MODULE-3

Sustainable Energy Systems

Introduction
Electricity is one of the most essential requirements of modern life. The most common methods
of generating electricity is from the thermal or hydro electric power plant. The efficiency of a typical
power plant is around 40%. The conversion of energy is stepwise in these plants. Efficiency of
generating electricity can be increased when there is direct conversion of chemical energy into
electrical energy and ELECTRO CHEMISTRY deals with the links between chemical reactions &
electricity.
Electrochemistry is the branch of chemistry, which deals with the study of inter conversion of
electrical energy and chemical energy.
It has wide applications to most practical surface phenomenon. Electrochemistry is the basis for the
much of the scientific underlying such as batteries, metallurgical processes, fuel cells, and other useful
charge storage devices.
Electrochemical cells
The devices which convert chemical energy into electrical energy and electrical energy into chemical
energy are called electrochemical cells. Cells consist of two electrodes immersed in suitable
electrolytes.
Classification of electrochemical cells
Electrochemical cells are classified as electrolytic cells and galvanic cells.

Electrolytic cells
Electrolytic cell is a device which converts electrical energy supplied from the external source
into chemical energy.
Galvanic cells
A galvanic cell is a device in which the free energy of a physical or chemical process is
converted into electrical energy.
Galvanic cell consists of two electrodes immersed in suitable electrolytes. The reactions at the two
electrodes in such cells tend to proceed spontaneously and produce electricity.
Galvanic cells are further classified as chemical cells, concentration cells and fuel cells.
Chemical cells
In a chemical cell, emf is developed from chemical reactions within the cell. Chemical cells
are further classified as
Primary cells (irreversible cells) reversing current in these cells cause a different reaction to
occur at one or both the electrodes.
Secondary cells (reversible cells), reversing the current reverses the cell reaction.
Reactions
The process of conversion of chemical energy into electrical energy is called electrochemical reaction.
Electricity is generated in a galvanic cell by the spontaneous reduction – oxidation (redox) reaction
taking place in a physically separated half cell. Half cell consists of a metal dipped in suitable
electrolyte. When two half cells are connected internally through a salt bridge and externally through
a voltmeter or a galvanometer, it forms a cell. The electrode at which oxidation takes place is the
anode and the electrode at which the reduction takes place is the cathode.
Oxidation reaction involves loss of electrons. When a metal M loses electrons it is oxidized to
n+
M ions. The oxidation reaction is written as:
M → Mn+ + ne-
Reduction reaction takes place at the cathode. Reduction is the gain of electrons,
Mn+ + ne- → M
Construction of a galvanic cell
A galvanic cell is constructed by connecting two half cells externally by a metal wire through
a galvanometer or a voltmeter. The electrolytes at the two half-cells are connected by a salt bridge.
Salt bridge is an inverted U – shaped tube containing saturated KCl or NH4NO3 solution in agar-agar
gel. Porous plugs at the ends of the U – tube prevent the bulk flow of solution. Salt bridge connects
the electrolytes internally without mixing them, decreases liquid junction potential and maintains
electrical neutrality of the electrolyte. In the absence of a salt bridge, electrolytes develop charge and
flow of electrons stops.
Ex. Daniel cell

NOTE: KCl and NH4NO3 are amongst the electrolytes in which transport numbers of cations and
anions are nearly the same. The solution of these salts, therefore, often used as the salt bridge since
the liquid junction potential is then reduced to zero.
A Daniel cell consists of a zinc rod dipped in the ZnSO4 solution and a copper rod dipped in copper
sulphate solution, connected by a metal wire.
Zinc being more electropositive undergoes oxidation.
Zn → Zn2+ + 2e- (1)
2+
Electrons are left behind on the zinc rod and Zn ions move into zinc sulphate solution.
At the copper half cell, Cu2+ ions from the CuSO4 solution gain electrons and are reduced to
Cu atoms.
Cu2+ + 2e- → Cu (2)
Reactions (1) and (2) occurring at each half cell are called half cell reactions.
When two half cell reactions are added we get a net cell reaction.
i.e., (1) + (2), Zn + Cu2+ → Zn2+ + Cu
Generally, electrons do not figure out in the net cell reaction. The co-efficient of half cell reactions are
adjusted to get the same number of electrons in each half – cell reaction.
It is evident from the above description, that in a galvanic cell, electrons move from anode to cathode.
Electrode potential (E)
It is a measure of the tendency of a metal to lose electrons (oxidation potential) or to gain
electrons (reduction potential) when it is in contact with a solution containing its own ions.
Reduction potential
It is a tendency of a half cell to undergo reduction reaction or it the measure of the tendency of
a half cell to gain electrons when it is in equilibrium with the other half cell.
Standard electrode potential (E0)
Standard electrode potential is the Electrode potential measured under standard conditions i.e.,
the temperature is 250C, 1 atm pressure and when electrolytes are of unit molar concentration.
Single electrode potential
It is the potential developed at the junction of a metal and the solution when a metal is in contact
with its own ions.
Notations and conventions
1. Anode of a galvanic cell is ‘negative’ since oxidation takes place at the anode to give metal ions
and electrons. Metal ions go into solution leaving behind electrons on the metal rod hence metal
acquires a negative charge.
2. The cathode of a galvanic cell is ‘positive’. At the cathode, metal ions in the solution take up
electrons from the metal rod and undergo reduction to give metal atoms. Metal rod becomes
electron deficient and acquires a positive charge.
3. Representation of a galvanic cell
Anode | Electrolyte in which anode is placed ||Electrolyte in which cathode is placed | cathode
The anode is always written on the left-hand side while the cathode is written on the right-hand
side. Single vertical lines indicate the interface or boundary between the metal and solution.
Double vertical line denotes the salt bridge. Arrow represents the direction of flow of electrons.
Daniel cell is represented as
→
Zn | ZnSO4 (C1) || CuSO4 (C2) | Cu
Or
→
Zn | Zn (C1) || Cu2+ (C2) |Cu
2+

C1 and C2 are the concentrations of the electrolytes.

4. Electrode potential
By international agreement, electrode potential always refers to the reduction potential of the
metal represented as E ֯Mn+/M and, under standard conditions, standard reduction potential (SRP)
is represented by E M ֯ n+/M
5. If oxidation potential of a metal is + X volts then its reduction potential is –X volts.
6. Emf of a cell is given by
Ecell = Ecathode - EAnode
Standard emf of the cell,
E c֯ ell = E c֯ athode – E A֯ node
Where E c֯ athode and E A֯ node are the SRPs of cathode and anode respectively.
7. Ecell is positive for the spontaneous cell reaction and the cell is a source of electrical energy.
 Ecell is negative for a non – spontaneous cell reaction and therefore the cell is not a source of
electrical energy.
8. In a galvanic cell, the metal with higher SRP is the cathode and the other with lower SRP is the
anode.
Nernst equation
The Equation for single electrode potential was derived by Nernst and is called the Nernst
equation. Nernst equation relates the electrode potential of the metal to the concentration of metal ions,
standard reduction potential, and temperature. It is derived based on thermodynamic considerations.

EMF of a cell
In a galvanic cell, if the net cell reaction is given by
aA+ +bB aA +bB+
Then emf of the cell is given by
0.0591
Ecell = E 0cell − log k
n
0.0591 [ B]b
Ecell = E 0cell − log a
n [ A]
0.0591 [Anodic species]moles
Ecell = E 0cell − log
n [Cathodic species]moles
0.0591 [Cathodic species]moles
Ecell = E 0cell + log
n [Anodic species]moles
Concentration cells
Electrolyte concentration cells
Two like electrodes immersed in electrolytes containing its own ions of varying concentrations
constitutes a concentration cell.
Or
It is a limited form of a galvanic cell that has two equivalent half cells of the same
material differing only in concentration.
The driving force for the cell reaction is the difference in the concentration of electrolyte and the
tendency for the solution concentrations to become equalized. Electrical energy is derived from the
free energy change accompanying the transfer of material from a higher concentration to a lower
concentration.
Concentration cell is represented as
M | Mn+ (C1) || Mn+(C2)| M
Ex.s
1. Two copper rods are separately placed in a solution containing Cu2+ ions of different
concentrations.
Cu |Cu2+ (M1) || Cu2+ (M2)| Cu
2. Two silver rods are separately placed in a solution containing Ag+ ions of different
concentrations.
Ag | AgNO3 (M1) || AgNO3 (M2)| Ag
The above cells are called concentration cells with transference; they include the liquid junction
potential. These are also called electrolyte concentration cells.
Electrode concentration cells
 In these cells, the potential difference is developed between two like electrodes at different
concentrations dipped in the same solution of the electrolyte.
They do not include the liquid junction potential.
Ex.s 1. Cd; Hg (C1) |CdSO4| Cd; Hg (C2)
Amalgams of the same metal cadmium of two different concentrations are immersed in CdSO4
solution of same concentration.
2. Pt; H2 (P1)| HCl| H2 (P2); Pt
Two hydrogen electrodes at different partial pressure of hydrogen in the same solution of
hydrogen ions constitute a cell of this type.
The reactions taking place in a concentration cell is,
At anode, M → Mn+ (C1) + ne-
At cathode, Mn+ (C2) + ne- → M
Net cell reaction is, Mn+ (C2) → Mn+ (C1)

The cell reaction is spontaneous when C2>C1. As the cell reaction proceeds, the solution which
was originally more concentrated (C2) becomes dilute and the solution which was originally dilute
(C1) becomes more concentrated. After some time, the concentration of the solution at both the half
cells becomes equal i.e., C1=C2 and the emf of the cell becomes zero. The cell is in equilibrium. Hence
in a concentration cell, emf depends on the ratio of concentrations of the solutions, as the ratio changes,
emf also changes and when the ratio is 1 i.e. C2/C1 =1, emf is zero.
Emf of a concentration cell
Consider a concentration cell,
M| Mn+ (C1) || Mn+ (C2)| M
Emf of the cell is given by,
Ecell = Ecathode – EAnode
Applying Nernst equation for single electrode potential, we get,
 0.0591 0.0591
Ecell = [E0 Mn+ /M + logC2 ]-[E0 Mn+ /M + logC1 ]
n n
0.0591 0.0591
Ecell = logC2 - logC1
n n
In a concentration cell, both anode and cathode are made up of same metal.
0.0591
Ecell = (logC2 -logC1 )
n
0.0591 C
Ecell = log 2
n C1
Case (i) When C1=C2, Ecell = zero, cell is in equilibrium
Case (ii) When C2>C1, Ecell is positive, cell reaction is spontaneous
Case (iii) when the ratio, C2/C1 changes, Ecell also changes, C2/C1 = constant then, Ecell is also
constant, :. Ecell α C2/C1
1.1.5 Numerical Problems
1. A Concentration cell was constructed by immersing two silver electrodes in 0.05 M and
1M AgNO3 solution. Write the cell representation, cell reactions and calculate the emf of the
cell.
Ans. Cell representation,
Ag|AgNO3 (0.05M) ||AgNO3 (1M) |Ag
+
At Anode : Ag → Ag (0.05 M) + e-
+ -
At cathode: Ag (1M) + e → Ag
---------------------------------------------------
+ +
Net cell reaction, Ag (1M) → Ag (0.05M)

2. The spontaneous Galvanic Cell Tin | Tin ion (0.024M)|| Tin ion (0.064M|Tin develops an
0
emf of 0.0126 V at 25 C, Calculate the Valency of Tin.

Ans.
0
3. The emf the cell Cd|CdSO4(0.0093M) ||CdSO4(xM) | Cd is 0.086 V at 25 C. find the value
of X
Ans. n = 2, C2 = x, C1 = 0.0093
Ecell = 0.086 V
 0.0591 C
Ecell = log 2
n C1
0.0591 x
0.83= log
2 0.0093
x (0.83)2
log =
0.0093 0.0591
log x - log0.0093 = 2.901
log x = 0.878
x = Antilog(0.878)
x = 7.55M
4. Represent the cell formed by the coupling of two copper electrodes immersed in CuSO4
solutions concentration of cupric ions in one electrode system is 100 times more concentrated
than the other. Write the cell reaction and calculate the potential at 300 K.
Ans. Cu |CuSO4 (X M) || CuSO4 (100X M) |Cu
C2=100x, C1 = X, n=2
At anode, Cu → Cu2+(X M) + 2e-
At cathode, Cu2+(100 M) + 2e- → Cu
Net cell reaction, Cu2+(100 M) → Cu2+(X M)

2.303RT C
Ecell = log 2
nF C1
2.303x8.314x300 100x
Ecell = log
2x96500 x
2.303x8.314x300
Ecell = x2
2x96500
Ecell = 0.0595 V
5. Calculate the cell potential of the following cell at 298K.
Ag |AgNO3 (0.005 M) || AgNO3 (0.5 M) |Ag
0.0591 C
E= log 2
n C1
n =1
C1 = 0.005
C2 = 0.5
0.0591 0.5
E= log
1 0.005
E = 0.1182V
6. The cell potential of Ag concentration cell is Ag |AgNO3 (0.002 M) || AgNO3 (X M) |Ag is
0.0751 at 250C. Write the cell reactions and calculate the value of X.
 0.0591 C
E= log 2
n C1
n =1
C1 = X
C2 = 0.002
E = 0.0751V
0.0591 X
0.0751 = log
1 0.002
X 0.0751
log = = 1.27
0.002 0.0591
log X = 1.27 + log 0.002
log X = −1.429
X = 0.0372M

5. Given the EMF of a concentration cell and the concentration in one half-cell, calculate
the unknown concentration in the other half-cell (e.g., Ag|Ag⁺(x M)
||Ag⁺(1.0 M)|Ag, E = 0.26 V)

Ans Given: For a concentration cell with identical electrodes: Cathode concentration= (1.0, M) ,
Anode concentration= (x,M) EMF cell=0.26, V
Cell Reaction
At the anode (lower concentration side, x M): Ag(s) → Ag+(𝑥 M) + 𝑒−
At the cathode (higher concentration side, 1.0 M): Ag+(1.0 M) + 𝑒− → Ag(s)

0.0592 = log ( 𝑥 )
4.39= log (1.0) – log (x) i.e. x= Antilog (4.39)

𝑥 = 4.07 × 10−5 M

[Link] emf of the cell Cd| CdSO₄(x)| |CdSO₄(0.025M) |Cd is 0.035V at 28°C. Find the value
of x with cell reaction.
Ans: X = 0.00163 M

Next-Generation Energy Devices:

Introduction:Battery: A battery is a device that stores chemical energy and converts it into electrical
energy to power devices. It consists of one or more electrochemical cells with an anode (-), a cathode
(+), and an electrolyte, which create a flow of electrons in a circuit.
Importance of batteries
The number of chemical reactions, which can be successfully harnessed to provide electrical
energy, is limited; the range of energy requirements for particular applications extends over many
orders of magnitude from 100mWh for a button cell to 20 KWh for an electric vehicle battery. The
same is true for power from 25-100 µW for a cardiac pacemaker to 50 kW for a military thermal
reserve battery. The diversity of use also requires many specific electrical characteristics which in turn
calls for different battery chemistry, materials & cell. Consumer electrical equipment know the
importance of batteries in regular life. There is high demand for packed electricity in the defence sector,
for communication systems, radio sensor, emergency signals, detonators, and submarines. Operating
public transport on electricity minimizes pollution. Utility items like flashlights, wrist watches, tape
recorders, photo flash devices, heart pacers etc are operated by batteries.
1.2.2 Classification of Batteries
Batteries are classified as
1. Primary cells
2. Secondary cells
3. Reserve batteries

Primary cells: Primary cells are designed for single use. The electrical energy available depends
on the quantity of active materials put in. They have limited shelf life & are not to be recharged.
Ex: Li - MnO2 cell, Zn - O2 cell.
Secondary cells: Secondary cells are also known as rechargeable batteries or accumulators or
storage cells. Secondary cells can be recharged with the help of an external source of electricity.
The cell reaction is reversible. The charge–discharge cycle can be repeated several hundred
times.
Ex: Pb-acid storage cell, Ni-Cd battery, Ni -MH battery, Li -ion battery
Reserve batteries: Reserve batteries are primary cells designed for emergency use particularly
in military applications. In reserve batteries, one vital component generally electrolyte is
separated from rest of the components prior to activation. The battery needs to be activated by
the addition of this component. The battery is capable of a good shelf - life as the chemical
reactions during storage is prevented by removing the vital component. In some of the reserve
batteries, water is separated or even heat may be the activator. Heating results in melting of the
electrolyte to cause conduction & reactions.
Ex: Zn-Ag2O, Mg - water activated batteries
Commercial cells
In principle, several hundreds of combinations of electrodes of inorganic & organic materials
are possible to form a battery. However, in practice, only a few combinations are feasible. Some of the
fundamental requirements of commercial cells are
1. Portability
2. Large emf
3. Electrode materials must be stable
4. Good shelf life
5. Long & useful life
6. Compact & agreeable power - weight ratio.
7. Rechargeable
8. High energy efficiency
9. Economically priced

Lithium Batteries
Due to a rapid increase in the use of portable electronic gadgets such as a laptop, mobile phones,
electric vehicles etc., there is an increasing demand for larger capacity, smaller size, lighter weight &
lower priced batteries.
Today Li batteries are dominating the market due to the following features and benefits
3. High energy density
4. High voltage (3.6 - 3.7V)
5. High drain capacity (Discharge rate up to 1.5 C)
6. Eco-friendly
7. Long cycle life (300 -500 cycles)
8. Quick recharging ability
9. A wide range of operating temperature (-20 to 60 oC)

Sony introduced lithium-ion batteries to the market in June 1991 and in 2002 about 752 million cells
were sold (15% of the market share). Present lithium-ion batteries range in energy storage capacity
from 200 to 250 Wh/L and from 100 to 125 Wh/kg.

Lithium-ion batteries
The Li-ion battery is a rechargeable battery best suited to mobile devices that require small-
size, and high performance. Its characteristics of high energy and high voltage (3.6V) powerfully fulfill
these three key requirements. Rechargeable lithium batteries using insertion electrode materials are
called lithium-ion rocking chair or swing batteries which are receiving great attention.
Construction:
Lithium-ion battery uses lithium intercalated transition metal oxide as cathode and lithium
intercalatable graphite/carbon/metal matrix composite as an anode. The cores of the lithium atoms
(i.e. the atoms without their outer electron, the lithium ions) occupy positions between the graphite
lattice layers (see figure). For every Li+ ion, there is an additional electron bound to a nearby C atom
in the graphite lattice so that the compound is electrically neutral. The compound is not stoichiometric,
i.e. the number of Li atoms is variable; the maximum lithium content is 1 Li atom for 6 C atoms.
Intercalation is a reversible process. Therefore, batteries with electrodes made from intercalation
compounds are rechargeable.
Lithium salt such as LiPF6 dissolved in organic solvents like propylene carbonate, ethylene carbonate,
dimethoxyethane or dimethyl carbonate is used as the electrolyte. Microporous polyethylene or
polypropylene is used as the separator. The container is made up of stainless steel or aluminum alloy.
Anode: Lithium intercalated graphite/carbon, metal matrix composite or polymer.
Anode current collector: Copper foil
Cathode: Partially lithiated oxides of nickel, cobalt and manganese: LiyNiO2, LiyCoO2, and
LiyMn2O4
Cathode current collector: Aluminium foil.
Electrolyte: LiPF6 in a mixture of organic solvents like propylene carbonate, ethylene carbonate,
dimethoxyethane or dimethyl carbonate
Separator: Microporous polyethylene or polypropylene.

Reactions
 Ecell = 3.6 V
Advantages:
1. High energy density.
2. Long life
3. High cell voltage.
4. Low self- discharge
5. Wide range of operating temperature (-20 – 40 ℃).

Uses
Used in the cell phone, note PC, portable LCD TV, portable CD player, semiconductor driven audio
etc.
Advantages of Li-ion battery as an electrochemical energy system for electric vehicles
• High energy density: The high energy density higher power density are the chief advantages
of lithium-ion battery technology. Electric vehicles need a battery technology that has a high
energy density.
• Self-discharge: Lithium-ion cells show much lower rate of self-discharge than other
rechargeable cells such as Ni-Cd and Ni-MH batteries.
• Low maintenance: Lithium-ion battery do not require maintenance to ensure their
performance.
• Cell voltage: The voltage produced by each lithium-ion cell is about 3.6 volts. Requires
Less number of cells in many battery applications and simplifies the power management.
• Load characteristics: The load characteristics of a lithium-ion cell are reasonably good.
They provide a reasonably constant 3.6 volts per cell.
• No requirement for priming: Lithium-ion batteries show no requirement for priming, and
they are supplied operational and ready to go.
• Variety of types available: There are several types of lithium-ion cell available enabling the
right technology to be used for the particular application needed.
• Lithium batteries provide much higher current levels and are ideal for power tools and electric
vehicles.
• Lithium-ion batteries provide good high-temperature performance.

Lithium-ion battery disadvantages

• Protection required: Lithium-ion batteries require protection from being over charged and
quick discharged and are to be kept within their safe operating limits.
 • Ageing: Lithium-ion batteries are able to withstand 500 - 1000 charge-discharge cycles before
the failure of a battery.
• Cost: They are expensive compared to Ni-Cd or Ni-MH batteries.

Sodium-ion battery:

Sodium-ion batteries (NIBs) were originally developed in the early 1980s, approximately over
the same time period as LIBs. In recent years, NIBs have drawn increasing attention for large-
scale energy storage, because of the natural abundance, low cost, and environmental
friendliness of sodium. Sodium ion batteries had more charge cycles than lithium ion.

Anode: Anode Hard carbon is most preferable due to its high capacity, good cycling stability.

Cathode: sodium transition metal oxides (such as NaCoO₂, NaFePO₄, or Prussian

blue analogs)

Electrolyte: ethylene carbonate, diethyl carbonate, dimethyl carbonate etc...

Separator: Microporous polypropylene or polyethylene

Working: During discharging: During the discharge of a sodium-ion battery, sodium ions move from
the anode (negative electrode) back to the cathode (positive electrode) through the electrolyte.
Simultaneously, electrons travel through the external circuit, creating electrical current.

At the anode, oxidation takes place releasing sodium ions and electrons:
Na𝑦C →𝑦 Na+ + 𝑦 𝑒− + C

At cathode, reduction takes place, releasing sodium ions and electrons:

Na𝑥−𝑦MO2 + 𝑦 Na+ + 𝑦 𝑒− → Na𝑥MO2

sodium ion battery develops a potential of 3.0 V. MO₂ (M = transition metal like Co or Fe).

During charging of a sodium-ion battery, sodium ions are de-intercalated (extracted) from the
cathode and move through the electrolyte to be intercalated (inserted) into the anode, while electrons
travel via an external circuit.

Applications: used in Electric vehicles, large scale energy storage technology like wind, solar
and wave.
Construction and Working of Ultra-Small Asymmetric Supercapacitor and its Applications in
IoT/Wearable Devices
Construction:

An ultra-small asymmetric supercapacitor (ASC) is made of two different electrode materials: one
faradaic (battery-type, e.g., metal oxides or conducting polymers) and one non-faradaic (EDLC-
type, e.g., activated carbon, graphene, or CNTs).

A thin, flexible substrate (polymer film) serves as the base.

A solid or gel polymer electrolyte (such as PVA/H3PO4) is used for ion transport.

The entire device is miniaturized into micro- or nano-scale dimensions to integrate with flexible
electronic circuits.

Working:

When voltage is applied, the faradaic electrode undergoes reversible redox reactions, while the
carbon-based electrode stores charge electrostatically.

This asymmetric design widens the operating voltage window compared to symmetric capacitors,
leading to higher energy density.

The device exhibits fast charge–discharge cycles, high power density, and long cycle life.

Applications in IoT/Wearables:

Power source for low-energy IoT sensors and wireless nodes.

Integrated into flexible and stretchable wearables such as smart textiles, fitness trackers, and
health monitoring devices.
Suitable for intermittent energy harvesting systems (solar cells, piezoelectric
harvesters).

Lightweight, eco-friendly, and mechanically robust, ideal for bendable and portable
electronics.

Long cycle life ensures reliable operation in implantable medical devices and compact
communication modules.

Sustainable Energy Devices:

Introduction:

Sustainable energy devices use renewable energy sources such as solar, wind, hydro, biomass,
geothermal, and fuel cells to generate electricity or heat while minimizing environmental impact.
These devices support the transition to a low-carbon economy by mitigating carbon emissions and
promoting energy security and affordability.

Fuel Cells
Fuel cells
Fuel cells are the galvanic cells, which convert the free energy of the electrochemical reaction
of a fuel-oxidant system directly into electrical energy.
Fuel cells consist of electrodes and electrolyte. The fuel and the oxidant are supplied continuously.
These fuel cells give a more efficient way to generate electricity as it avoids heat-to-work conversion
and directly converts chemical energy into electrical energy through electrochemical reactions. The
products formed in the fuel cells are not objectionable and government agencies classify the vehicles
run by fuel cells as zero-emission vehicles (ZEV). The first company to adopt fuel cells vehicles is
Honda. The cars run by fuel cells are called Honda FCCs.
Fuel cells differ from batteries. The major differences are
Batteries Fuel cells
Batteries are energy storage devices Fuel cells are energy conversion devices
Secondary batteries are rechargeable Fuel cells are not chargeable in a
conventional manner. However, they give
continuous direct current as long as the
reactants are fed at the electrodes
The reactants and products form integral In fuel cells there is a continuous movement
parts of batteries of fuel, oxidant & reaction products in and
out of cells.
Lower energy density, suitable for smaller, Generally higher energy density, suitable for
lighter applications larger vehicles

No emissions during use, but production Water and heat only (if hydrogen used)
impacts environment

Generally, less expensive Generally, expensive

Lower efficiency Higher efficiency
Construction, working principle, applications and limitations of solid-oxide fuel cell
(SOFCs):

A Solid Oxide Fuel Cell (SOFC) is an electrochemical device that directly converts the chemical
energy of fuels into electricity through a high-temperature electrochemical reaction.

Anode (negative electrode): Typically, a porous nickel–zirconia cermet, where

fuel (H₂ or hydrocarbons) is oxidized.

Cathode (positive electrode): Usually Porous layer strontium-doped lanthanum manganite,

where oxygen from air is reduced.

Electrolyte: A solid ceramic material, usually yttria-stabilized zirconia, which

conducts oxygen ions (O²⁻).

Interconnects: Conduct electricity and separate the cells.

Working Principle:
• Air (oxygen) is supplied to the cathode, where oxygen molecules are reduced to oxygen
ions (O²⁻). These oxygen ions diffuse through the electrolyte towards the anode.
• Fuel (e.g., hydrogen, natural gas) enters the anode, reacting with oxygen ions. The reaction
releases electrons, which flow through an external circuit, generating electricity. The
electrons return to the cathode to reduce oxygen molecules, completing the circuit.
These reactions are highly efficient and occur at the interface where gas, electrode material (e.g.,
Ni-YSZ for anode, LSM for cathode), and the electrolyte meet
Applications for SOFCs
Power generation in stationary power plants
Distributed power systems for hospitals, universities, and industries.
Auxiliary power units (APUs) for vehicles, ships, and aircraft.
Can run on natural gas, biogas, or hydrogen – flexible fuel options.

Limitations of SOFCs
High operating temperature (600–1000 °C) causes long start-up times. Material
challenges: thermal stress, electrode/electrolyte degradation. Expensive ceramic
materials and fabrication costs.
Limited portability (better for stationary applications). Requires
pure fuel or reforming units.

Photovoltaic Cells
▪ PV cells or Solar cells are often referred to as semiconductor devices that convert sunlight into
direct current electricity.
▪ Groups of PV cells are electrically configured into modules and arrays, which can be used to
charge batteries, operate motors, and to power any number of electrical loads. With the
appropriate power conversion equipment, PV systems can produce AC current compatible with
any conventional appliances.
Principle: It is based on the photoelectric effect.

1. Photogeneration of charge carriers (positive and negative charges) in a light absorbing material
The energy associated with a photon (E) is given by

E=h = hc /

Where h is Planck’s constant,

 C is the velocity of light and

 is the wavelength of light in nm.

When the solar radiations are incident on the solar cell normal to the plane, those photons, which
possess energy greater than the eg (energy gap) are absorbed and electron hole-pairs are formed.
Electrons are driven out into the external circuit.

2. Separation of positive and negative charges by a potential gradient within the material.
The electrons and holes can be made to flow through an external circuit (thereby accounting for
current) if a potential gradient exists within the cell. In case of silicon, the potential gradient is
established by keeping a layer of n-type silicon directly in contact with a p-type silicon i.e., by p-
n junctions.

The energy levels of the valence band and conduction bands in p-type semiconductors are slightly
higher than the energy levels in the n-type semiconductor. When p and n-types are in contact, a
jump in energy level occurs at the interface. A potential gradient arises across the junction and this
is enough to separate the electrons and holes.

Construction: Polycrystalline silicon wafers are made by wire-sawing block-cast silicon ingots
into very thin slices or wafers (250-350 m). The wafer is etched slightly to remove the saw
damage and to condition the surface for better light absorption. The wafers are usually lightly p-
doped. To make a solar cell from the wafer, a surface diffusion of n-type dopants is performed on
the front side of the wafer. This forms a p-n junction of a few hundred nanometers below the
surface.

Figure: Solar cell structure

The antireflection coating of silicon nitride or titanium dioxide is then applied in a layer, several
hundred nanometers thick.

The wafer is then metalized, whereby a full area metal contact is made on the back surface, and a
grid-like metal contact made up of fine fingers and larger ‘bus bars’ is screen printed onto the front
surface using silver paste.

The rare contact is also formed by screen printing a metal paste of aluminum. The metal electrodes
are then given heat treatment or sintering to make ohmic contact with the silicon.

Working:
 The energy associated with a photon (E) is given by E=h = hc/ ; where h is planks constant,
C is the velocity of light and  is the wavelength of light in nm. When the solar radiations are
incident on the solar cell normal to the plane, those photons, which possess energy greater than the
Eg are absorbed and electron hole-pairs are formed. Electrons are driven out into the external
circuit and could be stored and used for various applications.
Advantages of PV cell:

i. Electricity produced by solar cells is clean and silent.

ii. Small-scale solar cells can be installed in unused space like roof tops.
iii. The solar cell operates reliably for a long period of time with no maintenance.
iv. Solar energy is a renewable resource.
v. A photovoltaic system can be constructed to any size based on energy requirements.
vi. It does not generate emissions or radiations.
vii. It is very easy to operate compare to other power sources of renewable type.
Disadvantages

i. Incurs high cost of installation.

ii. Solar power is a variable energy source, with energy production dependent on the sun.
iii. Photo-Voltaic solar cells generate direct current (DC). It requires DC appliances or inverters
(to convert DC to AC) for use with solar cells based plants.
iv. Off grid applications require energy storage.
v. Less power will be generated during cloudy weather.

Production of Green Hydrogen by Photocatalytic Water Splitting Using TiO₂

Introduction: Hydrogen gas as a fuel has the potential to lessen the threat of global climate change
and help to avoid various undesirable effects caused by the mass consumption of fossil fuel.
Photocatalytic water splitting has been widely studied as a potential method to produce H2 from
renewable solar energy. Photocatalysts that can operate under visible light irradiation (λ>400 nm),
which forms the main part of sunlight, are highly desirable. Over the last decades, a mounting attraction
has been dedicated to the generation of hydrogen from solar-powered water-splitting devices as a direct
strategy to generating a clean and sustainable energy vector. Among the different options, a direct
photocatalytic process is the most straightforward, where a light absorber can produce hydrogen and
oxygen under light irradiation without an external bias.
Principle: Photocatalytic overall water splitting is a simple process in which hydrogen (H2) and
oxygen (O2) are produced from water by illumination with suitable light energy, i.e., λ ≥ band gap (Eg).
The photocatalyst should exhibit a suitable bandgap to harvest light, appropriate band-edge positions
that overlap the water splitting potential, stability against photo corrosion, and low-cost components.
The process of photocatalytic water splitting consists of four main steps:

(i) Absorption of photons with energies greater than the band gap,
(ii) Charge separation of photo-excited electron-hole pairs in the bulk catalyst,
(iii) Migration of charge carriers from the bulk to the surface of the catalyst, and
(iv) Simultaneous reduction of H＋ to H2 by electrons and oxidation of H2O to O2 by holes at
active sites on the catalyst surface.
Light Absorption:

When TiO₂ absorbs a photon with energy greater than its band gap (~3.2 eV for anatase), it excites
an electron (e⁻) from the valence band (VB) to the conduction band (CB), leaving behind a hole
(h⁺):
TiO2 + ℎ𝜈 ⟶ e− + h+
CB VB
The photogenerated electrons can reduce H＋ to H2 only if the potential of the conduction band is more
negative than the potential of H2 evolution (0 V versus NHE at pH 0). Likewise, photogenerated holes
can oxidize H2O to O2 only if the potential of the valence band is more positive than the potential of
O2 evolution (＋1.23 V versus NHE at pH 0)

Reduction (Hydrogen evolution): 2 H++2 e- → H2 (1)

Oxidation (Oxygen evolution): 2H2O +4h+ → 4H++O2 (2)

Overall reaction: 2H2O → 2H2 + O2 (3)

Advantages of TiO₂ Photocatalyst

• Abundant & Low-Cost: Titanium is widely available, cheap, and non-toxic.

• High Chemical Stability: Resistant to corrosion under UV and aqueous conditions.
• Environmentally Friendly: No CO₂ or harmful byproducts.
• Reusable: Can be recycled over many cycles.
• Tunable Properties: Doping (N, Ag, Ir) or heterojunction formation (CdS,
graphene) can extend absorption into visible light and improve efficiency.