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 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.

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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 and reduction reaction are physically separated.

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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

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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.
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

Fig.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

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active materials) directly into electrical energy. The negatively charged 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)

Fig.2. A schematic diagram of Daniel cell

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

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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.
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.

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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

Fig.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:
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)

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 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

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 energy Used for electrolysis apparatus like
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

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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
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.

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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
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

Fig. 1.3.2. 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+]

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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

[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 E ocell is the standard
emf of the cell.

Numericals

. Using the electrochemical series, calculate the emf of the cell Fe(s) /Fe2+(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−

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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

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.

Energetic of cell reactions:

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The relation between E and ∆G:
∆G = -nFE
Relation between E and ΔH
Enthalpy Change ΔH = nF[T(δE/δT)P –E] --------(5)

If we know emf and temperature coefficient of emf, ΔH can be calculated..

Relation between E and ΔS :
ΔS = nF(δE/δT)P ------------------(6)

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.

Fig 2: Battery voltage during charging Fig 3: Battery voltage during discharging

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

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finding the time ‘t’ taken for the battery to reach a minimum voltage, E cellmin 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. Electricity Storage Density:

Electricity storage density is a measure of the charge per unit mass stored in the
battery, The mass of the battery includes masses of the electrolyte, current collectors,
terminals, the case, and other subsidiary elements. To get high storage density the mass
of subsidiary elements should be minimum. For instance, 7g of lithium is required at
anode to give 96500 C whereas, for the same charge, 65g of zinc would be required.
d. 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.
e. 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.
f. 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

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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.
g. Energy Density:
Energy density is the ratio of the energy available from a battery to its mass (or volume)
(Wh/Kg) or Wh/L.
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.

h. 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

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
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

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 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. Flow Batteries: Flow batteries utilize liquid electrolytes stored in separate external
tanks to store energy, providing the advantages of scalability and flexibility in terms of
capacity. Vanadium redox flow batteries (VRFBs) are now the most prominent form.
However, continuing research aims to investigate other chemistries that can provide
better energy density and cheaper prices.
e. 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.
f. Sodium-Ion Batteries: Sodium-ion batteries are being investigated as a more
economical substitute for lithium-ion batteries, capitalizing on the ample availability
of sodium minerals. Although they generally have lower energy density than lithium-
ion batteries, they show potential for use in stationary energy storage applications that
emphasize cost-effectiveness above energy density.

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.

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

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solution (H2SO4) having a 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 (PbO2 & 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.

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− → 2 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:
Anode: PbSO4(s) + 2e- → Pb(s)+ SO42-(aq)
Cathode: 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.

18
 Discharge
Pb(s) + PbO2 + 2 H2SO4(aq) 2 PbSO4(s) + 2 H2O(l)
Charge

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.

19
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 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.

20
 • 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)
• 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

21
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

Nickel-metal hydride batteries consist of a positive plate containing nickel hydroxide as

its principal active material, a negative plate 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 positive and
negative plates 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

22
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 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 AB2 type alloys in which the
titanium and nickel serve as the host metals.

23
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.

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.

24
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

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

25
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

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.

26
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.

Schematic diagram of Rechargeable lithium ion battery

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:
LixC6 xLi+(solv) + 6C(s) + xe-………………………….(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
LiCoO2 electrode reversibly changes during charge and discharge as indicated in the
following equation:
At cathode:
CoO2(s) + xLi+(solv) + xe- LixCoO2(s)……………….(2)
Net cell reaction:

27
 LixC6(s) + CoO2 Discharge LixCoO2(s) + 6C………………….(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.
• 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.

28
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.

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

29
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.

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.

30
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 1.7 Fuel cell

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

Advantages of fuel cells

31
 • 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+
• 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

32
 Schematic Diagram of a Methanol Fuel Cell

Operation of Fuel Cell

Proton exchange membrane fuel cell (PEMFC)

33
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:

• 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.

34
• 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
-
O
+
H

Construction:

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.

35
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+

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.

36
(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 PEMFC, as shown in Fig. It basically requires H 2 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.

37
• 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.

• 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

38
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 & These special conditions are not
an optimum to an operative for their required
efficient functioning.
4. Do not get discharged and no need of Get-discharged when stored – up energy
charging is 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 Useful as portable power services.
generation.
7.Reaction products must be continuously No such problem
removed
8. No pollutants are generated (significant Pollutants are generated after their
environmental benefits) useful life
9. Produce power from fuels They cannot generate electricity from
fuels
10. Significantly higher power densities Lower power density
SAFETY CONCERNS WITH LITHIUM-ION BATTERIES

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.

39
 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 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.

40
 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.

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 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.
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 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.

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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