C C C C C C C C

F F F F O F F F F

F C F

F C F

F C F

F C F

O=S=O
Construction: -
O
+
H
Electrolyte:-Ion exchange polymeric membranes. This is an excellent insulator, but
an excellent conductor of H+ ions. The material used, consists of a fluorocarbon polymer
backbone, similar to Teflon, to which sulphonic acid groups are fixed to the polymer and cannot
leak out, but the protons of these groups are free to migrate through the membrane.

36
Electrodes:- Typical gas diffusion electrodes, made up of porous C impregnated with Pt
catalyst. Noble metal treated carbon fiber paper/cloth which is directly bonded to the polymer
membrane at an elevated temperature and pressure (The catalytic electrode/membrane
configuration is referred to as membrane electrodes assemble, MEA).
Fuel:- Hydrogen
Oxidant:- Air
Catalyst:-Platinum
Interconnect:- Carbon or metal
Operating temperature:- 40 – 80 oC.
Charge-carrier:-H+

Figure 12 Schematic
of a typical PEMFC
electrode, which displays three layers

(i) A Teflonized substrate (typically, carbon cloth)

(ii) A diffusion layer, generally formed by carbon particles of about 0.1 μm size with Teflon.
(iii) An active layer, where Pt catalyst grains are supported on carbon particles (Pt loading is
usually 0.4 mg/cm2or less) with or without Teflon.
Cell reactions and Function of PEMFC:
PEM fuel cells operate at around 80 oC and practical efficiency of 60 %. Power output is in the
range of 5-200 KW. They are ideal for transportation and portable power. Additional advantages
are their high response, small size and low cost. A polymer electrolyte membrane fuel cell is
unusual in that its electrolyte consists of a layer of solid polymer which allows protons to be
transmitted from one fact to the other. Porous carbon is used as the anode and cathode of the

37
PEMFC, as shown in Fig. It basically requires H2 and O2 as its inputs, though the oxidant may
also be ambient air, and these gases must be humidified. It operates at a low temperature
because of the limitations imposed by the thermal properties of the membrane itself. The
operating temperatures are around 90oC and a Pt catalyst is used.
At anode:
• H2(g) 2H+(aq) + 2e-
At cathode
1
• O2(g) + 2H+(aq) + 2e- H2O(l)
2
1
Overall reaction: H2(g) + O(g) H2O(l)
2
Applications:
• PEM fuel cells are used primarily for transportation applications and some stationary
applications.
• Due to their fast startup time, low sensitivity to orientation, and favorable power-to-weight
ratio, PEM fuel cells are particularly suitable for use in passenger vehicles, such as cars and
buses.
Advantages:
• The PEMFC has a solid electrolyte which provides excellent resistance to gas
crossover.
• The PEMFCs low operating temperature allows rapid start-up and, with the absence of
corrosive cell constituents, the use of the exotic materials required in other fuel cell
types, both in stack construction.
• PEMFCs are capable of high current densities of over 2 kW/I and 2 W/cm2.
Disadvantages:
• The low and narrow operating temperature range makes thermal management difficult,
especially at very high current densities, and makes it difficult to use the rejected heat
for cogeneration.
• Optimized proton and water transport properties of the membrane and proper water
management are crucial for efficient fuel cell operation. Dehydration of the membrane
reduces the proton conductivity and excess water can lead to the flooding of the
electrolyte. Both the conditions lead to poor performance.

38
 • Perflourinated membranes have a high cost.
• PEMFCs are quite sensitive to poisoning by trace levels of contaminants including CO,
sulfur species and ammonia.
Differences between the fuel cell and galvanic cell:
Fuel Cell Galvanic Cell

1. They do not store chemical energy They store chemical energy

2. Reactants are fed from outside the cell The reactants from an integral part of its
continuously construction.
3. Need expensive noble metal catalysts & an These special conditions are not required
optimum to an operative for their efficient
functioning.
4. Do not get discharged and no need of Get-discharged when stored – up energy is
charging exhausted.
5. Such cells never become dead as long as Limited life span in use
fresh reactants are available
6. Useful for long-term electricity generation. Useful as portable power services.
[Link] products must be continuously No such problem
removed
8. No pollutants are generated (significant Pollutants are generated after their useful
environmental benefits) life
9. Produce power from fuels They cannot generate electricity from fuels
10. Significantly higher power densities Lower power density
ENVIRONMENTAL IMPACT OF BATTERY PRODUCTION

The environmental consequences of battery manufacture differ based on several elements,

such as the battery type, the materials employed in its fabrication, the energy sources utilized
in the production process, and the existing recycling infrastructure. Below are a few crucial
factors to consider about the environmental consequences of battery manufacturing:

a. Resource Extraction: The extraction of primary resources for batteries, such as lithium,
cobalt, nickel, and graphite, can cause substantial ecological repercussions. Mining
activities can result in the degradation of habitats, pollution of soil and water, loss of
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 forests, and the relocation of indigenous tribes. Efforts to mitigate the environmental
consequences of resource extraction involve the use of responsible mining techniques
and the encouragement of material recycling and reuse.
b. Energy Intensity: The processes involved in producing batteries are frequently
characterized by high energy consumption, especially during the fabrication of electrode
materials and the construction of battery cells. The environmental ramifications of
battery manufacture are determined by the energy sources employed in the
manufacturing process. Utilizing fossil fuels in the industrial process can lead to the
release of greenhouse gases and the generation of air pollution. Adopting renewable
energy sources, such as solar or wind power, can decrease the environmental impact of
battery manufacturing by reducing carbon emissions.
c. Chemical Pollution: The process of battery manufacture necessitates the utilization of
many chemicals, a few of which possess the potential to be detrimental to both human
health and the environment if not handled with appropriate care. For instance, the
manufacturing process of lithium-ion batteries necessitates the use of solvents,
electrolytes, and coatings, which could include hazardous compounds. Strict rules and
strict adherence to industry standards are crucial to reduce chemical contamination
and guarantee the safe handling and disposal of dangerous substances.
d. Water Usage: Battery production procedures may need substantial water consumption
for purposes such as cooling, cleaning, and chemical processing. The strain on water
supplies and the impact on ecosystems might vary depending on the area and the
availability of local water. By implementing water conservation measures and practicing
water recycling wherever feasible, we may effectively reduce the negative effects
caused by water scarcity.
e. End-of-Life Management: Efficiently managing the disposal of batteries at the end of
their life cycle is crucial to minimize any negative effects on the environment. Improper
disposal or lack of recycling of batteries can result in the release of harmful chemicals
into the land and water, causing pollution and harm to ecosystems. Developing effective
recycling infrastructure and advocating for the reuse of battery materials can contribute
to minimizing the environmental impact of battery manufacturing and disposal.

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In summary, batteries are vital for facilitating the shift towards renewable energy and
electrification. However, it is imperative to carefully assess and mitigate their environmental
consequences at every stage of their existence, ranging from the extraction of raw materials to
their disposal at the end of their lifespan. Implementing sustainable practices, adopting
technical advancements, and establishing regulatory frameworks are essential for addressing
the environmental concerns linked to battery manufacture.

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