Applied Chemistry for Smart Systems (CSE stream)

Course Code: 1BCHES102/202

Module-3: Sustainable Energy Systems

Energy Systems: Introduction, basic overview of Nernst equation, construction and
working of concentration cell and numerical problems. Batteries-classification of
batteries, construction, working and applications of Li-Ion battery.
Next-Generation Energy Devices: Introduction, construction and working of
sodium ion battery for EV applications. Construction and working of ultra-small
asymmetric super capacitor and its applications in IoT/wearable devices.
Sustainable Energy Devices: Introduction, fuel cells, 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 by TiO2 catalyst and its advantages.

Nernst equation

The Nernst equation relates the electrode potential of a cell to the standard electrode
potential and the concentrations (or activities) of the involved species. It is fundamental
in electrochemistry for understanding how cell potentials change with concentration.

General form:
𝑹𝑻
𝑬 = 𝑬𝟎 − 𝒍𝒏𝑸
𝒏𝑭
Where:

• E = cell electrode potential, E⁰ = standard electrode potential

• R = gas constant = 8.314 J mol−1 K−1
• T = temperature in Kelvin
• n = number of electrons transferred in the redox reaction
• F = Faraday’s constant = 96485 C mol−1
[𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠]
• 𝑄 = 𝑅𝑒𝑎𝑐𝑡𝑖𝑜𝑛 𝑞𝑢𝑜𝑡𝑖𝑒𝑛𝑡 = [𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠]

Simplified form at 25 °C (298 K):

𝟐. 𝟑𝟎𝟑𝑹𝑻
𝑬 = 𝑬𝟎 − 𝒍𝒐𝒈𝑸
𝒏𝑭
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 𝟎. 𝟎𝟓𝟗𝟏 [𝒑𝒓𝒐𝒅𝒖𝒄𝒕𝒔]
𝑬 = 𝑬𝟎 − 𝒍𝒐𝒈
𝒏 [𝒓𝒆𝒂𝒄𝒕𝒂𝒏𝒕𝒔]

Case-I: If Ecell is positive, the reaction is spontaneous

Case-II: If Ecell is negative, the reaction is non-spontaneous
Case-III: If Ecell = 0, the reaction is in equilibrium.

Concentration cell
The concentration cells consist of identical electrodes immersed in the solutions of the
same electrolytes but with varying concentrations. The potential difference arises due to
differences in electrolyte concentration.

Construction

• Electrodes: The higher ion

concentration side is the cathode
(right side) and the lower ion
concentration side is the anode (left
side). The anode loses electrons
through an oxidation reaction. The
cathode gains electrons through a
reduction reaction.
• Salt Bridge: A salt bridge connects the two compartments (anode & cathode) to
maintain charge balance. It consists of a saturated solution of a salt such as KCl.
• Voltmeter: The voltmeter is used to measure the cell potential of the cell.

Cell representation: Concentration cell is represented as,

Cu/Cu+2 (C1) || (C2) Cu+2/Cu

Working

Anode: Cu Cu+2 (C1) +2e-

Cathode: Cu+2 (C2) +2e- Cu

Net cell reaction: Cu+2 (C2) Cu+2 (C1)

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The electrode potential for the concentration cell is represented by

Ecell = ECathode - EAnode

0.0591 0.0591
=(E⁰Cathode + log C2) - (E⁰Anode + log C1)
𝑛 𝑛
In a concentration cell, both electrodes are same, hence
𝟎.𝟎𝟓𝟗𝟏 𝐂𝟐
Ecell = log at 298K
𝒏 𝐂𝟏
Now, Ecell will be positive only if C2 > C1.

Numerical problems
A concentration cell is constructed by dipping copper rods in 0.001M and 0.1 M copper
sulphate solutions. Calculate the EMF of the cell at 298K.

Cell representation:

Cu/Cu+2 (C1= 0.001M) || (C2= 0.1M) Cu+2/Cu

Cell reactions:

Anode: Cu Cu+2 (C1) +2e-

Cathode: Cu+2 (C2) +2e- Cu

Net cell reaction: Cu+2 (C2 = 0.1M) Cu+2 (C1 = 0.001M)

0.0591 C2
Now, Ecell = log at 298K
𝑛 C1
0.0591 0.1
= log
2 0.001
= 0.0591 V

EMF of the cell Cu/CuSO4 // CuSO4/Cu is 0.0595V at 25°C. C1= 0.001M, C2 = X and n=
2. Find X value?

Cell representation:

Cu/Cu+2 (C1= 0.001M) || (C2= x M) Cu+2/Cu

Cell reactions:

Anode: Cu Cu+2 (C1) +2e-

Cathode: Cu+2 (C2) +2e- Cu

Net cell reaction: Cu+2 (C2 = x M) Cu+2 (C1 = 0.001M)

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 0.0591 C2
Now, Ecell = log at 298K
𝑛 C1
0.0591 x
0.0595 = log
𝑛 0.001
x = 0.103 M

EMF of the cell Ag/AgNO3 // AgNO3/Ag is 0.8V at 25°C. C2= 0.2M, Find C1 =?
Cell representation:

Ag/Ag+ (C1= x M) || (C2= 0.2) Ag+/Ag

Cell reactions:

Anode: Ag Ag+ (C1) +e-

Cathode: Ag+ (C2) +e- Ag

Net cell reaction: Ag+1 (C2 = 0.2M) Ag+ (C1 = x M)

0.0591 C2
Now, Ecell = log at 298K
𝑛 C1
0.0591 0.2
0.8 = log
1 C1
0.2 0.8
log =
C1 0.0591
0.2
log = 13.536
C1
0.2
= Antilog (13.536) = 3.4355 x 1013
C1
C1 = 5.83 x 10-15 M

Next-Generation Energy Systems

Battery

A battery is a device that converts chemical energy directly into electrical energy via an
electrochemical oxidation and reduction reaction.

Classification of Batteries

Batteries can be classified based on their rechargeability.

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(a) Primary Batteries (Non-rechargeable)

• Designed for single use; cannot be recharged.

• Chemical reaction is irreversible.
• Examples:

➢ Dry cell (Leclanché cell, Zn–C)

➢ Alkaline battery (Zn–MnO₂)

Applications: Flashlights, remote controls, toys, clocks

(b) Secondary Batteries (Rechargeable)

• Can be recharged multiple times with external current.

• Reactions are reversible.
• Examples:

➢ Nickel–cadmium (Ni–Cd)
➢ Lithium-ion (Li-ion) batteries

Applications: Cars, laptops, smartphones, UPS systems

(c) Reserve battery

• A battery that remains inactive until it is needed.

• The chemicals that produce electricity are kept separate to prevent self-
discharge.
• Activated by adding electrolyte, breaking a seal, or applying pressure/heat.
• Provides long storage life and instant power when triggered.

Applications:

• Military equipment (missiles, torpedoes, emergency radios)

• Spacecraft and satellites
• Emergency power supplies (lifeboats, rescue beacons)

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Li-Ion battery

Construction
Anode (negative electrode): Lithium intercalated graphite layer (LixC)
Cathode (positive electrode): Lithium metal oxide, e.g. LiCoO₂
Electrolyte: Lithium salt (LiPF₆) dissolved in ethylene carbonate + dimethyl carbonate
Separator: Porous polyolefin polymer film
Current Collectors: Copper foil for the anode, aluminium foil for the cathode.

Working Principle

The battery operates based on the reversible intercalation and de-intercalation of

lithium ions between the anode and cathode.

During Discharging (battery in use)

• Li⁺ ions move from anode → through electrolyte → to cathode.

• Electrons flow externally from anode → cathode, powering the device.
• The process is reversed compared to charging.
Anode:

Cathode:

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During Charging (external power applied)

• Li⁺ ions move from cathode → through electrolyte → into anode (graphite
layers).
• Electrons move externally from cathode → anode to maintain charge balance.
• Anode stores Li⁺ ions as Li-C₆ (lithiated graphite).

EV Applications of lithium-ion battery

• Main power source in electric cars, buses, and two-wheelers due to high energy
density and long driving range.
• Fast charging capability makes them suitable for modern EV charging
infrastructure.
• Lightweight design improves vehicle efficiency compared to other batteries.
• High cycle life and efficiency allow repeated charging–discharging, making
them reliable for EV operation.

Sodium-ion battery

Construction
• Anode (Negative Electrode): Sodium Intercalated Hard carbon
• Cathode (Positive Electrode): layered transition metal oxides (NaMO₂ M= Fe,
Mn, Cu, Mo)
• Electrolyte: Sodium salts (e.g., NaPF₆) dissolved in organic solvents (carbonate-
based).
• Separator: Microporous polymer membrane.
• Current Collectors: Aluminum foils to conduct electrons.

Working Principle
Discharging (Battery in use): Sodium ions (Na⁺) move from the anode to the cathode
through the electrolyte. Electrons flow through the external circuit, providing electrical
energy.

• Anode (oxidation reaction):

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 • Cathode (reduction reaction)

Charging process (external power applied): An external power source drives sodium
ions from the cathode back to the anode. Electrons also flow back into the anode.

• Cathode (oxidation reaction)

• Anode (reduction reaction)

EV Applications of sodium-ion battery

• Serve as an alternative power source for EVs where low cost is important,
since sodium is more abundant and cheaper than lithium.
• Provide good safety and thermal stability, reducing risks of overheating in
vehicles.
• Suitable for short-range and low-speed EVs such as e-rickshaws, scooters, and
small cars.
• Offer sustainability and resource availability, making them promising for
large-scale EV deployment in the future.

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Ultra-small asymmetric supercapacitor
An ultra-small asymmetric supercapacitor (ASC) is an energy storage device that:
• Uses two different electrode materials (asymmetric).
• Stores energy via a combination of electrostatic (double-layer) and faradaic
(redox) reactions.

Construction
Electrodes:
• Positive electrode (faradaic): Metal oxides (MnO₂, or conducting polymers)
• Negative electrode (EDLC-type): Activated carbon, graphene, or CNT
Electrolyte: a solid-state or gel electrolyte (Examples: PVA-H₃PO₄, PVA-KOH)
Separator: A thin ion-permeable membrane (cellulose nanofibers) between electrodes
to prevent short-circuiting while allowing ion flow.
Substrate: Built on a flexible or rigid substrate like glass or polyimide film.
Encapsulation: The entire cell is encapsulated with thin protective layers to prevent
moisture degradation.

Working Principle
Charging Process

• At the positive electrode (battery-type), ions from the electrolyte participate in

reversible redox reactions, storing charge faradaically.
• At the negative electrode (carbon-based), charge is stored electrostatically by
forming an electric double layer at the electrode–electrolyte interface.
• Electrons move from the negative to the positive electrode.

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Discharging Process

• The stored charges are released: the redox reactions at the positive electrode
reverse, while the electric double layer at the negative electrode collapses,
allowing current to flow through the external circuit. Ions return to their original
positions.

Applications of Ultra-Small Asymmetric Supercapacitors

Applications in IoT Devices

• Powering low-energy IoT sensors and nodes.

• Providing backup power for wireless communication modules.
• Enabling flexible and wearable electronics through compact design.
• Supporting self-powered IoT systems when integrated with energy harvesters
(solar, vibration, etc.).

Applications in Wearable Devices

• Power supply for smart watches, fitness trackers, and health-monitoring bands.
• Energy storage for flexible and stretchable electronic textiles.
• Backup power for medical wearables like ECG or glucose monitors.
• Integration with energy harvesters (body motion, solar) for self-powered wearables.

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 Clean Energy Chemistry
Fuel Cell
A fuel cell is an electrochemical device that converts chemical energy directly into
electrical energy using a fuel (usually hydrogen) and an oxidant (usually oxygen),
without combustion.

Construction of a Fuel Cell

Anode (Negative Electrode): Ni or Pt Where the fuel (e.g., hydrogen) is supplied and
oxidized.

Cathode (Positive Electrode): Pt Where the oxidant (usually oxygen or air) is reduced.

Electrolyte: Allows ions to move between electrodes but blocks electrons.

External Circuit: Connects the anode and cathode, allowing electrons to flow

Working Principle of a Hydrogen Fuel Cell

Overall Chemical Reaction:

At the Anode:
• Hydrogen gas splits into protons and electrons.
• Protons pass through the electrolyte.
• Electrons go through the external circuit, generating an electric current.

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At the Cathode:
• Oxygen combines with protons and electrons to form water.

Difference Between Fuel Cell and Battery

Feature Fuel Cell Battery

Energy Source External supply of fuel (e.g., hydrogen) Stores chemical energy
and oxidant internally

Operation Time Continuous (as long as fuel is supplied) Limited to stored energy;
needs recharging

Rechargeability Not recharged; refuelled by adding fuel Rechargeable or non-

rechargeable

Efficiency High (up to 60% or more) Moderate to high (depends

on type)

Pollution Zero emissions (with hydrogen fuel) Generate waste on disposal

Start-up Time Can have slow start-up Instant or quick start

Maintenance Higher; sensitive to fuel purity Lower

Cost Higher Generally lower

Common Use Vehicles, backup power, space missions Phones, laptops, EVs,
remote controls

Solid Oxide Fuel Cell (SOFC)

A Solid Oxide Fuel Cell (SOFC) is constructed as a layered structure, where each
component plays a specific role in the electrochemical conversion process.

Construction
A Solid Oxide Fuel Cell is built in a layered structure:

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Electrolyte: Porous solid ceramic oxide (yttria-stabilized zirconia)
Anode (Negative Electrode): Ni-YSZ cermet (nickel–
zirconia composite)-
Cathode (Positive Electrode): Strontium-doped
Lanthanum Manganite (LSM) –
Interconnects: Metallic/ceramic materials
Fuel Channel: Supplies fuel gas (hydrogen)
Air Channel: Supplies oxidant (oxygen from air)

Working Principle of SOFC

The SOFC works on the principle of electrochemical conversion of chemical energy

(fuel + oxidant) into electrical energy without combustion.

At the Cathode (Air side): Oxygen molecules receive electrons from the external
circuit and form oxide ions (O²⁻):

The oxygen ions (O²⁻) migrate through the solid electrolyte towards the anode.
At the Anode (Fuel side): Fuel (hydrogen) reacts with oxygen ions to form water and
release electrons.

Electron Flow: The released electrons from the anode travel back to the cathode
through the external circuit, producing electric current.

Overall Reaction:

Applications of SOFC
• Use in stationary power generation for residential and industrial electricity
supply.
• Applied in combined heat and power (CHP) systems, providing both
electricity and heat.
• Serve as auxiliary power units (APUs) in vehicles, ships, and aircraft.
• Integrated in hybrid systems with gas turbines to achieve very high efficiency.

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Limitations of SOFC

• High Operating Temperature: 600–1000°C causes material degradation and

limits start-up times
• Material Stability: Ceramic materials can crack due to thermal stress
• Cost: Expensive materials and manufacturing processes
• Durability Issues: Long-term operation can degrade electrodes and electrolyte

Photovoltaic solar cell

Photovoltaic (PV) cells are semiconductor devices that convert sunlight directly into
electricity using the photovoltaic effect.
Construction
• Semiconductor Material: Usually silicon (Si) in crystalline form
• P-N Junction: A junction between p-type and n-type silicon that creates an
electric field.
• Antireflective Coating (TiO2): Reduces light reflection and enhances
absorption.
• Metal Contacts: Allow current flow and external circuit connection.
• Encapsulation & Glass Cover: Protects the cell from environmental damage.

Working
• Sunlight Absorption: Photons strike the semiconductor, exciting electrons.
• Electron-Hole Pair Generation: Excited electrons move to the conduction band,
creating charge carriers.
• Charge Separation: The built-in electric field moves electrons to the n-side and
holes to the p-side.
• Electric Current Generation: Free electrons travel through an external circuit
from n-type to p-type for recombination with holes again to generate electricity.
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Applications of Photovoltaic Solar Cells
• Electricity Generation – Used for residential, commercial, and industrial power
supply.
• Space Applications – Widely used in satellites and space stations.
• Portable Devices – Powering calculators, watches, and small electronics.
• Solar Street Lighting – Used in street lamps, traffic signals, and garden lights.
• Electric Vehicles & Charging Stations – Supports clean transportation.

Limitations of Photovoltaic Solar Cells

• High Initial Cost – Installation and setup are expensive.

• Intermittent Power Supply – Depends on sunlight, less effective on cloudy/rainy
days or at night.
• Low Efficiency – Conversion efficiency is typically 15–25%.
• Large Area Requirement – Needs significant land/roof space for large-scale power.
• Environmental Impact – Manufacturing involves use of some toxic materials.

Green Hydrogen Production by Photocatalytic Water Splitting

Photocatalytic water splitting is a process to produce green hydrogen using solar

energy to split water (H₂O) into hydrogen (H₂) and oxygen (O₂). Titanium dioxide
(TiO₂) is a widely studied semiconductor photocatalyst due to its stability, non-toxicity,
and low cost.

Process Steps:
• Light Absorption: When TiO₂ is exposed to ultraviolet (UV) light, it absorbs
photons with energy equal to or greater than its bandgap (~3.2 eV).
• Excitation: This excites electrons (e⁻) from the valence band to the conduction
band, leaving behind holes (h⁺) in the valence band.
• Charge Separation: Electron-hole pairs are generated; electrons move to the
conduction band, holes remain in the valence band. These charges migrate to the
surface of the TiO₂ particles.

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Redox Reactions on Catalyst Surface:

• Reduction Reaction (at conduction band):

Electrons reduce protons (H⁺) from water to produce hydrogen gas (H₂):

• Oxidation Reaction (at valence band):

Holes oxidize water molecules to produce oxygen gas (O₂):

• Overall Reaction:

Advantages
• Produces clean hydrogen without
greenhouse gas emissions.
• Uses abundant solar energy and water,
making it sustainable and eco-friendly.
• Provides direct conversion of sunlight to
hydrogen fuel with high purity.

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