Applied Chemistry for Engineers (24CHE12/22)

MODULE 1
Energy Conversion and Storage

Fundamentals of Electrochemistry: Gibb’s free energy, Single electrode potential, Galvanic

cell, EMF, Reference electrode, derivation of Nernst equation and numerical, concentration cell
and numerical. (3 Hrs.)
Batteries: Introduction, classification, characteristics. Construction, working and applications of
Zn- air and Li -ion battery (2 Hrs)
Fuel cell: Definition and classification. Construction, working and applications of solid oxide
fuel cell (SOFC) (1 Hr)
Photo Voltaic Cells: Introduction, construction and working of silicon solar cell and dye-
sensitized solar cell, advantages and disadvantages of PV cells (2 Hrs)
Supercapacitors: Introduction and classification. Construction, working and applications of
electro chemical double layer capacitors. (1 Hr)

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
1
depending on the state of matter), the result is standard free energy change (∆G ο),

∆Gο=∆Hο- T∆Sο

When ∆G is zero, the system has reached an equilibrium state, when ∆G is negative, the forward
reaction is spontaneous, when ∆G is positive, the reverse reaction is spontaneous.

Change in Gibbs free energy (∆G),standard Gibbs free energy change (∆G ο) and equilibrium
constant (K) are related by Van’t Hoff’s equation

∆G= ∆Gο+ RT lnK

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.

Figure: Formation of Helmholtz double layer

When a metal is in contact with a solution of its own ions, two types of reactions are possible i. e.
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).
Reaction at anode (oxidation): 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.
Reaction at cathode (reduction): Mn++ ne-→M ----------(2)
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. The potential difference between 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.

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 halfcell. 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

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

At cathode: Cu2++2e- → Cu(s) ----------------------- (2)

The net cell reaction is obtained by adding equations 1 and 2Zn(s) + Cu2+(aq)) →Zn2+(aq) + Cu(s)

3
 Figure: A Galvanic cell

The electrons released at the zinc half-cell build up an electrical potential difference between
the electrodes. This is indicated by the voltmeter.
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 E cell.
It is expressed in volts.

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

Where Ecathode and 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 – Eο Anode

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
(In a galvanic cell the electrode with lesser reduction potential acts as anode and electrode with
higher reduction potential acts as cathode.)

4
 Reference electrode:

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/H 2/H+)
Secondary reference electrodes

They are commonly used to determine electrode potentials of other electrodes. Examples– silver-
silver chloride electrode, calomel electrode etc.

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

Hg| Hg2Cl2(s)| Cl-

Figure: Construction of calomel electrode

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.
5. The potential developed from calomel electrode depends on the concentration of KCl solution.
.
E=E0- log[Cl-]2
.
E=E0 - log [Cl-]

At 298 K, E= E0 – 0.0591 log [Cl-]

5
Nernst Equation for single electrode potential

n+
Single electrode potential (E), change in free energy (∆G) and the concentration M 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 ofelectricity
that flow and the energy available per coulomb.
Work = Number of coulombs x Energy available/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 = n x F x E (2)
-∆G = nFE (3)
Under standard conditions
ΔGο = -nFEο (4)

Where Eο is a constant called the standard electrode potential. For the reaction,
n+
M +ne ⇌ M
The equilibrium constant Kc is related to change in free energy by the
Van’t Hoff equation, ∆G= ∆G0 + RT lnKc

[ ]
Kc =
[ ]

ο [ ]
∆G= ∆G + RT ln (5)
[ ]
o n+
∆G =∆G + RT ln[M] – RT ln [M ] (6)

Substituting from equations 3&4 for ∆G and ∆G o

o n+
- nFE = -nFE + RTln[M]- RTln [M ] (7)
6
 Dividing equation 7 by -nF,

⁰ [ ] [ ᶯ ]
= + – (8)

Under standard conditions M=[Link] the above equation becomes

n+
E = Eο+ ln [M ] (9)
Where E = electrode potential; Eο = standard electrode potential; Substituting the values of R
= Universal Gas Constant [8.314J/K/mol]; T = temperature in Kelvin [298K]; F = Faraday
Constant [96500C/mol]; n=number of electrons involved.

𝟎.𝟎𝟓𝟗𝟏
E = Eo + log [Mn+]
𝒏

This is the Nernst Equation for the Single Electrode Potential.

Nernst Equation for Cell Potential
𝟎.𝟎𝟓𝟗𝟏 𝐂𝐨𝐧𝐜𝐞𝐧𝐭𝐫𝐚𝐭𝐢𝐨𝐧 𝐨𝐟 𝐬𝐩𝐞𝐜𝐢𝐞𝐬 𝐚𝐭 𝐜𝐚𝐭𝐡𝐨𝐝𝐞
E = Eo + log
𝐧 𝐂𝐨𝐧𝐜𝐞𝐧𝐭𝐫𝐚𝐭𝐢𝐨𝐧 𝐨𝐟 𝐬𝐩𝐞𝐜𝐢𝐞𝐬 𝐚𝐭 𝐚𝐧𝐨𝐝𝐞

Nernst Equation for Daniel Cell:

2+ 2+
Zn (s) + Cu (aq) Zn (aq) + Cu(s)
𝟎.𝟎𝟓𝟗𝟏 [𝐂𝐮²⁺]
E = Eo + log
𝐧 [𝐙𝐧²⁺]

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
7
solutions are different.
Concentration cell is represented as-
Cu(s) | Cu2+[M1] || Cu2+[M2] | Cu(s)

Construction:

Two copper electrodes are dipped in CuSO4 solutions 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 througha 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

.
EAnode = Eo + log [M1]

.
ECathode = Eo + log [M1]

. .
ECell = Eo Cathode + log [M2] – [Eo Anode + log [M1] ]

Eo Cathode = Eo Anode
. [ ₂]
ECell = log
[ ₁]

By the above equation

If [M1] = [M2] ,emf of the cell is zero (Ecell = 0)
If [M2] > [M1], emf is positive
[M2]
If is large, Ecell is large
[M1]
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Problems:
2+
1. Calculate the standard electrode potential of Cu /Cu if its electrode potential at25οC is
2+
0.296V and [Cu ] is 0.015M.
.
0.296 = Eo + log [0.015]
Eo = 0.35 V

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 [Link] the cell representation, cell reactions and calculate EMF of cell at
ο
30 C. Given that standard potentials of Cu and Fe electrodes are 0.34 and -0.41V respectively.
2+ 2
Representation of cell is Fe/Fe //Cu +/Cu

Cell reactions:
2+
At Anode: Fe → Fe +2e-
2+
At cathode: Cu + 2e-→ Cu

Overall reaction:
2+ 2+
Fe + Cu →Fe + Cu

. . .
E = (0.34- (-0.41)) + log = 0.76 V
.

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

0.0126V at 25ο[Link] the valency of tin.
. [ ₂]
ECell = log
[ ₁]
. .
n= log
. .

n =1.998=2

4. Two copper rods placed in copper sulphate solutions of equal concentrations are
connected to form a concentration cell

(a) What is cell potential?

(b) Calculate the cell potential if one of the solutions is diluted to1/5 thof its original
concentration
9
 . [ ₂]
(a) ECell = log
[ ₁]
Given M1=M2,
Hence cell potential=0

(b) Assume M2=1M then M1=1/5M

. [ ₂]
ECell = log
[ ₁]

. [ ]
ECell = log
[ / ]

.
ECell = log 5

ECell = 0.02955 x 0.699 = 0.0206 V

5. 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.
2+ 2+
The cell is represented as, Cu(s)/Cu (0.001M) // Cu (0.1M)/Cu(s)
2+
At the anode, Cu → Cu (0.001 M) + 2e-
2+
At the cathode, Cu (0.1 M) + 2e → Cu

. [ ₂]
ECell = log
[ ₁]

. [ . ]
ECell = log
[ . ]

.
= log 100

= 0.02955 x 2

ECell = 0.0591 V

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 BATTERY

A Battery is a device that consists of two or more galvanic cells connected in series or parallel
or both, which converts chemical energy into electrical energy through redox reactions.
Example: Lead- acid battery, Nickel-cadmium battery etc.

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.
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.

Figure: Construction of battery

Battery Characteristics:
1. Voltage:

Voltage (or Cell potential) is the electrical force that drives electric current between
electrodes. Voltage of a cell is given by the equation;
Ecell=(EC-EA)-ηA- ηC -iRcell

11
Where, ηA and ηC are overpotential at anode and cathode respectively. Over potentials should
be less to derive maximum voltage. Rcell is internal resistance of the cell. Internal resistance
should also be less to derive maximum voltage.
[Link]:
It is the charge in Ampere-hours (Ah) that can be withdrawn from fully charged cell or battery
under specified conditions. It is determined by Faraday’s relation:
WnF
C= (where, W=weight of active material; F=Faraday’s constant; M=Molar mass of active
M

material; n=number of electrons involved in cell reaction).

[Link] 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.
[Link] 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 performance.

CLASSIFICATION OF BATTERIES

Batteries are classified into:

1. Primary Batteries

2. Secondary Batteries

3. Reserve Batteries

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 [Link]: Zn-MnO2 battery, Zn-carbon battery (Leclanche cell), Zn-
air battery etc.
2. Secondary Batteries
A battery which after discharging can be recharged again by passing the electric current

12
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 forelectrical energy.
Example: Lead storage battery, Nickel Cadmium Battery, Li-ion 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.

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.

Construction:

Anode: Powdered Zinc

Cathode: Carbon
Electrolyte: KOH (5M)
Separator: Polyethylene

Figure: Zn-air battery

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,
13
𝒁𝒏/ KOH (5 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 + 𝟒𝑶𝑯− → 𝟐𝒁𝒏𝑶 + 𝟐𝑯𝟐𝑶+𝟒𝒆-

Cathode reaction: O𝟐 + 𝟐𝑯𝟐𝑶 + 𝟒e- → 𝟒𝑶𝑯−

The overall reaction is 𝟐𝒁𝒏 + 𝑶𝟐 → 𝟐𝒁𝒏𝑶

Zn-air battery has an energy density of about 100 W h kg-1. This is three times that of the
classical lead acid battery and twice that of Ni-Cd battery.
Advantages:

1. High capacity [Link] cost 3. Long shelf life

Disadvantages:

1. Limited power output 2. Short activated life

Applications:
It finds applications in hearing aids, electronic pager, rail road signaling, medical devices,
remote communications and military radio receivers.

14
 Lithium ion battery (secondary batteries)
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).
Representation: Li/Li+, C/LiPF6/Li-CoO2
Components:
1. Anode: Lithium intercalated graphite or Li xC6
2. Cathode: Partially Lithiated oxides of Ni, Co or Mn or Li yNiO2 / LiyCoO2
y = 1-x; where x, y used in non-stoichiometric compounds
3. Cathode current collector: Al/ Cu foil
4. Anode current collector: Cu foil
5. Electrolyte: Li salt (LiPF6, LiBF4) in an organic solvent (i.e. ethylene carbonate).
6. Separator: Microporous polyethylene or polypropylene soaked in electrolyte is used as
separator.
In Li-ion battery, the container is made up of stainless steel or aluminium alloy. At anode, lithium
atoms occupy the position between the graphite lattice layers. lithium ion move between the
electrodes, using an intercalated electrode material. Metal atoms and ions can enter layered solids
reversibly.

Figure: Li-ion battery

At anode:
Discharging

LixC6 xLi+ + xe- + 6C

Charging

15
At cathode: Discharging
+ -
Li1-xCoO2 + xLi + xe LiCoO2
Charging

Overall reaction:
Discharging

Li1-xCoO2 + LixC6 6C + LiCoO2

Charging

During discharge of battery, Li 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 powering portable electronic devices like cell phones, laptops, Cameras, Calculator,
Portable radio, electrical vehicles and aerospace applications.

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 the chemical energy contained in a readily available
fuel oxidant system is converted directly into electrical energy by means of electrochemical
processes in which the fuel is oxidized at the anode.
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:

16
 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

The electrons liberated from the oxidation process at the anode, can perform useful work when they
pass through the external circuit to the cathode.

Advantages:
1) Their power efficiency is high.

2) They are eco-friendly since the products of the overall reactions are not toxic.

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

4) They are used as auxiliary power generators in space vehicles. Fuel cells are usedin 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):

In this cell, a solid ion exchange membrane (fluorinated sulfonic acid polymer, nafion) which is a
good conductor for proton(H+) is used as an electrolyte. Polymer cannot withstand higher
temperature, thus operating temperature for this cell is around 100 ο[Link] electrolyte is
active in hydrated form. Water formed as reaction byproduct is used for hydration of membrane.
Most commonly used fuels in this cell are H2 gas and methanol. H2 gas must be free of CO which
acts as catalytic poison at low temperature. The catalyst used is platinum (Pt).
2. Alkaline Fuel Cell (AFC):
17
Concentrated KOH retained in solid matrix (usually asbestos) is used as an electrolyte in this fuel
cell. This cell can be operated at high temperature of 250 οC with 85%KOH ,or at low temperature
of 120οC with less concentrated 40% KOH.A wide range of electrocatalysts can be used
(e.g.,Ni,Ag,Au and noble metals).Air used as oxidant at cathode should be free of CO [Link]
CO2 readily reacts with the KOH to form K2CO3,thus altering the electrolyte. Most commonly
used fuel in this cell is pure H2 gas.
3. Phosphoric Acid Fuel Cell (PAFC):
The concentrated(100%) phosphoric acid retained in solid silicon carbide is used as an electrolyte
in this fuel cell, which operates at 150 to 220ο[Link] used in both the anode and
cathode is Pt. Fuel should be free of CO, which is a severe poison for Pt electro catalyst. Most
commonly used fuels in this cell are H2 gas, reformed natural gas and methanol.
4. Molten Carbonate Fuel Cell (MCFC)
The electrolyte in this fuel cell is a combination of alkali carbonates, which is retained in a
ceramic matrix of [Link] fuel cell operates at 600 to 700οC where the alkali carbonates
form a highly conductive molten salt, with carbonate ions providing ionic conduction. At the
high operating temperatures in MCFCs, Ni (anode) and nickel oxide (cathode) are adequate to
promote reaction. Noble metals are not required. Most commonly used fuels in this cell are H 2
gas, natural gas and gasified coal.
5. Solid Oxide Fuel Cell (SOFC):
The electrolyte in this fuel cell is a solid, nonporous metal oxide, usually Y 2O3 stabilized
[Link] cell operates at 1000οC where ionic conduction by oxygen ions takes place. The anode
used is Ni-ZrO2, and the cathode is Sr-doped LaMnO3. Most commonly used fuels in this cell are
H2 gas, natural gas and gasified coal. At low-temperature fuel cells (PEFC,AFC, PAFC), protons
or hydroxyl ions are the major charge carriers in the electrolyte, whereas in the high-
temperature fuel cells, MCFC and SOFC, carbonate ions and oxygen ions are the charge
carriers, respectively. Maximum efficiencies of 60%, 45%,60%,and 70% have been estimated
for industrial FC,PAFC,MCFC and SOFC, respectively.

18
 A summary of five types of fuel cells is given below:
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,250οC 220οC 600-700οC 1000οC
Charge H+ OH- H+ CO32- O2-
carrier
Anode Pt or Pt/C Pt/Pd/Au/Ni Pt/C Ni Ni
catalyst
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
transportatio
n

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 - ZrO2 ), 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.
19
 Figure: Solid oxide fuel cell (SOFC)

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.

Applications:

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.
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 SOLAR ENERGY

Conversion of solar energy into electrical energy

Solar energy is clean and renewable source of energy and alternative to fossil fuels.
Utilization of solar energy
1. Direct utility – when solar energy is directly converted to electric energy. Example:
PV cells
2. Indirect utility: Conversion of Solar energy to chemical energy, which later used as
energy sources. Example: Photosynthesis.
Photovoltaic cell
They are referred to as semiconductor devices that convert sunlight (electromagnetic radiations)
into direct current electricity. As long as light is shining on the solar cell, it generates electrical
power. When the light stops, electricity stops. Solar cells never need recharging like a battery.
Principle:
The energy associated with photon (E) is given as-
E = hν =hc/λ
Where h is planks constant
C is velocity of light
λ is wavelength of light

Figure: Silicon based solar cell

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 Construction and working of PV cell

 Consists of Ultra thin wafers of n type(phosphorous doped) on to top of boron doped Si

(p-type)
 A metallic grid forms one of the electrical contact of the diode and allows the light to fall
between grid lines
 An antireflective layer between grid lines increases the amount of transmitted light.
 The cells other electrical (bottom) contact is formed by Ag metal.
 When light radiation falls on p-n junction diode, e - - hole pairs are generated by absorption
of radiations.
 The electrons are drifted and collected to n-type. The holes are drifted and collected at p-
type end.
 When these ends are electrically connected the current flows between the two ends
through external circuits.

Importance of Photovoltaic cells

Photovoltaic cells can generate electricity for a wide variety of applications

 Solar energy, being unlimited, in exhaustible and renewable photo voltaic cells can be
considered as continuous energy source.
 Electricity can be generated in rural areas, individual families which are living far awayfrom
electric grid connections and in remote areas such as mountains.
 They can be used for domestic lighting, spinning of fans, grinding grains, transistor radios,small
TV sets and tape recorders.
 In agricultural sectors it is used for irrigation.
 In production activities such as milling, sawing and sewing.
 During the operation of solar cells, there is no harmful emission or transformation ofmatter
(generation of pollutants) nor any production of noise or other by-products.
 Photo Voltaic cells provide power for space craft and satellites, an extra-terrestrialdimension of
photovoltaic.

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Advantages of solar cells:
1. Low operating cost (no fuel)
2. No moving parts and no wear and tear
3. Ambient temperature operation
4. High public acceptance and excellent safety record

Limitations of solar cells

1. Energy can be produced only during day time
2. High installation costs
3. Poor reliability of auxiliary elements including storage
4. Lack of widespread commercially available system integration and installation

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 Dye-sensitized solar cell

Dye Sensitized solar cells (DSSC) are third generation photovoltaic cells .They are low-cost solar
cells belonging to the group of thin film solar cells.

Principle and Working

A modern DSSC is composed of a porous layer of titanium dioxide nanoparticles, covered with a
molecular dye that absorbs sunlight, like the chlorophyll in green leaves. Like in a conventional
battery, an anode (the titanium dioxide) and a cathode (the platinum) are placed on either side of a
liquid conductor (the electrolyte).

Sunlight passes through the transparent electrode into the dye layer where it can excite electrons
which flow into the titanium dioxide. The electrons flow toward the transparent electrode where
they are collected for powering a load. After flowing through the external circuit, they are re-
introduced into the cell on a metal electrode on the back, flowing into the electrolyte. The
electrolyte then transports the electrons back to the dye molecules.

Figure: Schematic representation of dye sensitized solar cell (DSSC)

The dye molecules are quite small (nanometer sized), so in order to capture a reasonable amount
of the incoming light the layer of dye molecules needs to be made fairly thick, much thicker than
the molecules themselves. To address this problem, a nanomaterial is used as a scaffold to hold

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 large numbers of the dye molecules in a 3-D matrix.

Advantages:

 DSSC are currently the most efficient third generation solar technology available.
 DSSC is a disruptive technology that can be used to produce electricity in a wide range of light
conditions, indoor and outdoor, enabling the user to convert both artificial and natural light into
energy to power a broad range of electronic devices.
Disadvantages:
 It is using the liquid electrolyte, which has temperature stability problems.
 Costly ruthenium (dye), platinum (catalyst) and conducting glass are needed to prepare a DSSC.
 Electrolyte solution contains volatile organic compound solvents, which must be sealed carefully as
they are hazardous to human health and the environment.

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 Supercapacitors
Owing to their superior performance of high power density, short charging time, long cycle life,
good temperature characteristics and better operation safety, supercapacitors are becoming a
critical device for energy storage that can replace some of the traditional chemical batteries.
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

Supercapacitors

Electrical Double Layer Capacitors Pseudocapacitors

Charge storage: Charge storage:
Electrostatically (Helmholtz Layer) Electrochemically (Faradiaic charge transfer)

Activated Carbons Carbon Aerogels

Conducting Polymers Metal Oxides

Carbon Nanotube (CNT), Graphene,

Carbid Derived Carbon (CDC)

Hybrid Capacitors
Charge storage:
Electrostatically & Electrochemically

Asymmetric Composites
Pseudo/EDLC


Classification of supercapacitors


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 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.

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.


Figure: Schematic representation of EDLC

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According to the formula for the capacitance,


Capacitance =

• 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.

Advantages:
• Long life: It works for large number of cycle without wear and aging.
• 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.

Diagram to show formation of double layer

Electrolyte
- +
▬
- +  +
+ Separator
- + +
+ 

Electric
double layer
Figure: formation of electric double layer

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 Disadvantage:
• They have Low energy density
• Individual cell shows low voltage
• Not all the energy can be utilized during discharge
• They have high self- discharge as compared to battery.
• 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.
• They are used in wireless communication system for uninterrupted service.
• There are used in VCRs, CD players, electronic toys, security systems, computers, scanners,
smoke detectors and coffee makers.
*****************

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Module 1 question bank

Q.1 Write a note on Gibb’s free energy, Single electrode potential, Galvanic cell, Cell potential
Q.2 Derive the relationship between electrode potential and concentration of electrolyte.
Q.3 An electrochemical cell consists of zinc electrode in 0.05M ZnSO 4 solution and nickel electrode in 0.4
M NiSO4 solution. The standard electrode potential of Zn and Ni are -0.76 V and -0.24V respectively.
Give the cell representation, cell reactions and calculate the EMF of the cell at 30 οC.
Q.4 What are concentration cells? A cell is obtained by combining two Cd electrodes immersed in
cadmium sulphate solutions of 0.1 M and 0.5 M at 25 οC. Give the cell representation, cell reactions and
calculate EMF of the cell.
Q.5 What are secondary batteries? Explain the construction and working of Lithium ion battery.
Q.6 What are Primary batteries? Explain the construction and working of Zn - Air battery
Q.7 Explain the construction and working of solid oxide fuel cell (SOFC) and write the reactions involved.
Q.8 What are super capacitors? Explain construction and working of EDLC.
Q.9 What are batteries? Write the classification of batteries with examples.
Q.10 “Photovoltaic cell is based on photoelectric effect” justify the statement by explaining the
construction and working of a typical silicon PV cell.
Q.11 Examine the theory behind solar energy to electrical energy by dye sensitized solar cells. Explain its
construction and working.
Q.12 What is reference electrode? Explain the construction of a secondary reference electrode.

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