Module-2: Sustainable energy systems 8 Hours

Batteries: Introduction and classification of batteries. Construction, working and applications of Li-ion battery.

Next generation energy systems: Introduction, construction and working of sodium ion battery and redox flow
battery for EV applications. Introduction to supercapacitors, construction and working of ultra-small asymmetric
supercapacitor in IoT/wearable device applications.

Clean energy: Introduction, fuel cell, difference between fuel cell and battery. Construction, working, applications
and limitations of solid-oxide fuel cell (SOFCs). Production of green hydrogen by photocatalytic water splitting
using TiO2 and its advantages.

Quantum Dots: Introduction, size dependent properties - quantum confinement effect, surface-to-volume ratio &
band gap. Quantum dot sensitized solar cells (QDSSCs)-construction, working and applications.

Self-learning: Synthesis and applications of Cd-Se quantum dots by wet chemical method.

BATTERIES

Galvanic cell: Galvanic cell is a device that converts chemical energy into electrical
energy through a spontaneous redox reaction.

Battery: A battery is an electrochemical device which consists of two or more

galvanic cells connected in series or parallel or both which produces electricity by
means of redox chemical reactions.

Basic components of battery

The basic components in a battery are anode, cathode, electrolyte and separator
1. Anode: The electro-active material at anode is oxidized and liberates
electrons to the external circuit.

The anode electro active material should have:

− Ease of oxidation (i. e., low reduction potential)
− Good conductivity
− High stability
− Ease of fabrication

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 2. Cathode: The electro-active material at cathode is reduced by accepting
electrons from the external circuit.

The cathode electro active materials should have:

− High reduction potential
− High resistant to the electrolyte
3. Electrolyte: It provides medium for transfer of ions between the anode and
cathode. It is commonly a solution (or slurry) of an acid, alkali or salts having
good ionic conductivity.
It should be:
− Safe to handle
− Non-reactive with the electrode
4. Separator: It is used to separate anode and cathode compartments to
prevent internal short circuiting. It is an electrical insulator.

Eg: Cellulose, cellophane, nafion membranes etc.

Classification of batteries:
1. Primary batteries: A battery which cannot be recharged because the cell
reactions are irreversible is called as primary battery. They are discarded when
the battery has delivered all its electrical energy. Example: Zn-MnO2 battery,
Li-MnO2 battery etc.
2. Secondary batteries: A battery which after discharging, can be recharged by
passing the electric current through it in the opposite direction and the cell
reactions are reversible is known as secondary battery. Example: Lead storage
battery, Nickel-cadmium battery etc.
3. Reserve batteries: In this battery, one of the components is stored separately
and is incorporated into the battery when required. Usually, electrolyte is
separately stored. Example: Mg-AgCl and Mg-CuCl batteries; both can be
activated whenever required just by adding water.

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Working of a battery:

Discharging: During discharge, oxidation takes place at the anode and reduction
takes place at the cathode. The reactions are spontaneous. Chemical energy is
converted into electrical energy. It acts as a galvanic cell during discharge.

Charging: During charging, reverse reactions take place. The reverse reactions are
non- spontaneous reactions. The battery is connected to an external power supply.
Electrical energy is converted in to chemical energy. During charging it acts as an
electrolytic cell.
LITHIUM BATTERIES

• Lithium is the most attractive anodic material for the design of the battery with
high energy density and it tops electrochemical series with least electrode
potential (-3.04V).
• Lithium was initially rejected in scientific community because of its vigorous
corrosive reaction in water, producing explosive H2. However, after the
exploration of non-aqueous solvents for the working of lithium based battery,
lot of developments happened in this area.
• Rechargeable lithium-ion batteries have high voltage, high energy density,
high cycle life and very low self discharge rate when not in use.
• It provides maximum voltage of 3.7 V after complete charge.

Construction:
Anode: Li atoms inserted in graphite carbon.
Cathode: Lithium-cobalt oxide (LiCoO2)
Electrolyte: Lithium salt in an organic solvent (LiPF6 in ethylene carbonate).
Separator: Polypropylene membrane

Cell representation: Li/Li+,C/LiPF6 in ethylene carbonate/Li-CoO2

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Working:

− The traditional batteries are based on galvanic action but Lithium-ion

secondary battery depends on an "intercalation" mechanism.

− This involves the insertion of lithium ions into the crystalline lattice of the
host electrode without changing its crystal structure.

Cell reactions:

At Anode: During discharging of battery, Lithium atoms present in graphite layer

(one Li atom present in every 6C atoms) are oxidized, liberating electrons and lithium
ions. Electrons flow through the external circuit to cathode and lithium ions flow
through the electrolyte towards cathode.

At Cathode: Cobalt ions are reduced and lithium ions are inserted into the layered
structure of CoO2.

Overall, the lithium ion is inserted and exerted into the lattice structure of anode and
cathode during charging and discharging.

During discharge current flows through external circuit and during charging external
current is applied to reverse the reactions.

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Advantages:

• They have high energy density than other rechargeable batteries.

• They are less weight.
• They produce high voltage about 3.7 V as compared with other batteries.
• They have improved safety, i.e. more resistance to overcharge.
• No liquid electrolyte means they are immune from leaking.

Applications: They are currently used for powering portable electronic devices like
cell phones, laptops, electric vehicles, power tools and aerospace applications.

Disadvantages of Lithium-ion battery (LIB):

• Availability of lithium is very limited

• Supply of battery grade Li2CO3 is also limited.
• Recycling of Li-ion batteries is difficult.

Next generation energy systems:

Sodium-ion Battery (SIB)

Na is inexpensive, more abundant than Li and its processing is more environmental

friendly. But energy density of SIB is less than LIB.

CONSTRUCTION AND WORKING OF SIB:

Construction:

1. Anode: Hard carbon

2. Cathode: Sodium inserted in the layered metal oxide (MO2 where M=Co, Mn)
3. Electrolyte: Sodium salt like NaPF6 dissolved in binary organic solvent mixture
such as ethylene carbonate-dimethyl carbonate.

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Working:

At anode: During discharging of battery, Sodium atoms present in carbon structure

are oxidized, liberating electrons and sodium ions. Electrons flow through the external
circuit to cathode and sodium ions flow through the electrolyte towards cathode.

C-Na C + Na+ + e-

At cathode: Transition metal ions are reduced and sodium ions are inserted in to the
layered structure of transition metal oxide.

Na+ + e- + MO2 NaMO2

Reactions are reversed during charging of the battery.

Applications:

• Sodium-ion batteries are applied in energy storage (for the grid, renewable
energy, and homes) and electric vehicles, due to their lower cost and abundance
of materials.
• They are also suitable for other applications like drones, telecommunications,
and consumer electronics.

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REDOX FLOW BATTERIES

A redox flow battery is type of electrochemical cell in which the chemical energy of a
reversible redox couple (present in electrolyte) reaction is converted into electrical
energy.

− In anodic chamber a redox couple dissolved in an electrolyte solution is stored

in external tank.
− In cathodic chamber, another redox couple dissolved in an electrolyte solution
is stored in external tank.
− Two tanks are separated by an ion exchange membrane separator.
− During working of battery, electrolytes from tank are circulated over the
electrodes with the help of a pump.

The main advantage of a redox flow battery is that the storage capacity depends on
the size of the electrolyte tanks and the concentration of reactants. Hence, large
amount of electrical energy can be stored for an indefinite period of time using large
electrolyte tanks.

Construction & Working of Vanadium Redox Flow Battery (VRFB)

Construction:

Anode: V2+/V3+ redox couple dissolved in sulfuric acid electrolyte solutions circulated
over carbon-based electrode.

Cathode: V4+/V5+ redox couple in the form of oxygenated species.

Separator: Nafion ion-exchange membrane

Carbon based electrodes are used as both anode and cathode.

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Working:

At anode: During discharging, V2+ is oxidized to V3+ liberating electrons. Electrons

liberated flow from anode to cathode compartment through external circuit.

V2+ V3+ + e-

At cathode: During discharging, V5+ is reduced to V4+ accepting an electron.

V5+ + e- V4+

During charging, the reactions are reversed.

Advantages of Vanadium Redox Flow Battery (VRFB)

1. The energy storage capacity depends on the size of the electrolyte tanks and
the concentration of reactants. Hence, large amount of electrical energy can be
stored for an indefinite period of time using large electrolyte tanks. It has great
potential as an energy storage device.
2. Power of the battery is independent of energy storage capacity. Power depends
upon the number and configuration of cell stacks.
3. It can remain charged or discharged for an indefinite period without any
damage.
4. Active redox species in both anode and cathode chambers is charged vanadium
species. Slight cross diffusion across the membrane will not result in permanent
loss of capacity.

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 5. It has long charge/discharge cycle lives: 15,000–20,000 cycles with a lifespan of
more than 20 years.
6. Electrolyte used is safe, non-flammable aqueous electrolyte.

Applications of Vanadium Redox Flow Battery (VRFB)

1. Used to store energy generated from renewable sources like solar and wind,
ensuring continuous power supply even when sunlight or wind is unavailable.
2. Provides reliable backup power for data centers, hospitals, and industrial
facilities during power outages.
3. Used for storing and delivering large amounts of energy required for fast-
charging electric vehicles.
4. Helps industries manage energy efficiently by storing excess power during
low-demand periods and using it during high-demand times.

SUPERCAPACITORS

Capacitors: A capacitor is an electrical device that stores electric charge and energy in
an electric field between two conductive plates separated by an insulating material
called a dielectric.

Supercapacitors: A supercapacitor is a powerful capacitor that can store more energy

and deliver it faster than ordinary capacitors, bridging the gap between capacitors and
batteries.
It works on the same principle as a capacitor but has very high capacitance due to the
use of electrodes with large surface area and electrolytes that allow more charge to be
stored.

Feature Battery Capacitor Supercapacitor

Stores energy in an
Energy Storage Stores energy through Stores energy electrostatically
electric field between two
Type chemical reactions and electrochemically
plates

High (can store a lot Medium (between battery and

Energy Density Low
of energy) capacitor)

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Feature Battery Capacitor Supercapacitor

Low (slow to deliver

Power Density High Very High
power)

Takes minutes to
Charging Time Very fast (seconds) Very fast (seconds to minutes)
hours

Discharging
Long duration Short duration Short to medium duration
Time

Few hundred to Hundreds of thousands to

Cycle Life Millions of cycles
thousand cycles millions of cycles

Requires more
Maintenance Very little maintenance Very little maintenance
maintenance

Used in mobiles, Used in filters, flash Used in regenerative braking,

Applications
laptops, EVs circuits power backup, hybrid vehicles

Graphene or activated carbon

Example Lithium-ion battery Ceramic capacitor
supercapacitor

− A supercapacitor consists of four main components: two electrodes, an

electrolyte, a separator, and current collectors. The electrodes are typically
made from high surface area materials like activated carbon, carbon nanotubes,
or graphene.
− The electrolyte can be aqueous (water-based), organic, or ionic liquid. Aqueous
electrolytes offer high conductivity but limit the operating voltage to about 1.2
V due to water decomposition. Organic electrolytes allow higher operating
voltages (2.5-3 V) but have lower conductivity.
− The separator is a porous membrane that prevents electrode contact while
allowing ion transport.

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In supercapacitors there are two main charge storage mechanisms:

1. Electric double-layer capacitance (EDLC): When voltage is applied across the

supercapacitor, ions in the electrolyte migrate toward the oppositely charged
electrode surfaces. Charges are accumulated at the electrode/electrolyte
interface without any chemical change. This forms an "electric double-layer,"
which is essentially two layers of charge separated by a very small distance,
acting as a capacitor. Energy is stored in this electric double layer (EDL) which
is formed at the interface between the electrode surface and the electrolyte.
They store energy purely through electrostatic attraction.
2. Pseudocapacitance: Charges are accumulated due to fast, reversible redox
reactions at the electrode surface. Materials like MnO2, ruthenium oxide or
conducting polymers are used as electrodes. These reactions contribute to more
charge storage. Hence, these devices have higher capacitance, higher energy
density than EDLCs but typically lower power density.

ULTRA-SMALL ASYMMETRIC SUPERCAPACITORS

− An asymmetric supercapacitor, store charge by combination of two different

mechanisms. One of the electrode stores charges by EDLC and other electrode
stores charges by pseudocapacitance.
− Two different electrode materials are used for the positive and negative
terminals. This design allows the supercapacitor to operate at a wider voltage
range.

Construction
Ultra-small supercapacitors are fabricated using advanced microfabrication technique
such as photolithography. Thin-film electrodes with precise dimensions are created
by depositing materials. It has following parts:

1. Cathode: It is pseudocapacitive electrode. Materials like MnO2 or conducting

polymers (polyaniline) are used.
2. Anode: It is EDLC electrode. It is made up of high surface area and good
electrical conductivity carbon material like activated carbon, carbon nanotubes

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 (CNT), graphene.
3. Electrolyte: Solution containing positive and negative ions. Eg: KOH
4. Separator: Thin, porous, polymer membrane placed between two electrodes.
5. Current Collectors: Thin, flexible, conductive foils. Eg: Aluminium, copper.

Working:
At anode:
During discharging i.e., when supercapacitor is connected to a load, an electric double
layer present at anode disintegrates releasing electrons, electrons move through the
external circuit to give electric current. K+ ions move through the separator from
anode to cathode.

During charging i.e. when voltage is applied across the supercapacitor, K + ions from
the electrolyte are attracted on to the surface of carbon electrode. They accumulate at
the surface, forming electric-double layer.

C-K+ C + e- + K+

At cathode:
During discharging, when MnO2 is used, Mn(IV) is reduced to Mn(III). To compensate
for the decrease in positive charge, K+ ion from electrolyte is intercalated in to the
MnO2 layer.

During charging i.e. when voltage is applied across the supercapacitor, Mn(III) is
oxidized to Mn(IV). K+ ions are released in to the electrolyte.

MnO2 + e- + K+ KMnO2

Applications:
1. Internet of Things (IoT)
a) IoT sensors typically require quick power bursts for wireless data transmission.
Supercapacitors can be quickly charged and provide power bursts for wireless
transmission.
b) Energy harvesting systems commonly used in IoT devices like solar panels
during daylight, vibration harvesters during movement, or thermal generators

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 during temperature fluctuations generate power irregularly.
c) Supercapacitors can be used to capture and store the energy harvested by other
devices, then deliver it rapidly when needed for sensor operation and data
transmission.
d) Supercapacitors exhibit long cycle life of over 1 million charge-discharge cycles.
In IoT applications such as sensors embedded in infrastructure or remote
monitoring systems, battery replacement would be impractical or impossible.
Supercapacitors are ideal for such applications due to their long cycle life.
2. Wearable Electronics
a) Ultra-small supercapacitors can be charged rapidly. Hence, in fitness trackers
and smartwatches, supercapacitors can handle the power demands of periodic
heart rate monitoring, GPS tracking, and wireless connectivity.
b) Supercapacitors are flexible and can be integrated into clothing or accessories.
This can be used to power embedded sensors for health monitoring, activity
tracking, or environmental sensing.
Clean Energy

FUEL CELLS
Definition: Fuel cell is a device used to convert chemical energy of fuel into electric
current by direct oxidation of fuel at anode and reduction of oxidant at cathode.

In a fuel cell, fuel is passed over anode (Eg: methanol or H2), liberating electrons,
Anode
Fuel Oxidized product + e-

The liberated electrons flow through the external circuit to cathode compartment.

At cathode, usually oxygen from air is reduced.

Differences between battery and fuel cells:

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 Battery Fuel Cell

A battery is a device that stores A fuel cell is a device that generates

chemical energy inside it and converts electricity continuously by combining a fuel
it into electrical energy when needed. (like hydrogen) with oxygen from the air.

It is a closed system, meaning all the It is an open system, meaning fuel and
chemicals needed for the reaction are oxygen are supplied continuously from
stored inside the battery. outside.

Once the stored chemicals are used up, As long as fuel and oxygen are supplied, the
the battery needs to be recharged or fuel cell can produce electricity
replaced. continuously.

Batteries have less energy density Fuel cells have more energy density

They may cause pollution or waste They are clean and eco-friendly, producing
when disposed of improperly. only water and heat as by-products.

Examples: Lithium-ion battery, Lead- Examples: Hydrogen fuel cell, Methanol

acid battery fuel cell

Solid-Oxide Fuel Cells (SOFCs)

Construction:
Solid oxide fuel cell operates at higher temperatures of 600-1000 °C. Main components
of SOFC are:
Anode: Nickel impregnated over ZrO2 is used as anode electro-catalyst for oxidation
of fuel.
Cathode: Strontium doped on LaMnO3 is used as cathode electro-catalyst for
reduction of oxygen atoms.
Electrolyte: Yttria stabilized Zirconium Oxide (Y2O3-stabilzed ZrO2).
Fuel: H2 or hydrocarbon fuel or gasified coal supplied over anode.
Oxidant: O2 from air supplied over cathode.

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Working:
Working of a SOFC when H2 is used as fuel is given below:
At anode, H2 is oxidized liberating electrons, which flow through the external circuit
to cathode.

At cathode, Oxygen from air is reduced to oxide ion

The electrolyte used in SOFC, Yttria Stabilized Zirconia (YSZ) is a porous, solid
material which is a very good conductor for oxide ions at higher temperature of 600-
1000 °C. Oxide ions formed at cathode are then transported through ceramic
electrolyte to anode where it combines with hydrogen ions to form water as product.

Applications of SOFCs:

1. SOFCs are widely used for electricity generation in power plants.

2. They operate on various fuels like natural gas, biogas, or hydrogen, provide
high efficiency (up to 60%) and low pollution.

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 3. SOFCs can provide on-site electricity and heating for homes, offices, hospitals,
or schools.
4. Used as backup or auxiliary power in vehicles (like trucks, ships, and
airplanes).
5. Used to power communication devices, sensors, or small tools in remote areas.

Limitations of SOFCs:

 SOFCs operate at 600°C to 1000 °C, which is much higher than other fuel cells.
Therefore, it requires expensive high-temperature materials that can withstand
heat and thermal stress.
 High temperatures can lead to thermal expansion and cracking of ceramic
components.
 Electrodes and electrolytes can degrade over time, reducing cell life.
 The use of ceramic electrolytes and special alloys makes SOFCs costly to
produce.

HYDROGEN AS A FUEL
− Hydrogen is considered one of the most promising clean energy carriers of the
future because it produces only water as a byproduct.
− To achieve sustainable and carbon-free hydrogen production, scientists are
developing methods to generate green hydrogen using renewable resources —
one of the most attractive being photocatalytic water splitting.

Production of green hydrogen by photocatalytic water splitting using TiO2

− Photocatalytic water splitting is a process that uses solar energy to split water
(H₂O) into hydrogen (H₂) and oxygen (O₂) with the help of a semiconductor
photocatalyst.
− In photochemical reaction, there is a semiconductor-electrolyte junction at
which the water splitting reaction takes place.
− The required potential for water splitting is generated at the semiconductor-
liquid interface.
− A semiconductor titanium dioxide (TiO2) is a commonly used photocatalyst for

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 splitting of water. Semiconductors have non-overlapping valence bands and
conduction bands with a band gap in between that of insulators and
conductors.
− When sufficient photochemical energy is applied, electrons will be excited into
the conduction band, leaving holes in the valence band and excess electrons in
the conduction band.
− These electron-hole pairs are formed at the junction of semiconductor photo
catalyst.
− Oxygen evolution happens via the holes by oxidation reaction.

H2O + 2h+ ½ O2 + 2H+

− Hydrogen ions are reduced by electron to liberate hydrogen.
2H+ + 2e- H2
Overall reaction:

TiO2
2

Advantages of hydrogen as fuel

• It is readily available.
• It doesn’t produce harmful emissions.
• It is environmentally friendly
• It can be used as fuel in rockets.
• It is fuel efficient. It is renewable.

Limitations/Disadvantages of hydrogen as fuel

• It is expensive.
• It is difficult to store.

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• It is highly flammable.

QUANTUM DOTS
− Quantum dots (QDs) are nanometer-sized semiconductor particles (typically
2–10 nm in diameter).
− They are so small that their electronic and optical properties differ from those
of bulk materials.
− Due to their tiny size, the motion of electrons and holes inside them is confined
in all three spatial dimensions, leading to unique quantum effects.
− Often called “artificial atoms” because they have discrete energy levels like
atoms.
− Example for QDs: CdS, CdSe, PbS, etc.

Quantum confinement effect:

In a bulk semiconductor, electrons and holes can move freely — their energy levels
form continuous bands (conduction band, valence band and band gap).
When the size of the semiconductor particle decreases below a critical limit, electrons
and holes are confined within a small volume and hence the energy levels become
quantized, hence the electrons are confined to small discrete energy levels. This effect
is called as quantum confinement effect.

Size-dependant Properties
Due to quantum confinement effect, properties of the quantum dots become size-
dependant.
(a) Surface-to-volume ratio: As the size of the QD decreases, the surface-to-
volume ratio increases sharply. This make QDs more chemically reactive
than bulk materials because surface atoms are exposed. This high
reactivity can be useful for catalysis, sensing.
(b) Band gap: The band gap is one of the fundamental properties of any
semiconductor, determining how it conducts electricity and interacts
with light. In QDs, we can engineer this property precisely by changing
its size. The band gap increases as the dot size decreases due to quantum
confinement.

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 (c) Optical Properties: When a quantum dot absorbs energy (from light,
electricity, or heat), electrons get excited from the lower energy state to
the higher energy state. When these excited electrons fall back down to
their ground state, they release energy as light. The color of this emitted
light depends directly on the size of the quantum dot. range of
wavelengths, creating somewhat muddy colors. Quantum dots have
specific energy gaps, emit very narrow bands of light, producing
extraordinarily pure and saturated colors.
(d) Electronic Properties: Quantum dots are so small, adding or removing
even a single electron requires significant energy due to the strong
electrostatic interactions in such a confined space. The electrical
conductivity of quantum dot materials depends on how well electrons
can move from one quantum dot to another. This transport process is
affected by several factors like size distribution of quantum dots and
spacing between dots.

Quantum dot sensitized solar cells (QDSSCs)

− Quantum Dot Sensitized Solar Cells (QDSSCs) are a type of third-generation
solar cell that use semiconductor quantum dots (QDs) as light-harvesting
materials.
− QDSSCs convert solar energy into electrical energy through photoexcitation of
electrons in quantum dots, which are then injected into a semiconductor
(usually TiO₂).

Construction:
A typical Quantum Dot Sensitized Solar Cell consists of the following layers:
1. Transparent Conducting Oxide (TCO) Glass:
• Usually FTO (Fluorine-doped Tin Oxide) or ITO (Indium Tin Oxide)
glass.
• Acts as a transparent front electrode to allow sunlight in and collect
electrons.
2. Semiconductor Layer (Photoanode):

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 • Typically, TiO₂ nanoparticles coated on the TCO glass.
• Provides a large surface area for quantum dot attachment.
3. Quantum Dots (Sensitizer):
• Materials like CdS, CdSe, PbS, etc.
• Absorb sunlight and generate electron-hole pairs.
• The size of QDs determines the absorption wavelength (tuneable band
gap).
4. Electrolyte (Redox Couple):
• Transfers charge by regenerating the oxidized quantum dot.
• Commonly used electrolyte: Polysulfide
5. The cathode or the counter electrode is made up of materials such as copper
sulfide

Working:
− When sunlight hits the cell, quantum dots absorb photons, exciting electrons
from the valence band to the conduction band, leaving holes behind.
− The excited electron is injected from the QD conduction band into the
conduction band of TiO₂
− The injected electron travels through the TiO₂ network to the TCO electrode
and then flows through the external circuit, generating electric current.
− The hole left in the QD is neutralized by the electrolyte.
− The counter electrode reduces the oxidized species in the electrolyte,
completing the circuit.

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Advantages
 The optical absorption of quantum dots can be tuned by changing their size,
enabling broad solar spectrum absorption.
 A single high-energy photon can generate more than one electron-hole pair,
improving theoretical efficiency beyond that of traditional solar cells.
 They have a favorable power to weight ratio with high efficiency. The mass and
 area savings as well as flexibility leads to miniaturization.

Disadvantages
 Common QDs like CdS and PbS are toxic heavy-metal compounds, posing
environmental issues.
 Liquid electrolytes can leak or degrade, affecting long-term stability.

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