Engineering Chemistry (22CHE12/22)

MODULE 1
Energy Conversion and Storage
Fundamentals of Electrochemistry: Gibb’s free energy, Single electrode potential, Galvanic cell,
Concentration cell, EMF, Derivation of Nernst equation and Numerical. (2Hrs)
Batteries: Introduction, classification, characteristics. Construction, working and applications of
Zn- air and Li -ion battery (2Hrs)
Fuel cell -Definition and classification. Construction, working and applications of solid oxide
fuel cell (SOFC) (1Hr)
Photo Voltaic Cells – Introduction. Construction and working of silicon solar cell and Dye-
sensitized solar cell, Advantages and disadvantages of PV cells (2Hrs)
Super Capacitors: Introduction and classification. Construction, working and applications of electro
chemical double layer capacitors. (1Hr)

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(∆G ο),

∆G ο=∆Hο -T∆Sο

Change in Gibbs free energy(∆G),standard Gibbs free energy change(∆Gο) and equilibrium
constant(K)are related by Vant Hoff equation.

∆G= ∆Gο+ RT lnK

When a reaction is at equilibrium (∆G=0)
Hence we can conclude that 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.
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

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.
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.

Nernst Equation

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= n x F x E ----------------(2)
-∆G= nFE -------------------------- (3)
Under standard conditions
ΔGο= - nFEο ----------------------------- (4)

Where E ο is a constant called the standard electrode potential.

For the reaction,

Mn+ + ne ⇌M
The equilibrium constant Kc is related to change in free energy by the Van’t Hoff
equation, ∆G= ∆G0 + RT ln Kc
[𝑀]
Kc=
[𝑀𝑛+]

[𝑀]
∆ G= ∆G ο + RT ln[Mn + ] -----------(5)

∆ G =∆G0+RTln[M] - RTln[Mn+]--------(6)

Substituting from Eqs.3&4 for ∆G and G0 ,

- nFE = -nFE0+ RTln[M]-RTln[Mn+]--------(7)

Dividing eqn.7 by -nF,

+
0 n
−𝑛𝐹𝐸 −𝑛𝐹𝐸 𝑅𝑇𝑙𝑛[𝑀] RTln[M ]
= + - -----------(8)
−𝑛𝐹 −𝑛𝐹 −𝑛𝐹 −𝑛𝐹

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

𝑹𝑻
E = Eο + ln [Mn+] ---------------------------------- (9)
𝒏𝑭

Where E = electrode potential; E ο = 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 = Eο + log [Mn+]
𝒏

This is the Nernst Equation for the Single Electrode Potential.

Nernst Equation for Cell Potential
𝟎.𝟎𝟓𝟗𝟏 𝒔𝒑𝒆𝒄𝒊𝒆𝒔 𝒂𝒕 𝒄𝒂𝒕𝒉𝒐𝒅𝒆
E = Eο + log
𝒏 𝒔𝒑𝒆𝒄𝒊𝒆𝒔 𝒂𝒕 𝒂𝒏𝒐𝒅𝒆

Nernst Equation for Daniel Cell:

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

E = Eο +
𝟎.𝟎𝟓𝟗𝟏 [Cu2+]
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
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-

ApplyingNernst equation-

Ecell=Ecathode -Eanode
0.0591
Eanode = Eο+ 𝑛
log[M1]

0.0591
Ecathode= Eο+ 𝑛
log[M2]

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

𝟎.𝟎𝟓𝟗𝟏 [𝐌𝟐]
Ecell= log
𝐧 [𝐌𝟏]

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]

Problems:

1. Calculate the standard electrode potential of Cu2+/Cu if its electrode potential at 25 ο C

is 0.296V and [Cu2+]is 0.015M.

0.0591
0.296= E0+ log[0.015], E0=0.35V
2

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 30 οC. Given that
standard potentials of Cu and Fe electrodes are 0.34 and-0.41V respectively. Representation of cell
 is Fe/Fe2+//Cu2+/Cu

Cell reactions are Anode:Fe→Fe2++2e-

Cathode:Cu2++2e-→Cu
Overall reaction:

Fe+ Cu2+→ Fe2++Cu

2.303𝑋8.314𝑋303 0.45
E= (0.34-(-0.41)+ log
2𝑋96500 0.25

=0.76V

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.

0.0591 [𝑀2]
Ecell = log
𝑛 [𝑀1]
0.0591 0.064
n= log
0.0126 0.024

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 th of its original concentration
0.0591 [𝑀2]
a) Ecell = 𝑛
log
[𝑀1]

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

0.0591 [1]
Ecell = log 1
2 [ ⁄5]

0.0591
Ecell = log5
2
 Ecell =0.02955X0.699=0.0206V

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.

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 [𝑀2]
Ecell = log
𝑛 [𝑀1]

0.0591 [0.1]
Ecell = log
2 [0.001]
0.0591
Ecell = log100
2

Ecell=0.0591V
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.

Battery Characteristics:
1. Voltage: Voltage (or Cell potential) is the electrical force that drive electric current between
electrodes. Voltage of a cell is given by the equation;
Ecell=(EC -EA)-ηA - ηC -iRcell
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.
2. Capacity: 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).

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 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 irreversible.
Example: Zn-MnO 2 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.

4. 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
Alkaline batteries use potassium hydroxide as an electrolyte.
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.
Construction:
Anode: Powdered Zinc
Cathode: Carbon
Electrolyte: KOH (5M)
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: 𝟐𝒁𝒏 + 𝟒𝑶𝑯− → 𝟐𝒁𝒏𝑶 + 𝟐𝑯 𝟐𝑶 + 𝟒𝒆-

Cathode reaction: 𝑶𝟐 + 𝟐𝑯𝟐𝑶 + 𝟒e- → 𝟒𝑶𝑯 −
The overall reaction is 𝟐𝒁𝒏 + 𝑶𝟐 → 𝟐 𝒁𝒏𝑶

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:
[Link] power out put [Link] 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(Li-MO2 ),where M is Cobalt ( Co ) or Manganese (Mn)

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: Li-C6⇌Li++e-+6C

Cathode: Li++e-+CoO2⇌Li-CoO2

Net reaction: Li-C6 +CoO2⇌Li-CoO2+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 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:

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 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)

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 H 2 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)
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 220 ο[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 LiAlO 2. The fuel cell operates at 600 to 700 οC 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 Y2O3 stabilized ZrO2 .The cell operates at 1000 οC where ionic conduction by
oxygen ions takes place. The anode used is Ni-ZrO2, and the cathode is Sr-doped
[Link] commonly used fuels in this cell are H 2 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.

A summary of five types of fuel cells is given below:

PEFC AFC PAFC MCFC SOFC
Electrolyte Nafion KOH(40%,85%) Liquid H3 PO4 Li/Na/K Yttria
carbonate stabilized
solution ZrO2
Temperature 50-100οC 90-120οC,250 οC 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 H 2 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 (LaSrMnO 3) (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- → H 2O + 2e-
Cathode: ½ O2+2e- →O2-
Overall reaction: H2 + ½ O2 → H2 O
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.

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

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.
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.

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

Advantages
 DSSCs 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, indoors and outdoors, enabling the user to convert both artificial and natural light
into energy to power a broad range of electronic devices.

Disadvantages
 The use of the liquid electrolyte, which has temperature stability problems.
 Another disadvantage is that costly ruthenium (dye), platinum (catalyst) and conducting glass
or plastic (contact) are needed to produce a DSSC.
 A third major drawback is that the electrolyte solution contains volatile organic compounds (or
VOC's), solvents which must be carefully sealed as they are hazardous to human health and the
environment.
Importance of Photovoltaic cells
Photovoltaic cells can generate electricity for a wide variety of applications
1. Solar energy, being unlimited, in exhaustible and renewable photo voltaic cells can be
considered as continuous energy source.
2. Electricity can be generated in rural areas, individual families which are living far away
from electric grid connections and in remote areas such as mountains.
3. They can be used for domestic lighting, spinning of fans, grinding grains, transistor radios,
small TV sets and tape recorders.
4. In agricultural sectors it is used for irrigation.
 5. In production activities such as milling, sawing and sewing.
6. During the operation of solar cells, there is no harmful emission or transformation of matter
(generation of pollutants) nor any production of noise or other by-products.
7. Photo Voltaic cells provide power for space craft and satellites, an extra-terrestrial
dimension of photovoltaic.
Advantages
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
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

Super capacitors
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

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

Electrolyte
- + 
+
▬ + 
- 
+
+
+


+ +Separator
- +
+
 
+
+ 
- +
Electric
double layer

Advantage
• 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.
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.
*******************