ENGINEERING CHEMISTRY

ELECTROCHEMISTRY

Principles of Electrochemistry

Gibbs free energy:

Gibbs free energy is a thermodynamic function that was defined in 1876 by Josiah
Willard Gibbs to predict whether a process will occur spontaneously at constant temperature
and pressure.

● Gibbs free energy is the energy that is available to do useful work in a system.

It is given by G=H-TS

G-Gibbs free energy, H-Enthalpy (Enthalpy is the amount of energy in a system capable of
doing mechanical work) , S-Entropy (Entropy is the measure of the disorder of a system)

T-Temperature

Change in Gibbs free energy (∆G) during a reaction at any set of conditions is given by,

∆G=∆H-T∆S

If the reaction occurs at standard state conditions (298K, 1 atm pressure or 1M concentration
depending on the state of matter),the result is standard free energy change(∆Gο),

∆Gο=∆Hο-T∆Sο

For a reaction at equilibrium ∆G = 0, For a spontaneous reaction ∆G is negative and for a non
spontaneous reaction ∆G is positive.

Electromotive force of the Cell (or) Cell potential

The potential difference which causes a current to flow from an electrode at higher
potential to that at lower potential is called the electromotive force(emf).The emf is
represented as Ecell. It is expressed in volts.

The measured EMF of a cell is Ecell=Ecathode-Eanode

Where Ecathodeand Eanode are the reduction electrode potentials of the cathode and anode
respectively.

Standard emf of a cell is defined as the emf of a galvanic cell when the reactants and
products of the cell reaction are at unit concentration or unit activity, at 298K at 1
atmospheric pressure and is given by the following equation:

Eοcell = Eοcathode - Eοanode

Equilibrium constant:

Chemical equilibrium is defined as the state at which the concentrations of all reactants and
products of a chemical reaction remain constant over time.

For a reaction aA+bB→cC+dD

[ Product ]
K= =¿ ¿
[ Reactant ]

Where K is equilibrium constant.

Cell Notations and Conventions

In a galvanic cell, For example Daniell cell Zn(s)/Zn2+(aq)//Cu2+(aq)/Cu(s)
*Oxidation reaction takes place at the anode side(lower reduction potential metals are highly
active and releases electrons at fast).
*Reduction reaction takes place at the cathode side(higher reduction potential metals are less
active so accepts electrons).
*Salt bridge is represented as(//)double vertical lines.
*Phase difference between the electrode and the solution is represented by(/)single vertical
line.
*For the spontaneous reaction Ecell is positive.
*For the non-spontaneous reaction Ecell is negative.
Galvanic Cell
Galvanic cells are devices which converts chemical energy into electrical energy.
The Daniel cell is an example of a galvanic cell. At the anode side zinc rod dipped in a 1M
solution of zinc sulphate . This forms one half-cell. At the cathode side copper rod dipped in
a 1M solution of copper sulphate solution, constitutes the other half cell. The Daniel cell is
represented by Zn(s)/Zn2+(aq)//Cu2+(aq)/Cu(s)

The two electrodes are connected internally by a salt bridge. A salt bridge consists of a
jelly containing KCl or a solution of KCl placed in a U-tube fitted with porous plugs at
either end. The salt bridge allows the flow of ions but prevents the mixing of the solutions
that would allow direct reaction of the cell reactants. The two electrodes are connected
externally by a wire through a voltmeter. Oxidation of Zn to Zn2+ and reduction of Cu2+ to
Cu occur at the zinc and copper electrodes are represented by equations 1 &2

Anode: Zn(s) →Zn2+(aq)+ 2e------------------------(1)

Cathode:Cu2+ +2e → Cu(s) ----------------------------(2)

The net cell reaction is obtained by adding equations 1 and 2

Zn(s)+ Cu2+(aq)) →Zn2+(aq)+ Cu(s)

The electrons released at the zinc half-cell build up an electrical potential difference
between the electrodes. This is indicated by the voltmeter.
Origin of single electrode potential:
Whenever, a metal is in contact with its own ions, it has a natural tendency to lose or gain
electrons. Because of this tendency the electrode gains a potential, which is known as single
electrode potential.

When a metal is in contact with a solution of its own ions, two types of reactions are possible
ie. oxidation and reduction.
The metal shows the tendency to go into the solution as metal ion by losing electrons. The
electrons accumulate on the electrode surface, making it negatively charged. The negatively
charged electrode surface attracts a layer of positively charge ions at the interface, developing
an electrical double layer at the metal solution interface. The electrical double layer is called
as HDL(Helmholtz double layer).
Anode (oxidation) reaction: M→ Mn++ne----------(1)
At the same time, metal ions in the solution show the tendency to get deposited as metal
atoms by consuming electrons.
Cathode(reduction) reaction: Mn++ne-→M----------(2)
The positively charged metal ions accumulate on the electrode surface, making it positively
charged. The positively charged electrode surface attracts a layer of negatively charged ions
at the interface, again establishing an electrical double layer.
Formation of an electrical double layer gives rise to a potential difference across the layer.
This potential difference between the metal and solution at the interface is called single
electrode potential.
Single Electrode potential or Reduction potential: The potential difference between a
metal and metal ions in its solution at equilibrium is called single electrode potential. It is
represented as E Mn+/M. Single electrode potential is always termed as its reduction potential.

Standard Electrode potential or Standard reduction potential (SRP): The potential

difference between a metal and metal ions in its solution of unit concentration, at 298K
temperature and at equilibrium is called standard electrode potential or standard reduction
potential. It is represented as Eo Mn+/M.
Eg. Eo Zn2+/Zn = - 0.76V , Eo Cu2+/Cu = + 0.34V
(Note. In a galvanic cell the electrode eith lesser reduction potential acts as anode and
electrode with higher reduction potential acts as cathode.)

Nernst Equation for single electrode potential

Single electrode potential (E), change in free energy( ∆ G) and the concentration Mn+ are
related by Nernst equation. According to thermodynamics, the decrease in free energy
(- ∆G) represents the maximum amount of work that can be obtained from a chemical
reaction.

- ∆G=Wmax------------------(1)

The work performed by an electrochemical cell depends on the number coulombs of

electricity that flow and the energy available per coulomb.
Energy available
Work=number of coulombs x
Coulomb

The number of coulombs is the product of number of moles (n) of electrons involved in the
cell reaction and the faraday(F).

Number of coulombs = nF
Energy available per coulomb is the cell potential E, since volt is equal to energy per
coulomb. The potential is maximum when the work derived from the cell is maximum.

Thus,
Wmax= nxFxE-----------------(2)
-∆G= nFE----------------------(3)
Under standard conditions
ΔGο= - nFEο---------------------------(4)

Where Eο is a constant called the standard electrode potential.

For a reaction,

Mn+ + ne ⇌ M
[M]
Kc=
¿¿

The equilibrium constant Kc is related to change in free energy by the Vant Hoff
equation.
∆G = ∆ G0 + RT ln Kc

[M]
∆ G= ∆ Gο + RT ln ¿ ¿ -----------(5)

∆ G =∆Gο+RTln[M]-RTln[Mn+]--------(6)

Substituting from Eqs.3&4 for ∆ G and ∆ Gο,

- nFE = -nFEο+ RTln[M]-RTln[Mn+]--------(7)

Dividing eqn.7 by -nF,

−nFE −nFE 0 RTln [M ]

= + - RTln ¿ ¿----------- (8) [M] =1
−nF −nF −nF
RT
E = Eο + nF ln [Mn+]--------------------------------(9)

2.303 RT n+
E = Eο + nF log [M ]--------Nernst equation for single electrode potential

Where E = electrode potential; E ο = standard electrode potential; R = Universal Gas

Constant [8.314J/K/mol], T= Temperature in Kelvin, F = Faraday Constant
[96500C/mol]; n= Valency of the metal.

At room temperature,25oC, Substituting the values of R = Universal Gas Constant

[8.314J/K/mol]; T = temperature in Kelvin [298K]; F = Faraday Constant [96500C/mol];
n= Valency of the metal.
0 .0591 n+
E = Eο + n log [M ]

Nernst equation for cell potential

0 .0591 [ Reactants]
E = Eο + n log [ Products]
 OR
0 .0591 [species at cathode]
E = Eο + n log [species at anode ]
Eg. Nernst Equation for Daniel Cell:

Zn (s) + Cu2+ (aq) Zn2+ (aq) + Cu(s)

0 .0591
E = Eο + n log
[Zn]¿ ¿

0 .0591
E = Eο + n log
¿¿ [Zn] =1, [Cu] =1

1. Calculate the electrode potential of copper at 25οC when it is dipped in 0.015 M

Cu SO4 solution. Given SRP of Copper is 0.34V .

Nernst equation for single electrode potential

0.0591
Ecell = log[Mn+]
n

0.0591
Ecell = 0.34+ log [0.015]
2

Ecell = 0.296V

2. A galvanic cell is obtained by the combination of Fe rod immersed in ferrous sulphate

solution of concentration 0.25M and Cu rod immersed in copper sulphate solution of
concentration 0.45M.Give the cell representation, cell reactions and calculate EMF of cell at

30οC. Given that standard potentials of Cu and Fe electrodes are 0.34 and -0.41V

respectively. Cell Notation : Fe/Fe2+//Cu2+/Cu

Cell reactions:

Anode: Fe → Fe2++2e-

Cathode: Cu2++2e-→Cu

Overall reaction: Fe+ Cu2+→ Fe2++Cu

0 .0591 [ Reactants]
E = Eο + n log [ Products]
0 .0591
E = (Eο cathode – E0Anode) + [Fe ]¿ ¿
n log

2.303 X 8.314 X 303 0.45

E=(0.34-(-0.41)+ log = 0.76V
2 X 96500 0.25
Electrolyte Concentration Cells

A concentration cell is an electrochemical cell in which the electrode material and the
solution in both the half-cells are composed of the same substances but only the concentration
of the two solutions are different.
Concentration cell is represented as-
Cu(s) | Cu2+[M1] || Cu2+[M2] | Cu(s)
Construction-

Two copper electrodes are dipped in copper sulphate solution of different concentrations.
The Cu electrode which is in contact with dilute solution acts as anode and that with
concentrated solution acts as cathode, and the two solutions are connected through a salt
bridge.

The flow of electrons takes place from dilute solution to concentrated solution, such a cell
is called concentration cell with transference.

At Anode:-

Cu(s) → Cu+2(aq) [M1] +2e-

At Cathode:-
Cu2+(aq) [M2] + 2e- →Cu(s)
Net cell reaction:-
Cu2+(aq) [M2 ]+ 2e-⇌ Cu(aq)2+ [M1 ]+ 2e-

Applying Nernst
equation-

Ecell=Ecathode-Eanode

0.0591
Eanode = Eο+
n
log[M1]

0.0591
Ecathode= Eο+
n
log[M2]

Ecell= Eο+0.0591/n log[M2]-(Eο+0.0591/n log[M1])

Ecell= 𝟎.𝟎𝟓𝟗𝟏 log [𝐌𝟐]

𝐧 [𝐌𝟏]

By the above equation

If [M1] = [M2] , emf of the cell is zero (Ecell = 0)

If [M2] > [M1], emf is positive

[ M 2]
If is large, Ecell is large
[ M 1]

1.The concentration cell tin/tin ion (0.024M)//tin ion(0.064M)/tin develops a potential of

0.0126V at 25οC.Calculate the valency of tin.

0.0591 [ M 2]
Ecell = log
n [ M 1]
0.0591 0.064
n= log
0.0126 0.024

n =1.998=2

2. Two copper rods placed in copper sulphate solutions of equal concentrations are connected
to form a concentration cell a)What is cell potential? Calculate the cell potential if one of the

solutions is diluted to1/5th of its original concentration

0.0591 log [ M 2]
a) Ecell = n [ M 1]
Given M1=M2,
Hence cell potential=0
b)Assume M 2=1M then
M1=1/5M
0.0591 [ M 2]
Ecell = log
n [ M 1]

[1]
0.0591
Ecell = log 1
2 [ ]
5
 0.0591
Ecell = log5
2

Ecell =0.02955X0.699=0.0206V

3. A concentration cell is constructed by dipping copper rods in 0.001M and 0.1M CuSO4
solutions.Calculate the emf of the cell at 298K.

Solution:
The cell is represented as,

Cu(s)/Cu2+(0.001M)//Cu2+(0.1M)/Cu(s)

At the anode, Cu→Cu2++2e-

At the cathode, Cu2++2e-→Cu

0.0591 [ M 2]
Ecell = log
n [ M 1]

0.0591 [0.1]
Ecell = log
2 [0.001]
0.0591
Ecell = log100
2
Ecell=0.0591V
4. EMF of the cell Cu/CuSO4 (0.001M)//CuSO4(X)/Cu is 0.0595V at 25οC.Find X value.

Here M1=0.001M , M2=X and n=2

Apply Nernst equation for concentration cell

0.0591 [ M 2]
Ecell = log
n [ M 1]
Ecell X n X
=log
0.0591 M1
X
Antilog¿ ) =
M1
X = 0.001x Antilog¿ )
X = 0.001x103 = 0.103M

TYPES OF ELECTRODES

In electrochemistry, we encounter various types of electrodes depending upon the purpose for
which they are used.

1.Metal-metal ion electrode: Metal dipped in a solution of its own ions.

Example: Cu/Cu2+,Zn/Zn2+,Ag/Ag+
 2. Metal-metal salt ion electrode(Metal-insoluble salt electrode):These electrodes consists
of a metal in contact with a sparingly soluble salt of the same metal dipped in a solution
containing anion of the salt.

Example: Calomel electrode (Hg/Hg2Cl2/ Cl-)

Silver-Silver chloride electrode (Ag/AgCl/Cl-)

3. Gas electrode: An inert electrode like platinum is in contact with gas molecules and also
in contact with ionic solution of the same gas molecules.

Example: H2 electrode( Pt/H2/H+)

4. Ion selective electrode: These electrodes have the ability to respond to certain specific
ions and develop a potential in a mixture by ignoring other ions. Example: Glass
electrode(selective to H+ ions)

REFERENCE ELECTRODES

Reference electrodes are the electrodes with reference to those, electrode potential of any
electrode can be measured.

Standard hydrogen electrode is the primary reference electrode. It is represented as ( Pt/H2/H+)

Secondary reference electrodes

They are commonly used to determine electrode potentials of other electrodes. Examples –
Silver-Silver chloride Electrode, Calomel Electrode.

Calomel Electrode
It is a metal-metal salt ion electrode. The electrode is represented as-

Hg| Hg2Cl2(s)| Cl-

Construction-
1) The calomel electrode consists of a solid Mercurous chloride in contact with mercury
placed at the bottom of the long glass tube.
2) Mercurous chloride [Hg2Cl2] and the mercury paste is placed over mercury; the remaining
part of the tube is filled with KCl solution.
3) A platinum wire is dipped in mercury; it is used for external electrical contact.

4) The calomel electrode may act as anode or cathode depending on the nature of the other
electrode.

If it acts as anode-
2Hg + 2Cl- →Hg2Cl2 + 2e-

If it acts as cathode-
Hg2Cl2 + 2e- →2Hg + 2Cl-
The net reversible electrode reaction
is Hg2Cl2(s)+ 2e⇌2Hg+2Cl-
The potential developed from calomel electrode depends on the concentration of KCl
solution.
2.303 RT
E=E0- log[Cl-]2
nF
2.303 RT
E=E0 - log [Cl-]
F

At 298K,

E= E0 – is
The electrode potential 0.0591 log by
decided
-
[Clthe
] concentration of chloride ions and the electrode is
reversible with chloride ions.

*The electrode potential of decinormal(0.1N ) calomel electrode is 0.334V.

*The electrode potential of normal (1N)calomel electrode is 0.281V.

*The electrode potential of saturated calomel electrode is 0.242V.

Applications
 Used as a reference electrode for the determination of pH.

 It is used in potentiometric titrations.

ION- SELECTIVE ELECTRODES - These electrodes have the ability to respond to

specific ions and develop a potential in the mixture and ignoring the other ion. The
potential developed at the electrode is a function of the concentration of that ion in the
solution.

GLASS ELECTRODE

Principal - When two solutions of different pH are separated by a thin glass membrane, a
potential is developed and this potential is proportional to the pH value.
 Construction:
 It consist of a long glass tube with a thin glass membrane bulb at the bottom which is
made up of a special type of corning glass(Na2SiO3).
 The corning glass has low melting point and high electrical conductivity.

 The bulb is filled with 0.1M HCl and is inserted with a Ag|AgCl electrode in it. It is also
used for external contact.
 1M HCl is taken in a beaker and the electrode is immersed inside it. They cell is
represented as:

Due to the difference in the concentration of ions and the pH a potential is developed
at the membrane- [Eb] boundary potential or junction potential.

0.0591 C 1
At 25oC Eb = log
n C2

0 .0591 0.0591
Eb = logC1 - logC2
n n

0.0591
If [C2] is kept constant, - logC2=K
n
0.0591
Eb= logC1+K
n

Thus total potential EG = Eb + Ereference

0.0591 log[C1]
EG = + K + Ereference
n
Let [K + Ereference] = EοG

EG= EοG+ ¿ 0.0591 log [C1]

n
¿ 0.0591 log [H+]
EG = EοG +
n

(pH = - log [H+]) (n = 1 for H+)

EG=E0G-0.0519PH
 Determination of pH using glass calomel electrodes:

To determine the pH of a given solution, the glass electrode is dipped in a given solution
whose pH needs to be determined.

Hg/Hg2Cl2/Cl-/ solution of unknown pH / Glass /0.01M HCl /AgCl /Ag

The glass electrode is coupled with calomel electrode and dipped in the solution whose pH to
be determined. Calomel electrode acts as anode and glass electrode acts as cathode.

Ecell=Ecathode-Eanode

Ecell=EG-Ecalomel(Since, Esat.
calomel =0.24V)

Ecell = EoG – 0.0591pH - E Calomel

pH =
E 0G−Ecalomel−Ecell
0.0591

Advantages of glass
electrodes:
1) Glass electrode can be used in the presence of oxidizing and reducing agents.

2) Electrode does not get poisoned.

3) It is simple to operate and is used in industries, agricultural labs, etc.

4) Accurate results are obtained between pH range 1-9. By using special glass electrode pH
1- 14 can be measured.
Disadvantage

1) Because of high resistance of glass, simple potentiometers cannot be used. It

requires sensitive electronic potentiometers for emf measurement.
2) The electrode can be used up to a pH 13 but becomes sensitive to Na+ ions above pH
9 resulting in an alkaline error.
 Applications of ion selective electrodes

1)It is used to find the concentrations of electrolyte solution at anodes and cathodes.

2)To measure the level of CO2 in blood sample.

BATTERIES
PRINCIPAL COMPONENTS OF A BATTERY:

The basic electrochemical unit in a battery is the galvanic cell. The major components of a
battery are described below:
1. Anode or negative electrode : It releases electrons to the external circuit by undergoing
oxidation during electrochemical reaction.
2. Cathode or positive electrode : It accepts electrons from the external circuit and reduction
of an active species occurs.
3. Electrolyte : It is the active mass in the anode and cathode compartments. A solution of an
acid, alkali or salt having high ionic conductivity is commonly used as electrolyte. Solid
electrolytes with appreciable ionic conductivity at the operating temperature of the cell are
also used.
4. Separator : It separates the anode and the cathode in a battery to prevent internal short-
circuiting. It is permeable to the electrolyte and maintains the desired ionic conductivity.
The main function of the separator is to transport ions from the anode compartment to the
cathode compartment and vice versa. Fibrous forms of regenerated cellulose, vinyl
polymers and polyolefins, cellophane and nafion membranes are used as separators.
Battery Characteristics:
1.Voltage: The voltage available from a battery depends upon the emf of the cells which
constitute the battery system. The emf of the cell depends on the free energy change in the
overall cell reaction. As given by Nernst equation,
 0 .0591 [ Reactants]
E = Eο + n log [ Products]
2.Capacity: It is the charge in Ampere - hours (Ah) that can be withdrawn from fully charged cell or
battery under specified conditions. The capacity of a battery depends on the size of the battery, larger
the size, higher the capacity. It is determined by Faraday’s relation:

WnF
C=
M
(where, W=weight of active material; F=Faraday’s constant; M=Molar mass of active material;
n=number of electrons involved in cell reaction).
3. Cycle life: The number of charge/discharge cycles that are possible before failure occurs
in the case of secondary batteries is called as cycle life. The cycle life of a battery is
affected by corrosion in contacts and shedding of active materials from electrodes.
4. Shelf life:
It is essential for most batteries to be stored, sometimes for many years, without self
discharge or corrosion of electrodes. Shelf life is defined as duration of storage under
specific conditions without any loss in its performance.

CLASSIFICATION OF BATTERIES

Batteries are classified into:

1. Primary Batteries

A battery which cannot be recharged and discarded when the battery has delivered all its
electrical energy is called Primary Battery.
They are non- rechargeable because the cell reactions are irreversible.
Example: Zn-MnO2 battery, Li-MnO2 battery
2. Secondary Batteries

A battery which after discharging can be recharged again by passing the electric current
through it in the opposite direction to that of discharge is known as Secondary Battery.
They are rechargeable because the cell reactions are reversible.

The secondary battery is also called as storage battery as it is the storage device for
electrical energy.
Example: Lead storage battery, Nickel Cadmium Battery, etc.

3. Reserve Batteries

One of the components is stored separately and incorporated into the battery when
required. Usually, the electrolyte is stored separately. Such batteries are called
Reserve Batteries.
They are used to deliver high power for relatively short period of time in missiles,
trajectory and other weapon systems.
Example: Mg-AgCl and Mg-CuCl batteries both are activated by adding water.
Alkaline Battery
Batteries which use an alkali as electrolyte (KOH or NaOH) are called alkaline batteries.
Example: Zinc-Air Battery (Primary battery)

Zinc- air battery consists of a porous carbon plate as cathode. The cathode is activated for
better reduction of oxygen and treated with water repellants. The anode consists of
rectangular flat plates of zinc placed on either side of the cathode. The electrolyte is KOH.
The outer container is made of glass or ebonite.

Components of a battery:

Anode: Powdered Zinc

Cathode: Carbon

Electrolyte: KOH

Separator: Polyethylene

Zinc-air battery is a primary battery. Its advantage is that air does not contribute to the mass of the
battery, hence offers high energy density. The battery is represented as,
𝒁𝒏/ KOH(6 𝑴)/ A𝒊𝒓, 𝑪
When air is passed through the cell, zinc is oxidized to ZnO at the anode, during discharge.
The oxygen of the air reacts with water at the cathode. The half-cell reactions are

Anode reaction: 𝒁𝒏 + 2𝑶𝑯− → 𝒁𝒏𝑶 + 𝑯𝟐𝑶 + 2𝒆-

Cathode reaction: 1/2𝑶𝟐 + 𝑯𝟐𝑶 + 2 𝒆- → 2𝑶𝑯−
The overall reaction is 𝒁𝒏 +1/2 𝑶𝟐 → 𝒁𝒏𝑶
Advantages:
1. High capacity 2.Low cost 3. Long shelf life 4. High energy density
Disadvantages:
1. Limited power output 2.Short activated life
Applications:
It finds applications in hearing aids, electronic pager, railroad signaling, medical devices,
remote communications and military radio receivers.
 Secondary Batteries:

Lithium Ion Battery:

Lithium-ion battery is a rechargeable battery best suited to mobile devices that require
small size, light weight and high performance. It has high energy and high voltage
(3.6V).
Components:

Representation: Li/Li+, C/LiPF6/Li-CoO2

1. Anode: Lithium carbide.

2. Cathode: Lithium cobalt oxide(LiCoO2 ),where M is Cobalt( Co )

3. The electrolyte consists of Li salt in an organic solvent (LiPF6, LiBF4) in ethylene carbonate.
In anode, lithium atoms occupy the position between the graphite lattice layers.

4. Microporous polyethylene or polypropylene is used as separator. The container is made up

of stainless steel or aluminium alloy
In Li-ion battery, lithium ion move between the electrodes, using an intercalated electrode

material. Metal atoms and ions can enter layered solids reversibly. Such a process is
referred as intercalation.

During discharging of a battery,

Anode :LiC6⇌Li++e-+6C

Cathode: Li++e-+CoO2⇌LiCoO2

Net reaction: LiC6 +CoO2⇌LiCoO2+6C

During discharging of battery, Lithium atoms present in graphite layer (one Li atom is present
for every 6C atoms) are oxidized, liberating electrons and lithium ions. Electrons flow
through external circuit to cathode and lithium ions flow through the organic electrolyte
towards cathode. At cathode, lithium ions are reduced to lithium atoms and are inserted in to
the layered structure of metal oxide.
During charging of battery, lithium atoms present in layered structure of metal oxide are
oxidized, liberating electrons and lithium ions. Electrons flow through external circuit and
lithium ions flow through the organic electrolyte towards graphite carbon electrode. At
graphite electrode, lithium ions are reduced to lithium atoms and are inserted in to the
layered structure of graphite.
Applications:

Used in: Cameras, Calculator, cell phones, Portable radio, TV, Laptops.
Advances in Batteries
There is no “God Battery”, We believe that no single technology will dominate the industry
at large. Each of these five key factor starter lighting & ignition (SLI) batteries for internal
combustion engine (ICE) vehicles, Electric vehicles (EV), Electronic devices (ED),
Stationary battery energy storage (BES) and Other (aviation, drones, power tools, etc.). All
these have very different requirements on factors such as power density, capacity, cycle
lifetime, energy density, capital cost, charging time, reliability and safety. Winning solutions
remain unclear, and success will require a combination of next-generation innovation and
improvements to current technologies to meet evolving needs. Each technology has intrinsic
limitations to their technical and economic windows of operations, whereby extending one
performance feature (energy density, say) quickly goes at the expense of others (such as
safety or costs).
Lithium- batteries waste a lot of energy in the form of heat; to this end, they tend to degrade
at a faster rate too. They also require extra (and expensive) components to pump oxygen in /
out in an open cell configuration – one that is extremely different from conventionally sealed
batteries. One of the bigger hurdles researchers have faced when exploring this technology is
the mismatch between the voltages involved when charging / discharging a lithium-air
battery.

In the new battery, the same electrochemical reaction takes place between lithium and
oxygen-that is, it uses oxygen to drive a chemical reaction with the battery’s lithium during
the discharge cycle. The difference is that with current lithium-air batteries, the oxygen is
expelled to the atmosphere during the reverse reaction in the charging cycle, but in the new
variant, the reaction takes place without ever letting the oxygen revert to a gaseous form.
Instead, it stays inside the battery as solid lithium oxides.

The way the researchers overcame this issue is with improvements they made at the
nanometer level. Here, both the lithium and oxygen are confined tightly within a mixture of
cobalt oxide-particles they referred it as “nanolithia”. By doing this, the transitions between
LiO2, Li2O2, and Li2O, can all take place within the solid material. Under normal
circumstances, the nanolithia particles would be super unstable. By embedding them within a
cobalt oxide matrix (sponge-like material that has pores just a few nanometers). This matrix
stabilized the particles and served as a catalyst for the transformations.
 You can’t overcharge (and thus, damage) it: Finally, due to the fact that the chemical
reaction is naturally self-limiting, when it’s overcharged it shifts over to a different form that
prevents further activity. “With a typical battery, if you overcharge it, it can cause irreversible
structural damage or even explode,” But with the nanolithia battery, “the battery was
overcharged for 15 days, to a hundred times its capacity, but there was no damage at all”

Fuel cells
Introduction The principle of the fuel cell was discovered in 1839 by Sir William Grove,
who has been acknowledged as the “Father of the Fuel Cell”.
A fuel cell is a galvanic cell in which electrical energy is directly derived from the
chemical energy contained in a readily available fuel oxidant system.
Like any other electrochemical cell, the fuel cell has two electrodes and an electrolyte.
However, the fuel and the oxidizing agents are continuously and separately supplied to the
two electrodes of the cell, at which they undergo reactions. These cells are capable of
supplying current as long as they are supplied with the reactants.
A fuel cell essentially consists of the following arrangement:

Fuel / electrode / electrolyte / electrode / oxidant

At the anode, fuel under goes oxidation:

Fuel→Oxidation product+ ne-

At the cathode, the oxidant gets reduced:

Oxidant+ ne-→ Reduction products

Advantages

1) High power efficiency, eco-friendly

2) They are since the products of the overall reactions are not toxic

3) They can produce direct currents for long periods at a low cost.

Applications: They are used as auxiliary power generators in space vehicles. Fuel
cells are used in car engines, domestic lighting and heating.
Limitations

1. Cost of power is high as a result of the cost of the electrodes

2. Fuels in the form of gases and oxygen need to be stored in tanks under high pressure.

3. Power output is moderate

4. To have an appreciable voltage, a battery of fuel cells must be available.

 Classification of fuel cells:

Based on operating temperature and nature of electrolyte, fuel cells are classified as:

1. Polymer Electrolyte Fuel Cell(PEFC)

2. Alkaline Fuel Cell(AFC)
3. Phosphoric Acid Fuel Cell(PAFC)
4. Molten Carbonate Fuel Cell(MCFC)
5. Solid Oxide Fuel Cell(SOFC)
PEFC AFC PAFC MCFC SOFC
Electrolyte Nafion KOH(40%,85%) Liquid H3PO4 Li/Na/K Yttria
carbonate stabilized
solution ZrO2
Temperature 50-100οC 90-120οC,250 οC 220οC 600-700οC 1000οC
Charge carrier H+ OH- H+ CO32- O2-

Anode catalyst Pt or Pt/C Pt/Pd/Au/Ni Pt/C Ni Ni

Fuel Pure Pure H2 Pure H2,Natural H2,Natural
H2,Methanol H2,Methanol, Gas, gasified gas,
Reformed coal gasified
Natural gas coal
Applications Back-up Military, space Distributed Large Large
power, power electricity electricity
portable generation distributed distributed
power, generation generation
transportation

SOFC(Solid oxide fuel cell)

SOFCs are the most efficient fuel cell electricity generators currently being developed world-
wide. SOFC uses a solid ceramic as electrolyte, which operates at very high temperature
(600 – 1000oC)

Anode material : Nickel doped Zirconia cermet (Ni - ZrO 2 ), It is a mixture of Ni and yttria
stabilized Zirconia(YSZ) skeleton. Here Ni acts as a catalyst and YSZ conducts oxide ions.
Cathode material: Strontium doped Lathanum manganite (LaSrMnO3) (LSM) , it is good
material for oxygen reduction, good electronic conductivity and stable material.

Electrolyte Material: Number of solid oxide electrolyte materials are used in SOFC s. The
most used electrolyte is YSZ(Yttria-stabilized zirconia). It is good conductor for oxygen ions
and insulator for electrons. It is impervious to liquid and pervious to gas.
Working of SOFC:
The syn gas (mixture of hydrogen gas and carbon monoxide) dissociates into hydrogen and
CO. Hydrogen gas passes through the anode and gets oxidized by oxide ions.
From cathode the oxide ions diffuse through the electrolyte towards fuel rich anode and react
with hydrogen. The liberated electrons pass through the external circuit.
(Syngas can be produced from many sources, including natural gas, coal, biomass, or virtually any
hydrocarbon feedstock, by reaction with steam (steam reforming), carbon dioxide (dry reforming) or
oxygen (partial oxidation)
Reactions:
Anode:
H2 + O2- → H2O + 2e-
Cathode: ½ O2+2e- →O2-
Overall reaction: H2 + ½ O2 → H2O

Advantages (Benefits)
High power density, High cell operating temperature permits internal production of H 2 and
CO, Higher system efficiency, constant power production, fuel choice.
Application:
1. SOFC technology has been developed for a broad spectrum of power generation
applications like
Portable electronic appliances, power tools, laptops, cell phones, power backups,
transportation, power distribution.

Advances in Fuel Cells

Scientists, Technologists and manufacturing Industries at present working on improving key
elements of the present fuel cell stack technology. Presently, focusing mainly on advances in
catalyst Technology. Hydrogen fuel cell design employs catalyst layers coated on either side
of a proton-exchange membrane (PEM), to catalyze the desired oxygen reduction and
hydrogen oxidation reactions at the cathode and anode, respectively.
PEM Fuel Cells Proton exchange membrane (PEM) (or “solid polymer”) fuel cells use an
electrolyte that conducts hydrogen ions (H +) from the anode to the cathode. The electrolyte is
composed of a solid polymer film that consists of a form of acidified Teflon. PEM fuel cells
are currently the most promising type of fuel cell for automotive use and have been used in
the majority of prototypes built to date. As a result, the remainder of this course will focus
exclusively on PEM fuel cells. PEM fuel cells typically operate at 160 to 195 ºF (70 to 90 ºC)
and a pressure of 1 to 2 barg.PEM fuel cells are currently the most promising type of fuel cell
for automotive use and have been used in the majority of prototypes built to date. As a result,
the remainder of this course will focus exclusively on PEM fuel cells.

Schematic representation of PEM fuel cell

Direct Methanol PEM Fuel Cells

PEM fuel cells can also run using methanol fuel directly, rather than hydrogen. Although the
energy released during this reaction is less than when using pure hydrogen, it results in a
much simpler fuel storage system and circumvents the need to produce hydrogen. In a direct
methanol PEM fuel cell, the cells are supplied with a liquid mixture of methanol and water at
the anode, and air at the cathode. At 130 ºC, a noble catalyst immediately decomposes the
methanol according to the reaction:
CH3OH + H2O  6H+ + CO2 + 6e–
Oxygen, from the air, ionizes and reacts with the hydrogen to form water:
3 /2O2 + 6e– + 6H+  H2O
Combining the anode and cathode reactions, the overall cell reaction results in pure water and
carbon dioxide. This technology is still in its infancy, but holds great promise for the future.
 Super capacitors
Supercapacitor can be defined as a energy storage device that stores energy
electrostatically by polarising an electrolytic solution. A supercapacitor is a type of
capacitor that can store a large amount of energy, typically 10 to 100 times more energy per
unit mass or volume compared to electrolytic capacitors.
Classification of supercapacitors:
On the basis of mechanism of energy storage, supercapacitors can be divided into three
general classes:
 Electrochemical double-layer capacitors (EDLC): The capacitance is rendered by the
adsorption/desorption of charges at the junction of electrode-electrolyte.
 Pseudocapacitors: The capacitance is due to Faradaic processes, such as oxidation-
reduction reactions which involve the transfer of charge between electrode and electrolyte.
 Hybrid capacitors: The capacitance is due to combination of formation of electrical double
layer as well as oxidation-reduction reactions process

Electrical double layer super capacitors (EDLS);

• Electrical double layer super capacitors are also known as ultra capacitors or supercapacitors.
 Unlike batteries no chemical reaction takes place when energy is being stored or
discharged and so ultra capacitors can go through hundreds or thousands of charging cycles with
no degradation.
Principle:
Energy is stored in supercapacitor by polarizing the electrolytic solution. The charges are
separated via electrode –electrolyte interface.
 Schematic representation of EDLC
Construction:
Supercapacitor consists of a porous electrode, electrolyte and a current collector (metal
plates). There is a membrane, which separates, positive and negative plated is called
separator.
Working:
There are two carbon sheet separated by separator. The geometrical size of carbon sheet is
taken in such a way that they have a very high surface area. The highly porous carbon can
store more energy than any other electrolytic capacitor. When the voltage is applied to
positive plate, it attracts negative ions from electrolyte and when the voltage is applied to
negative plate; it attracts positive ions from electrolyte. Therefore, there is a formation of a
layer of ions on the both side of plate. This is called ‘Double layer’formation. For this
reason, the supercapacitor can also be called Double layer capacitor. The ions are then stored
near the surface of carbon and the distance between the plates is in the order of angstroms.
According to the formula for the capacitance,
Dielectric constant of medium X area of the plate
Capacitance = -----------------------------------------------------------------
Distance between the plates

• Supercapacitor stores energy via electrostatic charges on opposite surfaces of the electric
double layer. They utilize the high surface area of carbon as the energy storage medium,
resulting in an energy density much higher than conventional capacitors.

• The purpose of having separator is to prevent the charges moving across the electrodes.

• The amount of energy stored is very large as compared to a typical capacitor

because of the enormous surface area created by the porous electrodes and the
small charge separation (10 angstroms) created by the dielectric separator.
 Diagram to show formation of double layer
Electro
lyte
▬ - + 
+ +
+ 
- 
+
+ 

+ Separ

- +  +
+ ator
+ 
+ 
- +
Electric double
-layer
+
•
Advantage
- + and aging.
Long life: It works for large number of cycle without wear
• Rapid charging: it takes a second to-charge completely+
-
• Low cost: it is less expensive as compared to electrochemical battery.
• High power storage: It stores huge amount of energy in + a small volume.
• Faster release: Release the energy -much faster than battery.
Disadvantage
• They have Low energy density -
•
•
Individual cell shows low voltage
-
Not all the energy can be utilized during discharge
• - to battery.
They have high self-discharge as compared
•
-
Voltage balancing is required when more than three capacitors are connected in series.

•
Applications:
-
They are used in electronic applications such as cellular electronics, power conditioning,
uninterruptible power supplies (UPS)-
•
•
-
They used in industrial lasers, medical equipment.
They are used in electric vehicle and for load leveling to extend the life of batteries.
• - system for uninterrupted service.
They are used in wireless communication
•
-
There are used in VCRs, CD players, electronic toys, security systems, computers, scanners,
smoke detectors and coffee makers.
Advances in supercapacitors -

-
Supercapacitors are commonly used wherever a quick energy boost is needed, as an
alternative to a rechargeable battery. The most prevalent type of supercapacitors, EDLCs

- provide thousands or tens of thousands of times the

(electrical double layer capacitors),
capacitance of normal capacitors while their energy density makes them 10 times smaller
- lithium ion (Li-ion) battery, offers higher energy
than batteries. The alternative, a secondary

-
density with reduced self-discharge, but they effectively wear out after a number of
charge/discharge cycles. They also suffer from safety-related concerns such as thermal
runaway, which can be catastrophic.There is another device type on the market which
combines the best features of EDLCs and Li-ion batteries. Called Li-ion capacitors, or
hybrid capacitors, they are effectively a combination of the two technologies.
Inside a Li-ion capacitor (pictured below), the positive electrode is made of activated carbon.
This is immersed in a liquid electrolyte (similar to the Li-ion salt solution used in batteries)
together with the negative electrode, made of a carbon-based material doped with lithium
ions. A separator prevents direct electrical of a carbon-based material doped with lithium
ions. A separator prevents direct electrical contact. Pre-a carbon-based material doped with
lithium ions. A separator prevents direct electrical contact. Pre-doping the negative electrode
with lithium ions reduces its electrical potential, meaning a higher output voltage can be
obtained without a high potential at the positive electrode, up to around 3.8V. Compared to a
Li-ion battery, in which the ions are inserted or extracted (intercalated or deintercalated) into
the carbon lattice, ions in the Li-ion capacitor are simply adsorbed or desorbed on the
electrode surface, there is no crystalline change taking place.

--------------------