Nagar Yuwak Shikshan Sanstha’s

Yeshwantrao Chavan College Of Engineering

An Autonomous Institution Affiliation to Rashtrasant Tukadoji Maharaj University,Nagpur

Department of Applied Chemistry

Name of the course: Engineering Chemistry
Course code: GE2103
Unit II: Battery Technology

By
Dr.Ramesh .G.Surose
Assistant Professor
Department of Chemistry
YCCE Nagpur.
Dr.Ramesh.G.Surose
 Syllabus
Thermodynamic functions: Energy, Entropy and free
energy.
Electrochemistry :Basic electrochemistry, half cell potentials,
Nernst’s equation, Faraday’s laws for electro deposition,
Battery Technology: Classification of batteries: Primary,
Secondary- Electricity storage density, power density, energy
efficiency, cycle life, shelf life.Rechargeable alkaline storage
batteries, Ni-metal hydride.Lithium ion batteries and H2-O2
Fuel cell.
Dr.Ramesh.G.Surose
Thermodynamics: The branch of science that deals with the study
of different forms of energy and the quantitative relationships
between them.

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System : Refers to the portion of universe which is under
observation.

Type of system Mass flow Work Heat

Isolated ☓ ☓ ☓
System

Open System ✓ ✓ ✓

Closed System ☓ ✓
Dr.Ramesh.G.Surose ✓
Surrounding
Everything else in the universe except system is called surroundings.
The Universe = The System + The Surroundings.

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Thermodynamic Properties
Thermodynamic properties are defined as characteristic features
of a system, capable of specifying the system’s state.
Thermodynamic properties may be extensive or intensive.
Extensive property
An extensive property is a property whose value depends on the
quantity or size of matter present in the system.
For example: Mass, volume, enthalpy Entropy ,free energy •
Intensive property
Intensive properties do not depend upon the size of the matter or
quantity of the matter present in the system.
For example: temperature, density, pressure.
Dr.Ramesh.G.Surose
State Functions : Property of system which depend only
on the state of the system and not on the path.
Example: Pressure, volume, temperature, internal
energy, enthalpy, entropy etc.

Path Function /non state function : Depend on path

Example : Work ,heat

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Energy : The capacity for doing work. It may exist in potential,
kinetic, thermal, electrical, chemical, nuclear, or other various
forms. There are, moreover, heat and work—i.e., energy in the
process of transfer from one body to another.
Entropy : It is a property of matter that measures the degree of
randomization or disorder.
Entropy change is an extensive property.
 For a reversible process at equilibrium, ΔS = 0
 For a process to be spontaneous in isolated system , ΔS should
be positive,i.e. ΔS > 0.

Dr.Ramesh.G.Surose
Free energy: It is defined as” the maximum amount of energy which
is available to a system during a process that can be converted into
useful work”.
Free energy of a system is a measure of its capacity to do useful
work. It is represent by the symbol G (Gibb’s) and related to
enthalpy (H) and entropy(s) as blow,
G = H – TS
Free energy is state function, change in free energy is related to
enthalpy change and entropy change at absolute temperature.
ΔG = ΔH – T ΔS
1.If ΔG is negative ,the process is spontaneous
2.If ΔG is zero, the process is in equilibrium .There is no net
reaction in either direction.
3.If ΔG is positive .the process is non-spontaneous.
Dr.Ramesh.G.Surose
Electrochemistry : A branch of chemistry which deals with the study
of interrelation between chemical changes and electricity is called
electrochemistry i.e. the branch of chemistry that deals with the
chemical changes produced by electricity and the production of
electricity by chemical changes.
Cell: A device consisting of two electrodes in contact with an
electrolyte which convert chemical energy to electrical energy or
vice-versa.
Types of cell : (i) Electrolytic cell (ii) Electrochemical cell

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Types of cell :
(i) Electrochemical cell : A cell in which produce electrical energy
through spontaneous chemical reaction i.e. It converts
chemical energy to electrical energy.
Example : Dry cell , Daniel cell
(ii)Electrolytic cell :A cell in which electrical energy can be used to
create chemical energy i.e. It converts electrical energy to chemical
energy.
Example : Electrolysis of NaCl

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 Electrochemical cell Electrolytic cell
A cell in which electrical energy
A cell in which produce electrical
can be used to create chemical
energy through spontaneous energy
chemical reaction

It converts chemical energy to It converts electrical energy to

electrical energy. chemical energy
The redox reaction are non-
It is based upon the redox
spontaneous and take place only
reactions which are spontaneous
when energy is supplied
Anode is negative and cathode is Anode is positive and cathode is
positive negative
Example : Dry cell , Daniel cell Electrolysis of NaCl.
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Oxidation : A reaction which involves the
 Loss of electrons
 Addition of oxygen
 Removal of hydrogen
Loss of Electron

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Reduction : A reaction which involves the
 Gain of electrons
 addition of hydrogen
 removal of oxygen
Gain of Electron

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Redox reaction : In a reaction if one reactant gets oxidized while the
other gets reduced , such reactions are known as oxidation-reduction
reaction or redox reaction.

Oxidation

heat
CuO(s) + H2 Cu(s) + H2O(l)

Reduction
Substance oxidized act as reducing agent
Substance reduced act as oxidizing agent

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Electrode Potential: A difference of electrical potential developed
between the metal electrode and its surrounding salt solution at
equilibrium is called single electrode potential.
Oxidation potential: A difference of electrical potential developed
at an electrode due to oxidation when a metal electrode is in
contact with its own electrolytic solution at equilibrium is called
oxidation potential.
Reduction Potential: A difference of electrical potential developed
at an electrode due to reduction when a metal electrode is in
contact with its own electrolytic solution at equilibrium.

Dr.Ramesh.G.Surose
Standard Oxidation Potential: A difference of electrical potential
potential developed at an electrode due to oxidation when a metal
or a gas at partial pressure of 1 atm. is placed in a solution of its
own ions at unit activity and measured at 298K is called standard
oxidation potential.
Standard Reduction Potential: A difference of electrical potential
developed at an electrode due to reduction when a metal or a gas at
partial pressure of one atm. is in contact with a solution of its own
ions at unit activity and measured at 298K is called standard
reduction potential.
E.M.F: The potential difference between the electrodes
corresponding to an external flow of electrons from left hand side
electrode(anode) to right hand side electrode(cathode)measured
across the terminals of the cell in an open circuit i.e. when no
current flows in the circuit is called emf of the cell.

Dr.Ramesh.G.Surose
 Oxidation potential of metal = - Reduction potential or
Reduction Potential of metal = - Oxidation Potential

Ecell = (reduction potential of cathode) – (Reduction potential of anode)

i.e. Ecell = Ecathode – E anode

Ecell = Eright – Eleft

Ecell = (oxidation potential of anode) – (oxidation potential of cathode)

Ecell = (Oxidation potential of anode) + (Reduction potential of cathode)

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Cell representation:
Anode written on left hand side.
Cathode written on the right hand side.
A single vertical line ( | ) is drawn between two chemical species
that are in different phases but in physical contact with each
other (e.g., solid electrode | liquid with electrolyte).
Two half cell separated by salt bridge which represent by using
two vertical line like (||).

Example: Representation of galvanic cell

Zn | ZnSO4 (1M) || CuSO4 (1M) | Cu

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Dr.Ramesh.G.Surose
Electrode potential and electrolyte concentration( Nernst Equation)
Electrode potential depends on the concentration of
metallic ions in solution the variation of electrode potential
with concentration of metallic ion solution is given by
Nernst equation.
2.303RT [M ]
n
M  ne  M  EE  0
log
nF [M n ]

At 298 K
2.303RT
 0.0591
F
0.0591 [Product]
0.0591 [M ] EE  0
log
EE  0
log n [Reactants]
n [M n ]
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 Where E = Electrode potential of the metal
E0 = Standard electrode potential
R = Gas constant (8.314 J / mole per degree
T = Temperature in K (Absolute temperature)
n = Number of electrode involved in the half cell reaction
F = One faraday (1 F = 96000 coulombs)
[M] = Activity of metal in the metal phase
[Mn+] = Activity of metal ions in the solution.
General electrochemical reaction of the type:

Nernst equation can be written as:

Dr.Ramesh.G.Surose
 2 2
Zn ( s )  Cu aq  Zn aq  Cu (s)
2
2.303RT [Cu ][ Zn ]
Ecell  Ecell 
o
log
2F [ Zn ][Cu 2 ]
since [Zn] and [Cu] = 1
2
2.303RT [ Zn ]
Ecell  Ecell 
o
log 2
2F [Cu ]

Dr.Ramesh.G.Surose
Faraday’s Laws Of Electro deposition

First Law: The weight of a substance liberated or deposited at any

electrode during electrolysis is directly proportional to the
quantity of electricity passed.
WαQ
where Q= c x t is the total quantity passed through the solution
measured in coulombs OR is the product of current in amperes &
t is the time in seconds for which it is passed OR
W= Z x c x t
where Z is the proportionality constant called as Electrochemical
equivalent (ECE)
Dr.Ramesh.G.Surose
Second Law: When two different electrolytes are connected in
series, the ratio of weights of the substances liberated or deposited
at respective electrodes is same as the ratio of their chemical
equivalent weights.

W1 E1
------ = ------
W2 E2

Dr.Ramesh.G.Surose
Batteries:- Batteries are most commonly used energy storage
device. Batteries are electrochemical devices which convert
chemical energy into electrical energy. That is, they use chemical
reactions to produce electricity. Such electrochemical devices are
called galvanic cells.
Batteries are used in many day-to-day devices such as cellular
phones, laptop computers, clocks, and cars. Batteries are
composed of at least one electrochemical cell which is used for the
storage and generation of electricity.
Presentation of battery

Dr.Ramesh.G.Surose
Energy density : The ratio of a battery's available energy to its volume
Units : watt hour/liter
Specific energy: The ratio of energy to mass
Units: watt hour/Kg
Power density :The ratio of the power available from a fully
charged battery to its volume
Units: watt/liter.
Specific power :The ratio of power to mass
Units:watt/kg

Dr.Ramesh.G.Surose
Energy efficiency of a secondary battery:
For a secondary cell, the ratio of the output on discharge to the
input required to restore it to its initial state of charge under
specified conditions.
Can be measured in ampere-hour, voltage, and watt-hour
efficiency

shelf life : It is the length of time a battery can remains in storage

without losing its capacity.

Dr.Ramesh.G.Surose
Dr.Ramesh.G.Surose
Specifications Primary Battery Secondary Battery
These batteries can not be These batteries can be recharged

Recharging recharged or reused. or reused.

Reaction Irreversible reactions occur Reversible reactions occur

only once, can be used as long as

Number of times
it can be used. active materials are present. more than once by recharging

It is used in portable devices, It is used in automobiles, digital

cameras, laptops, flash lights,
Application watches, transistors, radios etc. electronic equipments etc.
Self discharge
rates Lower Higher
Initial cost Lower Higher
Life Cycle cost Higher Lower
Regular maintenance needed,
Disposable, can not be recharged. Periodic recharging required.
Leclanche cell, Dry cell, lithium Lead storage battery, Ni-Cd
Examples cell Dr.Ramesh.G.Surose
battery, Lithium Ion Cell
 Rechargeable
batteries

Rechargeable Rechargeable Alkaline Rechargeable

Acidic Batteries non-aqueous
Batteries electrolyte
Batteries

Ni-Cd,NI-H2,Ni- MH
Lead Accumulator Lithium Ion

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 Ni-metal hydride battery
Construction :
Cathode ( positive electrode) :Nickel hydroxide
Anode ( negative electrode ):MH Alloys like LaNi5 or ZrNi2 capable
of absorbing H2
Electrolyte : KOH

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Working

Dr.Ramesh.G.Surose
Advantages:
•Environmentally friendly
•Excellent leakage protection
•Quick recharge capacity
•Simple storage and transportation
•Voltage per unit cell 1.3 v
•Energy density 184 Wh/L
• No chances of O2 evolution during charging.
• Accept both higher charge and discharge rates.
Limitations:
• Limited service life( 200-300 cycles)
•Storage time is less( 3 yrs.)
•High self discharge 2 % per day
•Requires regular full charge to avoid formation of crystals
•Decrease in performance if stored at high temp.

Dr.Ramesh.G.Surose
 General Applications
•Electric vehicles
•Medical instruments and equipment
•Automotive batteries,
•High power static applications (Telecoms, UPS and Smart grid).
LRV (Light Rail Vehicles)
•Electric locomotives
•High speed trains
•In photovoltaic applications ( specially in remote areas)

Dr.Ramesh.G.Surose
Dr.Ramesh.G.Surose
 Lithium ion battery
• Lithium ion batteries are the example of secondary batteries.
• This type of battery has revolutionized the energy storage
technology and enabled the mobile revolution.
• Lithium-ion batteries are used globally to power the portable
electronics that we use to communicate, work, study, listen to
music and search for knowledge.
• Lithium ion batteries have also enabled the development of
long-range electric cars and the storage of energy from
renewable sources, such as solar and wind power.

Dr.Ramesh.G.Surose
 Lithium Ion Battery
Construction
•Anode (negative electrode) – Most commercially popular negative
electrode is graphite (carbon),soft carbon and hard carbon.
•Cathode (positive electrode) – is generally metal oxide typically 3
electroactive oxide metals are used as cathode.
Li-CoO2 - lithium cobalt oxide
Li-Mn2O4 - lithium manganese oxide
Li-NiO2 - lithium nickel oxide
•Electrolyte – made up of lithium salt in an organic solvent.(non
aqueous )
LiPF6 – lithium hexaflurophosphate
LiClO4 – lithium perchlorate
LiF3- lithium triflorate
•Seperator – is a fine porous polymer film (membrane)

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Dr.Ramesh.G.Surose
Working:-
Charging: During charging lithium ions flow from the positive to
negative electrode through the electrolyte. When no more ions will
flow, the battery is fully charged and ready to use.
Discharging -:- During discharging ions flow back from the negative
to positive electrode. When all the ions move back the battery is fully
discharged.
On positive electrode half-reaction (with charging being
forwards) is:

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The negative electrode half-reaction is:

The overall reaction has its limits. Over discharge

supersaturates lithium cobalt oxide, leading to the production
of lithium oxide, possibly by the following irreversible reaction:

Dr.Ramesh.G.Surose
 Advantages:-
 Wide variety of shapes and sizes.
 Excellent storage life, longest service life
 Rechargeable
 Quick charging capacity
 High energy density
 Much lighter than other secondary batteries.
 Fast charging rate.
 Components are environmentally safe as there is no free lithium
metal.
 They produce high voltage. 3.6V to 4.1 V
 store significant amounts of energy from solar and wind power,
making possible a fossil fuel-free society.
 Working temperature is suitable for wide range, it can work
under such circumstances of -20~60 deg.C.
 Excellent cycle life ;500 or more cycles.
Dr.Ramesh.G.Surose
Applications :-
•It is used in cameras and calculators.
•They are used in telecommunication equipments and instruments.
•Used in portable radios and TV’s.
•They are used to operate laptops, computers and mobile phones.
•Used in long-range electric cars and the storage of energy from
renewable sources, such as solar and wind power.
Disadvantages:
•They are expensive.
• Requires protection circuit to maintain voltage and current in safe
limits since overcharging converts Li oxide to metallic Li with chances
of explosion
Dr.Ramesh.G.Surose
Fuel Cell : A fuel cell is a device that converts the chemical energy
from a fuel into electricity through a chemical reaction with
oxygen or another oxidizing agent.
Alkaline fuel cell (H2 – O2 fuel cell) :
Construction : It consist of porous carbon as cathode and anode
containing suitable catalyst. Conc. NaOH or KOH solution which
is placed in between electrodes to act as electrolyte. Hydrogen and
oxygen gas are bubbled through porous electrodes into NaOH or
KOH solution.

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Dr.Ramesh.G.Surose
Working:
At the Anode : Hydrogen is oxidized according to the reaction:
Producing water and releasing two electrons.

At the cathode : Producing hydroxide ions.

Dr.Ramesh.G.Surose
Advantages
•High efficiency of energy conversion (75 – 83%) from chemical
energy to electrical energy.
•No emission of gases and pollutants.
•Low maintenance cost.
•It produces drinking water of potable quality.
•Save fossil fuels.
Disadvantages
•Alkaline batteries are bulkier than other lithium batteries which
give much higher energy.
•A defective battery charger can cause the alkaline batteries to
explode.
•Alkaline batteries kept in devices that are not used for a long time,
can leak and thus completely ruin the device itself because of the
corrosive nature of the leaked material.
Dr.Ramesh.G.Surose