VIVEKANANDA INSTITUTE OF TECHNOLOGY

GUDIMAVU, KUMBALAGODU, BANGALORE-74

Course: Applied Chemistry for Smart Systems (CSE stream)

Module-3

Sustainable Chemistry for Energy Devices

 Module-3 Sustainable Chemistry for Energy Devices
Batteries: Introduction, basic overview of Nernst equation, concentration cell and numerical problems,
classification of batteries, construction, working and applications of Li-Ion battery.

Next-Generation Energy Systems: Introduction, construction and working of sodium ion battery.
Construction and working of ultra-small asymmetric super capacitor and its applications in IoT/wearable
devices.

Clean Energy Chemistry: Introduction, fuel cell, difference between fuel cell and battery, construction,
working principle, applications and limitations of solid-oxide fuel cell (SOFCs) and solar photovoltaic cell
(PV cell). Production of green hydrogen by photocatalytic water splitting using TiO2 method and its
advantages.

Electrochemistry is the branch of chemistry which deals with the relationship between electrical energy and
chemical energy and inter-conversion of one form into another.

Electrochemical cells
An electro chemical cell is a device which converts chemical energy into electrical energy or electrical
energy into chemical energy.

Electrochemical cells are of two types: galvanic cell and electrolytic cell.

Galvanic cell: A galvanic cell is an electrochemical cell in which chemical energy is

converted into electrical energy. Electrical energy can be obtained with the help of a
redox reaction. The oxidation and reduction take place in two separate compartments.
Each compartment consists of an electrolyte solution and a metallic conductor, which
acts as an electrode. The compartment containing the electrode and the solution of the
electrolyte is called half cells.

For example, the Daniell cell is a galvanic cell in which zinc and copper are used for a
redox reaction to take place.

Zn(s) + Cu+2(aq) → Zn+2 + Cu(s)

At anode (oxidation half),

Zn(s) →Zn+2 + 2e–

At cathode (reduction half),

Cu+2(aq) + 2e– → Cu(s)

Salt bridge: The salt bridge is usually an inverted U-tube filled with a concentrated
solution of inert electrolytes. It is used to maintain the charge balance and to complete
the circuit by allowing the flow of ions through it.
 Electrode potential: It is the tendency of metal to get oxidize or reduced when dipped
in solution of its own ions.
Electromotive force/ Cell potential (E.M.F.):
The potential difference between two electrodes of a galvanic cell which causes the flow of
current from anode (higher potential) to cathode (lower potential) is called the E.M.F.

Eocell= ECathode– Eanode

ECathode= standard reduction potential of the cathode.

Eanode= standard reduction potential of the anode

Electrolytic cell: Electrolytic cell is a type of electrochemical cell in which electrical energy is
converted into chemical energy.
For example, in the electrolysis of molten sodium chloride, sodium chloride is melted (above 801 oC), two
electrodes are inserted into the melt, and an electric current is passed through the molten salt. The chemical
reaction that takes place at the electrodes is as follows:

● Sodium-ion migrates to the cathode, where sodium ion gains one electron and reduces to sodium metal.
Na+ + e–→ Na

● Chloride ions migrate towards the anode, where it loses one electron and gets oxidised to chlorine gas.

Cl–→1/2 Cl2 + e–

The overall reaction is the breakdown of sodium chloride into its elements

2NaCl→ 2Na(s) + Cl2(g)

Nerst Equation
Nerst equation is used to calculate the electrode potential cell which depends upon the nature of the
electrode, temperature and the concentrations of the ions in solution.

The Nernst equation is mathematically expressed as:

E = E° - (RT/nF) ln(Q)
Where,

 Ecell = cell potential of the cell

 E0 = cell potential under standard conditions
 R = universal gas constant
 T = temperature
 n = number of electrons transferred in the redox reaction
 F = Faraday constant
 Q = reaction quotient
 At 298 K, the Nernst equation can be expressed as follows:
E = E0 – 0.0591/n log10 Q

Concentration cells

The electrochemical cells which are obtained by dipping same metal in same electrolyte solutions of
different concentration are called concentration cells. In concentration cells, emf arises due to difference in
concentration of electrolyte solution.
Ex: A typical example of Electrolyte concentration cell is as shown below.

Anode Cathode

Cu2+ Cu2+

The cell consists of two Cu metal rods, one dipped in 0.1M CuSo4 solution(M1) and another Cu rod dipped
in 1M CuSo4 solution (M2) concentration in two different containers (M2 > M1). These two electrodes are
connected externally by metallic wire and internally by a salt bridge.

The cell can be represented as Cu/ CuSo4 (0.1M) // CuSo4 (1M)/Cu. By convention, the electrode with low
concentration acts as anode, at which oxidation takes place. On the other hand, the electrode with higher
concentration acts as cathode, at which reduction takes place. Therefore, electric current arises due to the
difference in concentration of electrolyte around the electrodes and the Hence, the direction of flow of
current is from electrode of higher concentration to the electrode with lower concentration.

At anode: Cu Cu2+ (M1) + 2e –

At cathode: Cu2+ (M2) + 2e- Cu

Cu2+ (M2) Cu2+ + (M1)

Expression for emf of cell: The e.m.f of such cell can be calculated as follows;

For Anode: E = E 0+ 0.0591 log(M1) ........................................ (1)

n
0
For Cathode: E = E + 0.0591 log(M2).................................. (2)
n
But, Ecell = Ecathode – Eanode .............................................. (3)
 Equation (1 ) and ( 2) in equation (3) gives;

Ecell = [E0+ 0.0591 log(M2)] - [ E0+ 0. 0591 log(M1)]

n n

- ----------------- (4)
Ecell= 0.0591 log M2/M1

Where, M2>M1and at 298K

Note: At any other temperature, the same equation can be re written as

Ecell= 2.303RT log M2/M1 - ------------ (5)

nF

From equation (4) it is clear that,

1. When the concentration of the electrolyte is same in two half cells i.e., when
M2 = M1; then, log(M2/M1) = 0
Hence, Ecell = 0 and hence no net current flows through the cell.
2. When M2> M1; log (M2/M1) value is positive. So Ecell is positive.
Therefore, the direction of flow of electrons in from electrode at low concentration to that at high
concentration.
3. Higher the value of (M2/M1) ratio, higher will be the value of cell potential.
Eg: If the ratio of (M2/M1) increases from 0.01 to 0.1 (10 times) then the voltage doubles.

Note: Refer class work book for solved problems on concentration cells

Batteries

Introduction:

Battery is a device consisting of two or more Galvanic cells connected either in series or parallel to produce
electrical energy. It acts as a portable source of electrical energy.
Classification of Battery: Batteries are classified in to following three types.
i) Primary batteries
ii) Secondary batteries and
iii) Reserved batteries

i) Primary batteries: The batteries which cannot be recharge and reused are called primary batteries.
In primary batteries, redox reaction cannot be reversed by supplying current from external source.
Hence, they are also known as Irreversible batteries or non-rechargeable batteries. They are
designed for single discharge.
 Eg. Dry cell, Zn air (Zn- O2) battery, Li-MnO2 battery, Leclanche cell ( Zn-Mno2), Magnesium
Cell ( Mg- MnO2) etc.,

ii) Secondary batteries: The batteries which can be recharge and reused are called secondary batteries.
In secondary batteries, redox reaction can be reversed by supplying current from external source.
Hence, they are also known as reversible batteries or rechargeable batteries. They are designed for
multiple discharge. In secondary batteries the externally supplied electrical energy will be stored in
the form of chemical energy and hence, they are also known as storage batteries.
Eg. Lead acid battery, Ni-MH battery, Lithium ion battery, Sodium ion battery etc.,

iii) Reserve batteries: The batteries in which one of the key component is kept separated from the rest
of the battery and it is added to the battery prior to usage is called Reserve batteries. Since, the key
components is separated, the problem of self-discharge is essentially eliminated. Generally,
electrolyte solution is kept outside the battery.
Eg; Li-V2O5, Mg-AgCl battery, Zinc Silver oxide battery, Lithium thionyl chloride battery etc.,

Basic concepts – The principal components of a battery:

The basic electrochemical unit of a battery is a galvanic cell. The components of such a cell are shown
schematically in the figure.

Terminals

Seal with vent

Anode Cathode

Anode active materials Cathode active materials

Separator

Electrolyte
Principal components of a battery

The principal components of a battery are:

1. The anode or negative electrode – It gives out electrons to the external circuit by undergoing
oxidation during electrochemical reaction.
2. The cathode or positive electrode – It accepts the electrons from the external circuit and causes the
reduction of some substances.
3. The electrolyte – The electrolyte is commonly a solution or slurry of acids, alkalies or salts having
high ionic conductivity. Solid electrolytes with appreciable ionic conductivity are also used at the
operating temperature of the cell.
 4. The separator – The materials which electronically isolate anode and cathode in a battery to prevent
internal short circuiting are referred to as separators. They are permeable to the electrolyte so as to
maintain desired ionic conductivity. Thus, their main function is to transport ions from anode to
cathode compartment and vice versa. Materials such as fibrous cellulose, vinyl polymers,
polyolefins, cellophane and nafion membranes are commonly used as separators.

The group of batteries in which Lithium metal is used as anode are called Lithium batteries.
Lithium metal is widely used as anode material in Lithium batteries this is because
1. It is a light metal

2. It has very low reduction potential value (-3.05V).

3. It has high electro chemical equivalence.

4. It has good electrical conductivity.

Lithium-ion battery(LIB): It is a secondary battery which can be recharge and reused. It is capable of
producing high voltage up to 3.7V after complete charging.
Anode: Lithium metal intercalated in layers of Graphite (Li-C6)
Cathode: Lithium- metal oxide (Li- CoO2).
Electrolyte: Lithium salts such as LiPF6 dissolved in mixed organic solvents like ethylene carbonate and
dimethyl carbonate.
The anode and cathode are separated by synthetic micro porous polymer separator which allows only Li+
ions to pass through. The battery can be represented as
Cell representation: Li/Li+, C/LiPF6/LiCl in ethylene / Li-CO2
Reactions during Discharging:
At Anode: The Li atoms in graphite layer undergoes oxidation producing electrons and Li+ ions. The
electrons flows from anode to cathode through external circuit and Li+ ions through electrolyte solution
Li-C6 Li+ + 6C + e-
At Cathode: The Li+ ions undergo reduction to lithium metal. The Li atoms are inserted in to the layered
structure of cobalt oxide.
Li+ + e- + CoO2 Li - CoO2

Reaction during Recharging:

At Anode: The Li atoms in cobalt oxide layer undergoes oxidation producing electrons and Li+ ions. The
electrons flows from anode to cathode through external circuit and Li+ ions through electrolyte solution
Li - CoO2 Li+ + e- + CoO2
At Cathode: The Li+ ions undergo reduction to lithium metal. The Li atoms are inserted in to the
layered structure of graphite
Li+ + 6C + e- Li-C6

Applications: Li- ion battery is used in

1. Cellular phones 2. Lap tops 3. Computers 4. Electric vehicles. 5. Military devices 6. Power tools
[Link] space etc

Next-Generation Energy Systems

Sodium-ion battery (SIB)

The sodium-ion battery (SIB) is a type of rechargeable battery analogous to the lithium-ion battery
but using sodium ions (Na+) as the charge carriers.

Anode: Na metal intercalated in graphite on copper foil

Cathode: Cathode material is layered Sodium oxides (NaCoO2)

Electrolyte: Sodium – ion batteries can use aqueous as well as non-aqueous electrolyte. NaClO4, NaPF6,
etc. dissolved in mixed organic solvents (propylene carbonate, ethylene carbonate, dimethoxy ethane, etc.).
Thin aluminium foil is used as the current collector.
Separator: Polymer separator or glass fiber.

Cell Potential: 1.85 to 3.45 V

SIBs generally contain two electrodes, one anode and one cathode. A polymer separator is placed between
the two electrodes which allows only sodium ions to move freely between the electrodes.
During discharging, sodium ions are extracted from the anode and move towards the cathode through
electrolyte. During charging the reverse process occurs where sodium ions are extracted from the cathode
and reinserted into the anode. The discharge and charge reactions are given below.
During discharging:
At anode: C-Na Na+ + e- + C

At cathode: Na+ + e- + CoO2 Na-CoO2

During recharging:

At anode: Na-CoO2 Na+ + e- + CoO

At cathode: Na+ + e- + C C-Na

Applications: Cellular phones, laptops, electric vehicles and power tools

Ultra-small asymmetric super capacitor

Construction
An ultra small asymmetric supercapacitor is made up of 2 different electrodes: one pseudocapacitive
electrode and other one is electric double layer capacitive electrode.

- Cathode (Pseudocapacitive electrode): materials like manganese dioxide, ruthenium dioxide, or

conducting polymers are used.
- Anode (Electric double layer capacitor electrode): Activated carbon, carbon nanotubes, or graphene are
used.
- Separator: It is a thin, porous polymer membrane placed between the two electrodes, dipped in electrolyte,
and allows ions to pass through while preventing the electrodes from contacting each other and causing a
short circuit.

- Electrolyte: KOH, in flexible devices - organic electrolytes, ionic liquids, or polymer gels are used.

- Current collectors: Thin, flexible conductive metal foils like aluminium or copper, in contact with
electrodes, are used to collect current.

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

Clean Energy Chemistry

Working
During discharging: when the supercapacitor is connected to the load (LED), the stored energy is released.

At anode: The electric double layer present at the anode disintegrates, releasing electrons

C- K+ → C+ + K+ + e-

Electrons move through the external circuit from anode to cathode. This flow of electrons through the
external circuit constitutes the electric current that powers the device. K+ ions move through the separator
from anode to cathode.

At the cathode: when manganese dioxide is used, Mn(Ⅳ) is reduced to Mn(Ⅲ). K+ ions from the
electrolyte are intercalated into the manganese dioxide layer:

MnO2 + e- + K+ → KMnO2

During charging: when voltage is applied across the supercapacitor

At Cathode: Mn (Ⅲ) is oxidized to Mn(Ⅳ), and K+ ions are released into the electrolyte.

At anode: K+ ions from the electrolyte are attracted to the surface of the carbon electrode, accumulating and
forming the electric double layer

C + e- + K+ → C- K+
Applications in IOT/ wearable devices
- 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 device.

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.

Clean Energy Chemistry

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: The electrochemical cells which convert the chemical energy of fuel and oxygen directly into
electrical energy through redox reaction produce electrical energy

 They produce electrical energy and heat continuously as long as fuel and oxidizing agent (O2) are
supplied.
 Fuel cells are similar to batteries, consisting of an anode, cathode, and electrolyte.
 In a fuel cell, fuel and oxygen are continuously supplied to the anode and cathode respectively. Fuel
undergoes oxidation at the anode, liberating electrons, and oxygen undergoes reduction at the
cathode by accepting electrons. The flow of electrons produces current, and these cells are capable of
supplying current as long as they are supplied with reactants.

At anode: Fuel → Oxidized product + n e-

At cathode: O2 + n e- →Reduced product
Fuel + O2 → Oxidized + reduced Product
 Difference between fuel cell and Battery

Aspect Fuel Cell Battery

Generates electricity continuously Stores chemical energy and

Energy Role
from fuel supply releases it until depleted

Requires constant external supply Contains internal reactants, no

Fuel Source of fuel (e.g., hydrogen) and external supply needed during
oxygen use

Operates as long as fuel is Operates until internal

Operation Time
supplied chemicals are exhausted

Refuel/Recharging Refueling takes minutes (like

Recharging can take hours
Time fueling a car)

Generally higher energy density, Lower energy density, suitable

Energy Density
suitable for larger vehicles for smaller, lighter applications

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

Cost Typically, more expensive Generally, less expensive

Efficiency Higher efficiency Lower efficiency

Solid Oxide Fuel Cells

Solid oxide fuel cell is an electrochemical device that directly converts the chemical energy of fuel,
hydrogen, and oxygen into electrical energy. It operates at higher temperature of 600- 10000c.

Construction
Main components of solid oxide fuel cells are:

 Anode: Nickel impregnated over zirconium dioxide is used as anode electrocatalyst for oxidation of
fuel.
 Cathode: Strontium doped Lanthanum Manganite (LaMnO3) is used as cathode electrocatalyst for
reduction of oxygen.
 Electrolyte: Yttria-stabilized zirconium oxide (YSZ)
 Fuel: Hydrogen or hydrocarbon fuel is supplied over the anode.
  Oxidant: Oxygen from air is supplied over the cathode.

Working
At the anode, hydrogen is oxidized, liberating electrons which flow through the external circuit to the
cathode.
H2 → 2H+ + 2e-

At the cathode, oxygen from the air is reduced to oxide ions.

½ O2 + 2e- → O2-

The electrolyte, yttria-stabilized zirconium oxide, is a porous solid material that is a very good conductor of
oxide ions at a higher temperature of 600-10000 C. Oxide ions formed at the cathode are then transported
through the electrolyte to the anode, where they combine with hydrogen ions to form water as a product.

The overall reaction is:

1/2 O2 + 2H+ → 2H2O

Applications of SOFCs

 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.
Solar Photovoltaic Cell (PV Cell)
It is a semiconductor device that converts solar energy directly into electricity. The conversion is based on
the principle of photovoltaic effect.

Photovoltaic cell mainly consists of a p-n junction diode made from Si semiconductor. It has two electrical
contacts; one is a metallic grid over n-type and second is a layer of silver metal at the back of p-type
semiconductor. An antireflective layer (SiN) is coated in between the metal grids to prevent reflection of
solar light. When sunlight having suitable frequency (E = hv) falls on p-n diode, electrons are ejected from
p-type semiconductor creating an electron – hole pair. These ejected electrons move to n-side through p-n
junction. Since p-n junction allows only one-way movement of electrons, these electrons must flow
through the external circuit to recombine with holes present in p-side of semiconductor. This movement of
electrons through external circuit generates an electric current. Electrical energy obtained from a PV-
cell is directly proportional to area of the cell exposed to light radiation and intensity of incident light
radiation which can eject electrons.

Applications

 Biogas solar cell – transportation, solar cells in calculators, solar cell panels
 PV-cell system can be used to supply electricity for water pumps, laptops computers and military
vehicles
 PV-cell is used for LED bulbs etc

Limitations

 Relatively low power conversion efficiency.

 Performance depends on sunlight availability, output drops on cloudy days or at night
 Requires high-purity silicon, increasing manufacturing costs
 Initial installation is more expensive compared to some conventional energy sources
Production of green hydrogen by photocatalytic water splitting using TiO2 method

Photocatalytic water splitting is a solar-driven process. It uses a semiconductor catalyst such as TiO₂ to absorb
light energy (typically UV) and drive the splitting of water into hydrogen (H₂) and oxygen (O₂). This generates
green hydrogen, a clean fuel with zero carbon emissions.

Dopants such as palladium and silver are introduced to the titanium dioxide structure, which creates a new
energy level that narrows the band gap, allowing the catalyst to absorb more visible light and improving
efficiency. A co-catalyst is also introduced to titanium dioxide, which improves the transfer of electrons for
hydrogen evolution or enhances the oxidation of water for oxygen evolution.

There are 4 important steps involved in semiconductor photocatalysis:

1. Photon absorption: When TiO₂ absorbs a photon with energy greater than its band gap, it excites an
electron (e⁻) from the valence band (VB) to the conduction band (CB), leaving behind a hole (h⁺)

TiO2 +ℎ𝜈 ⟶ e CB − + h+VB

2. Charge Transfer: Electron hole pair formed transfer to semiconductor (TiO 2) – electrolyte junction
where co-catalyst are deposited.
3. Recombination: Co-catalysts (Pt, Ni, Ru) are often deposited on TiO₂ to enhance H₂ production and
suppress electron–hole recombination.
4. Redox Reactions:
Water Oxidation (Oxygen Evolution): The holes oxidize water molecules at the catalyst surface:
2H2O+4h+ ⟶O2+4H+
Hydrogen Evolution: The electrons reduce protons (H⁺) to form hydrogen gas:

4H+ +4e− ⟶2H2

Overall reactions: H2O → ½ O2 + H2
 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.