Dept of Chemistry - SAI VIDYA INSTITUTE OF TECHNOLOGY

Module – 1
Electrochemistry and Battery Technology
Course Objectives:
To provide students with knowledge of engineering chemistry for building technical
competence in industries, research and development in the field of Electrochemical and Battery
technology.

Course Outcome:
On completion of this module, students will have knowledge in Electrochemical and
concentration cells. Classical and Modern batteries and fuel cells.

Introduction:
Electrochemistry is the branch of chemistry, which deals with the interaction of matter
and electrical energy i.e., producing electrical energy from chemical reaction (spontaneous
process) or bringing out chemical reactions by applying electrical energy (non spontaneous
process). A device used for producing an electrical current from a chemical reaction (redox
reaction) is called an electrochemical cell. It gives the relationship between electrical, chemical
phenomenon and the laws of interaction of this phenomenon. The laws of electrochemistry form
the basis of electrolysis and electro synthesis.

Single electrode potential:

It is defined as the potential developed when an electrode is in contact with a solution of
its own ions. It is denoted as E.

Standard Electrode potential:

It is defined as the potential developed when an electrode is in contact with a solution of
1M concentration, at 298 K and 1 atm pressure. It is denoted as Eo.

Nernst equation:
Nernst derived an equation to establish relationship between electrode potential and
concentration of metal ion.
Due to the power output from an electrochemical cell, the free energy decreases i.e.

Under standard conditions the free energy ∆G is given by the equation

E° is a constant called standard electrode potential.

Consider a reduction reaction:

For spontaneous reaction, the change in the free energy depends on the concentration of
reacting species.

Substituting the value of Kc in above equation, we get

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 Dept of Chemistry - SAI VIDYA INSTITUTE OF TECHNOLOGY

Substitute for ∆G and ∆G° in above equation

Under standard conditions [M] = 1

Dividing eq (5) by –nF we get

Converting ln to log we get

Substituting for R = 8.314, T = 298K and F = 96500 in eqn (6) we get

or

In general Nernst equation is,

Reference electrode
Reference electrode is that whose potentials is known and used for determination of
potential of other electrodes.
Note: Types of reference electrodes:
Beyond syllabus:
Primary reference electrode:
Whose potential is fixed as zero at all temperature and pressure. Example: Standard
hydrogen electrode (SHE).
Secondary reference electrode:
Whose potential is known in connected with SHE. Secondary reference electrodes have
several advantages over SHE. These electrodes are commonly used for determining the electrode
potentials of other metals. The two commonly used secondary reference electrodes are calomel
electrode and silver-silver electrode.

Calomel Electrode:
Construction:

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 Dept of Chemistry - SAI VIDYA INSTITUTE OF TECHNOLOGY
Calomel electrode consists of long glass tube with two side tubes. One at the top to fill sat
KCl solution and the other side tube is connected to the salt bridge. Mercury is placed at the
bottom which is covered with a layer of Hg and Hg2Cl2 (calomel ) paste. The remaining portion
is filled with saturated KCl solution. A platinum wire is dipped into the mercury and is used to
provides external electrical contact. The calomel electrode is represented as,

Working:
Calomel electrode behaves as anode or cathode depending upon the nature of other
electrode.
The half-cell reaction when it acts as an anode is

The half cell reaction when it acts as a cathode is

The electrode reaction is,

Applying Nernst equation,

E= Eo - 0.0591 log [Hg]2[Cl-]2

n [Hg2Cl2]

E= Eo - 0.0591 log [Cl-]

2
The calomel electrode potential is depends on the concentration of chloride ions in KCl. If
the concentration of chloride ions increases, the potential decreases and vice versa. (The
potential of calomel is inversely proportional to the concentration of chloride ions)
The potential of calomel electrode is measured with respect to SHE and it depends on
concentration of KCl solution used.
Conc. KCl 0.1N 1N Saturated KCl
Potential (V) 0.334V 0.281V 0.242V
Applications:
• Used to determine the potential of the other electrodes.

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DR.PRASHANTH.P.A/Mr.RAVEENDRA.R.S/Mrs.S.SATHYANARAYANI/Mrs.BHAGYA.N.P
 Dept of Chemistry - SAI VIDYA INSTITUTE OF TECHNOLOGY
• It is commonly used as reference electrode in all potentiometric determinations.
• Electrode potential is reproducible.

Silver - Silver Chloride Electrode:

Construction:
It consists of a long glass tube in which saturated KCl solution is filled. A silver wire is
coated with AgCl by electrolytic process and placed inside the tube and which provides external
electrical contact. The electrode is represented as,

Working:
The electrode behaves as anode or cathode depending upon the nature of other electrode.
The half-cell reaction when it acts as an anode is

The half-cell reaction when it acts as a cathode is

The electrode reaction is

Applying Nernst equation to the above equation,

The Ag – AgCl electrode potential is depends on the concentration of chloride ions in

KCl. If the concentration of chloride ions increases, the potential decreases and vice versa. (the
potential of Ag – AgCl is inversely proportional to the concentration of chloride ions)
The potential of Ag - AgCl electrode is measured with respect to SHE and it depends on
concentration of KCl solution used.
Conc. KCl 0.1N 1N Saturated KCl
Potential (V) 0.29V 0.22V 0.199V

Applications:
1. As a secondary reference electrode in ion selective electrodes.
2. In determining whether the potential distribution is uniform or not in ship hulls and old
pipelines protected by cathodic protection.
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DR.PRASHANTH.P.A/Mr.RAVEENDRA.R.S/Mrs.S.SATHYANARAYANI/Mrs.BHAGYA.N.P
 Dept of Chemistry - SAI VIDYA INSTITUTE OF TECHNOLOGY

Measurement of standard electrode potential using calomel electrode:

The electrode potential of unknown electrode is measured by connecting to a saturated
calomel electrode through salt bridge. (The potential of saturated calomel electrode is fixed to
0.24V for sat KCl solution).
Ex: Zinc electrode coupled with saturated calomel electrode.
To measure the standard electrode potential of Zn, Zn electrode is dipped in Zinc chloride
solution and coupled with saturated calomel electrode through voltmeter. Zinc electrode acts as
anode and SCE acts as cathode. The emf of the cell is measured through voltmeter.
Representation of the cell is

The two half-cell reactions are:

The standard electrode potential is calculated by substituting the potential values in the relation

Ion-selective electrodes
The electrode, which responds to a specific ion in a mixture by ignoring other ion is
known as ion selective electrode. It consists of a thin membrane in contact with ion solution.

Glass Electrode:
This electrode works on the principle that when a thin, low resistivity glass membrane is
in contact with a solution containing H+ ions, a potential develops across the membrane and the
solution. Potential developed depends on the concentration of hydrogen ions in the solution.
Cell representation: Ag / AgCl / HCl (0.1M) / Glass/ unknown solution
Construction:
It consist of a long glass tube with a thin walled glass bulb contains 0.1 M HCl [C1].
Ag/AgCl electrode placed in to the solution to provide electrical contact. The glass electrode is
dipped in unknown solution of concentration C2, the potential developed across the membrane by
the exchange of ions with the composition of glass is known as the boundary potential Eb (E1 &
E2). Even when C1=C2 a small potential is developed across the membrane is called as
asymmetric potential.

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DR.PRASHANTH.P.A/Mr.RAVEENDRA.R.S/Mrs.S.SATHYANARAYANI/Mrs.BHAGYA.N.P
 Dept of Chemistry - SAI VIDYA INSTITUTE OF TECHNOLOGY

Working:
E1 & E2 is the potential developed at inner and outer membrane respectively
The boundary potential is,

Where n = 1

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 Dept of Chemistry - SAI VIDYA INSTITUTE OF TECHNOLOGY

Determination of pH of a Solution using Glass Electrode

The potential of a glass electrode depends on the concentration of H+ ions. Hence, pH of
a solution can be determined by using glass electrode and calomel electrode assembly. The cell
assembly is represented as
Hg/Hg2Cl2/Cl- // solution of unknown pH / glass/0.1 M HCl / AgCl / Ag

The emf of a cell is determined by using voltmeter.

Ecell is the difference b/w glass electrode potential EG and the calomel electrode potential ESCE

Electrolyte Concentration Cells :

It is galvanic cell, which consists of two identical electrodes which are in contact with
the same solution of electrolyte at different concentrations.
Example:
Consider two silver electrodes that are in contact with the AgNO3 solution of different
concentrations (M1 and M2) connected through voltmeter. The electrolytes are connected through
salt bridge.
The cell representation Ag/ AgNO3 (M1)// AgNO3 (M2)/Ag
Where M1 and M2 are the molar concentration of the Ag+ ions in the two half-cells.

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DR.PRASHANTH.P.A/Mr.RAVEENDRA.R.S/Mrs.S.SATHYANARAYANI/Mrs.BHAGYA.N.P
 Dept of Chemistry - SAI VIDYA INSTITUTE OF TECHNOLOGY

The current produced in the cell due to migration of ions from higher concentration to
lower concentration. This takes place until the concentration in the two Half -cells become
equal(M1=M2) hence the production of current becomes zero.
Apply Nernst equation for the cell reaction,

Battery Technology
Introduction
A battery is a portable energy source with three basic components-an anode (the negative
part), an cathode (the positive part), and an electrolyte. As current is drawn from the battery,
electrons start to flow from the anode through the electrolyte, to the cathode. A device enables
the energy liberated in a chemical reaction to be converted directly into electricity. The term
battery originally implied a group of cells in a series or parallel arrangement, but now it is either
a single cell or group of cells. Examples: It ranges from small button cells used in electric
watches, lead acid batteries used for starting, lighting and ignition in vehicles with internal
combustion engines. The batteries are of great importance based on the ability of some
electrochemical systems to store electrical energy supplied by the external source. Such batteries
may be used for emergency power supplies, for driving electric vehicles, etc. For the commercial
exploitation, it is important that a battery should provide a higher energy, power density along
with long shelf life, low cost and compatible rechargeable units.

Classification of Batteries:
Batteries are classified as primary (non-rechargeable), secondary (rechargeable) and
reserve (inactive until activated):

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 Dept of Chemistry - SAI VIDYA INSTITUTE OF TECHNOLOGY
Primary battery:
The batteries, which produce electrical energy at the expense of free energy of active
materials and produce energy only as long as active materials are present. These are not
rechargeable batteries and are to be discarded after the use. These batteries are called as primary
battery.
Example: Dry cell. Zn-MnO2
Secondary battery:
The rechargeable batteries that produce electrical energy at the expense of free energy of
active materials. These active materials are capable of restoring at respective electrodes on
recharge and prepare for discharge once again. Such batteries are called secondary battery.
Example: Lead acid battery, NiMH battery, Ni-Cd battery
Reserve battery:
The high current batteries in which active materials are isolated from electrolyte due to
their reactivity and are brought into contact whenever high potential is required for application
are called reserve battery.
Example: Magnesium-water activated batteries, zinc-silver oxide batteries, etc.

Characteristics of a battery:
Cell potential / Voltage:
The cell potential or voltage of the battery is determined theoretically,
Ecell = (EC – EA) - ηA – ηC - iRcell
Where EC & EA are reduction potential of cathode and anode, ηA & ηC are over potential at the
anode and cathode and iRcell is the internal resistance.
To attain the maximum cell potential or voltage from the battery, difference in the standard
electrode potential must be high, the electrode reaction must be fast to minimize the over
potential and internal resistance must be low.

Current:
“Is measure of the rate of flow of charges in a battery”.
To attain the maximum current from the battery, difference in the standard electrode potential
must be high, the electrode reaction must be fast to minimize the over potential and internal
resistance must be low.

Capacity:
“The total amount of charge stored in a battery in Ampere hours.”
The theoretical capacity may be calculated using faradays relation, C = WnF/M, where W
and M is weight and mass of the active material respectively and n is the number of moles of the
electro active material.

Electricity storage density:

“Amount of electrical energy stored per unit weight of the battery.”

Energy efficiency:
The ratio of output energy to the input energy. Higher the efficiency, very good is the
battery.
% Energy efficiency=Energy released during discharge x 100
Energy required during recharge
Cycle life:

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 Dept of Chemistry - SAI VIDYA INSTITUTE OF TECHNOLOGY
“The total number of discharge and recharge cycles that are possible before the failure
of the battery”. It is applicable only to secondary battery, higher the cycle life, better is the
battery.

Shelf-life:
“The duration of storage of a battery without self discharge is known as shelf life of a
battery”. It referred to storage duration of battery. If shelf life is high, better is the battery.

Zinc-air battery
Reactive species at anode: Granulated Zn
Reactive species at cathode: pure oxygen from air
Electrolyte: KOH
Separator: polypropylene
Voltage: 1.45V
The zinc-air, electrochemical system can formally defined as zinc/potassium
hydroxide/oxygen battery but commonly known as “zinc-air” cell.

Construction:
It consists of nickel-plated steel cans acting as anode and cathode..
1. The anodic can contain the zinc powder and electrolyte in the form of granules with a gelling
agent.
2. The cathode active material is carbon sheet impregnated with MnO2 (to increase the
conductivity of cathode) with multiple air holes punched at the bottom to provide air access to
the cathode. The sheet is laminated with Teflon layer (to diffuse the oxygen faster to cathode
side) on one side.
3. The anodic and cathodic compartments are separated by polypropylene
4. The alkaline electrolyte is potassium hydroxide.
5. The output voltage is 1.45 Volts.
Working:
When the battery discharge, the following reactions takes place at respective electrodes.

Application:
• Used in hearing aids,

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 Dept of Chemistry - SAI VIDYA INSTITUTE OF TECHNOLOGY
• In telecommunication devices such as pagers and wireless headsets
• In medical devices such as patient monitors, recorders, nerve & muscle stimulators and
drug infusion pumps.

Nickel-metal hydride battery (Ni-MH)

Anodic active material: MH
Cathodic active material: NiO (OH)
Electrolyte: 6M KOH
Separator: polypropylene
Voltage: 1.35V

Construction:
1. In a Ni-MH cell, a hydrogen in the form of metal hydride (VH2) acts as anodic active material
and nickel oxy hydroxide as cathodic active material.
2. Both the anodic and cathodic compartments are made of Nickel grids and filled with its
respective active materials.
3. The electrolyte used is potassium hydroxide solution.
4. Polypropylene used as a separator that separates the two electrodes and behaves as a medium
for absorbing the electrolyte.
5. The output voltage is 1.35V.

Working:
When battery is discharging/charging, the following reactions takes place at respective
electrodes.

Applications:
• Used in Cellular phones and laptops
• In Emergency lights and Power tools
• In electric vehicles

Lithium battery:

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 Dept of Chemistry - SAI VIDYA INSTITUTE OF TECHNOLOGY
Lithium is the lightest of metals and it can float on water. The electrochemical properties
of lithium are excellent and it is a highly reactive material. These properties give Lithium the
potential to achieve very high energy and power densities in high-density battery applications
such as automotive and standby power. Lithium batteries are primary batteries in which lithium
metal (or) lithium compound acts as a Anode. A lithium cell can produce voltage from 1.5 V to
about 3 V based on the types of materials used.
There are two types of lithium-based batteries available.
1. Lithium batteries
2. Lithium-ion batteries
In lithium batteries, a pure lithium metallic element is used as anode. These types of
batteries are not rechargeable.
In lithium-ion batteries, lithium compounds are used as anode. These batteries are known
as re-chargeable batteries. Therefore, Lithium ion batteries are considered as best than pure
Lithium based batteries.
By comparison, lithium-ion batteries are rechargeable batteries in which lithium ions move
between the anode and the cathode, using an intercalated lithium compound as the electrode
material instead of the metallic lithium used in lithium batteries.

LiMnO2 battery
Anodic active material: Lithium
Cathodic active material: MnO2
Electrolyte: Lithium halide (LiCl, LiBr, LiClO4 and LiAlCl4)
Separator: polypropylene
Voltage: 3.0

Construction:
1. Lithium Manganese Dioxide cell, is a primary battery. Anodic active material is Lithium metal
(in the form of disc) and cathode is manganese dioxide (in the form of a pellet).
2. The electrolyte is lithium halide dissolved in organic solvent.
3. Separator is polypropylene impregnated with the electrolyte. It provides an electrical contact
between the two electrodes.
4. The output voltage is 3.0V.

Working:
When battery is discharging, the following reactions take place at respective electrodes.

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 Dept of Chemistry - SAI VIDYA INSTITUTE OF TECHNOLOGY

Application:
• Outdoor use (requiring a low temperature range)
• In high-discharge devices, which include digital cameras, electric watches, hearing aids,
walkie-talkies, portable televisions, handheld video games, etc

Lithium-ion battery:
Anodic active material: Li+ / graphite
Cathodic active material: LiCoO2
Electrolyte: Lithium salt
Separator: polypropylene
Voltage: 3.6V

Construction:
1. In lithium-ion battery ( Li-ion battery or LIB), the lithium ions (electrons) move from the
negative electrode (anode) to the positive electrode (cathode) during discharge and back when
charging.
2. Anode is made of carbon material with a high energy density and large doping capacity of
lithium ion. Cathodes are metal oxide material containing lithium with capable of dedoping
lithium ion during charging and undergo lithium doping during discharging.
3. Electrolyte is made of lithium salts in an organic solvent (LiPF6, LiBF4 or LiClO4 in
an organic solvent, such as ether,). Lithium ion migrates between the two electrolytes via an
organic solvent.
4. Separator used is polypropylene.
5. The output voltage of this battery is 3.6V.

Working:

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 Dept of Chemistry - SAI VIDYA INSTITUTE OF TECHNOLOGY
During charging lithium ion in cathodic side (positive electrode) is migrated and move
towards anodic side (negative electrode) and during charging lithium ions move from anode to
cathode.

Application:
• The Li-ion batteries are used in mobile phones, cameras, calculators, LCD TVs, pagers,
to operate laptop computers and aerospace application

FUEL CELLS
Fuel cell is a device, which converts chemical energy of the fuel, and oxidant into
electrical energy.Electrical energy is obtained by the combustion of fuels in these galvanic cells.
Here, the fuels are supplied from outside and do not form integral part of the cell. These do not
store energy. Electrical energy can be obtained continuously as long as the fuels are supplied and
the products are removed simultaneously. In these aspects, fuel cells differ from conventional
electrochemical cells.
“Fuel cells are galvanic cells which converts chemical energy of the fuels into electrical energy
through catalyzed redox reactions with elimination of minimum harmful biproducts”.
Fuel is represented as
Fuel / electrode / electrolyte / electrode / oxidant
At anode, fuel undergoes oxidation, when battery discharge potential, the following reactions
takes place at respective electrodes.
Fuel oxidized product + ne
At cathode, oxidant is reduced, oxidant + ne reduced product

Limitation of Fuel cell

1. Power output is moderate.

2. Fuels are to be stored in tanks under very high pressure in tanks.
3. The refueling and the starting time of fuel cell vehicles are longer and the driving range is
shorter than in a “normal” car.
4. It generates only DC and should be converted to AC.

Advantages of fuel cells:

1. Do not pollute the atmosphere
2. Electrical energy can be obtained continuously.
3. Fuel cell provides high quality of DC power.
4. Fuel cells have a higher efficiency than diesel or gas engines.

Difference between conventional cell and fuel cell

S. No Conventional battery Fuel cells

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DR.PRASHANTH.P.A/Mr.RAVEENDRA.R.S/Mrs.S.SATHYANARAYANI/Mrs.BHAGYA.N.P
 Dept of Chemistry - SAI VIDYA INSTITUTE OF TECHNOLOGY
1 Battery makes electricity from the Fuel cell makes its electricity
energy it has stored inside the battery from fuel in an external fuel tank
2 Battery may run dead Fuel cell will make electricity as
long as fuel is supplied
3 Store chemical energy Do not store chemical energy
4 Reactants are not supplied and the Reactants are supplied
products are not removed continuously and the products are
removed simultaneously
5 Construction cost is high Construction cost is low
6 Life time is less Life time is higher than battery
7 Battery produce electricity depends on fuel cell will produce electricity as
concentration of the electrolyte long as it has a fuel supply
8 Recharge of the cell is required. Recharge of the fuel cell is not
required.

Methanol – oxygen fuel cell

Fuel: CH3OH
Oxidant: Oxygen
Electrolyte: H2SO4
Voltage: 1.2V

Construction:
1. It consists of anodic and cathodic compartments. Both the compartments contain platinum
electrode.
2. Methanol containing H2SO4 is passed through anodic compartment. Oxygen is passed through
cathodic compartment.
3. Electrolyte used is of sulphuric acid.
4. A membrane made of cellulose is provided which prevents the diffusion of methanol into the
cathode.
5. The output voltage is 1.2V.

Working:

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 Dept of Chemistry - SAI VIDYA INSTITUTE OF TECHNOLOGY

Application:
• Used in military applications
• Large-scale power productions.

Note:
1. KOH is not used as electrolyte as it reacts with CO2 and gets converted into carbonate.
Thus, conductivity of the electrolyte decreases as well as the efficiency.
2. The advantage of acid electrolyte is that the CO2, a product of the reaction can be easily
removed.

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