UNIT-II

Energy storage and conversion devices

Abstract
This unit mainly focuses on the advanced energy systems used in day-to-day life. In
the beginning it starts from basics of battery technology, commercial lithium batteries
used in electronic gadgets along with advanced lithium air batteries. Further it explores
the innovation in the field of super capacitors and their importance in energy storage.
Finally, it covers the green energy systems such as fuel cell and solar energy. Over all
this unit helps the learners in exploring the knowledge of energy storage devices for
various applications in modern engineering practices.
Blow-up Syllabus
Sl Topic to be taught Duration
No
1 Battery: Introduction, types, characteristics 1 hour
2 Components/materials, construction, working and applications 1 hour
of Lithium cobalt oxide battery along with advantages and
limitations
3 Construction and working of Metal air batteries along with their 1 hour
advantages and limitations.
4 Super-capacitors: Introduction, types (EDLC, pseudo capacitors, 1 hour
hybrid capacitors), with examples.
5 Construction and working mechanism of EDLC, pseudo 1 hour
capacitors, hybrid capacitors along with applications.
6 Energy conversion devices: Introduction, characteristics, 1 hour
materials, working and applications of H2-O2 and
7 Construction, working and applications of direct methanol fuel 1 hour
cells
8 Construction and working of Quantum dot sensitized solar cells. 1 hour
9 Materials used in solar energy conversion Self-study

2.1. Battery technology

Introduction to electrochemistry
Electrochemistry deals with chemical reactions that produce electricity and the changes
associated with the passage of electrical current through matter. The reactions involve electron
transfer, and so they are oxidation-reduction (or redox) reactions. Many metals may be purified
or electroplated using electrochemical methods. Devices such as automobiles, smartphones,
electronic tablets, watches, pacemakers, and many others use batteries for power. Batteries use

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chemical reactions that produce electricity spontaneously and that can be converted into useful
work. All electrochemical systems involve the transfer of electrons in a reacting system. In
many systems, the reactions occur in a region known as the cell, where the transfer of electrons
occurs at electrodes.
Introduction to battery:
CELL: A cell designates a single unit. The conversion of chemical energy into electrical
energy is a function of cells or batteries.
BATTERY: A Battery is an electrochemical cell or often several electrochemical cells
connected in series that can be used as a source of direct electric current at a constant voltage.
Uses: Batteries are used in calculators, watches and pacemakers for heart hearing aids,
computers, car engines, standby power supplies, emergency lightning in hospitals,
electroplating industrial tractions and military and space applications. Batteries
have revolutionized the telecommunication system and are ushering a new era of transportation
with the possible replacement of petrol driven automobiles by the electrically powered ones.
In modern days portability of electronic equipment in the form of handsets has been made
possible by batteries.

Components of Battery: The cell consists of three major components.

● Anode: The anode selected with the following properties in mind; efficiency as a reducing
agent, high coulombic output (Ah/g) good conductivity, stability, ease of fabrication and
low cost.

● (Cathode: The cathode must be an efficient oxidizing agent, be stable when in contact with
the electrolyte, and have a useful working voltage.

● Electrolyte: The electrolyte must have good ionic conductivity but not be electrically
conductive. This would cause internal short circuiting. Electrolyte should be non-reactive
with the electrode materials.

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 Fig. 2.1: Structure of typical battery

Mechanism of working of battery: During discharging, the Battery acts as voltaic cell i.e.
oxidation takes place at the negative electrode (anode) and reduction takes place at the positive
electrode (cathode). During charging, The Battery acts as an electrolytic cell. The current flow
is reversed and oxidation takes place at the positive electrode (anode) and reduction takes place
at the negative electrode (cathode).
Criteria for commercial batteries
An efficient commercial cell should have following basic characteristics

● Portability: cells should be easily transportable without any environmental issues

● Compact: Battery should be more compact and lightweight

● Economy: Batteries should have less price with continuous electric supply.

● Power and energy density: batteries should have high power and energy density

● Recharging; It should be able to charge as well as discharge battery in faster rate with
recyclability

● Cycle and shelf life: Batteries should be having high cycle life and shelf life without
self-discharge.

Classification of batteries:
Majorly batteries are classified into three categories

● Primary battery: non-rechargeable (cell reactions are irreversible) - Self-discharges

whether used or not, leclanche cells (Zn/C) - Popular low-cost system, Applications: Torch
light, portable radios, toys, novelties, etc. Mg/MnO2 CELLS - High-capacity system:
Applications: Military communication equipment, voting machines, etc.

● Secondary battery: Rechargeable (cell reactions are reversible), Lead-Acid Battery

(Pb/H+), Nickel-Cadmium Battery (Ni-Cd), Nickel-Iron Battery (Ni-Fe), Nickel-Metal
hydride Battery (Ni-MH), Lithium battery (Li-LiMxOy), lithium-Ion battery (C-LiMxOy),
Lithium-Ion Polymer Battery (C-LiMxOy)

● Reserve battery: one of the key cell components, usually the electrolyte, is kept isolated
from the rest and is added at the time of need Examples: Mg/Cu 2Cl2, Mg/AgCl (sea water
activated battery), Applications: Torpedoes, Sea beacons (Mainly in Meteorology and

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 Defense fields), Li/FeS2 (Thermally activated battery). Applications: In Missiles and
rockets.
Battery Characteristics
The suitability of any battery for particular application is based on certain characteristic
properties. Some of
the important characteristics of battery are
The suitability of any battery for particular application is based on certain characteristic
properties. Some of the important characteristics of battery are

⮚ Voltage (V): In general, high voltage is desired from any battery. The voltage of any
battery depends on the emf of the cells which constitute the battery system. The emf of
the cell depends on the free energy in the overall cell reactions as given by Nernst
equation.
2.303𝑅𝑇 𝑃𝑟𝑜𝑑𝑢𝑐𝑡
𝐸 cell= 𝐸°cell− 𝑙𝑜𝑔 𝑙𝑜𝑔
𝑛𝐹 𝑅𝑒𝑎𝑐𝑡𝑎𝑛𝑡

Where Ecell = Ecathode – Eanode

From the above equation, emf of the cell and the voltage available from the battery is
dependent on the standard electrode potential difference between the cathode and anode,
temperature and the extent of the cell reaction. To get required high voltage, the difference
in the standard electrode potential should be more; temperature of the reaction should be
low. The conductivity of the electrolyte should be high.

⮚ Current (A): Current is a measure of the rate at which the battery is discharging. Higher
the rate of spontaneous reaction, higher is the current. Higher the surface area of the
electrodes, higher is the rate of reaction. Current is measured in Ampere (A).
𝑉
𝐼=
𝑅
Where I is the current, V is voltage and R is resistance of the battery.

⮚ Capacity (Ah): Capacity is a measure of the amount of electricity that may be obtained
from the battery. It is expressed in Ah (ampere hours). It is proportional to the amount of
charge in Coulombs that may be transported from anode to cathode through the external
circuit. The charge (C) in Coulombs is given by the Faraday’s relation:

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 Where, C is Capacity of battery (in Ah), W is Weight of the active material (Kg), n is
number of electrons involved in discharge reaction, F is Faraday’s constant, 96500 C/mol,
M is Molar mass of electro active materials.

⮚ Energy density (Wh/Kg): It is the amount of electricity stored in the battery per unit
weight of the battery. i.e., it is the capacity per unit weight. It can be expressed in
Coulombs/kg or in Ah/kg. The weight includes the weight of all components of the battery
(i.e. total weight of active material, electrolyte, terminals etc.). A high storage density
depends on a good battery design and also the appropriate selection of electrode reaction.
𝐼(𝑐𝑢𝑟𝑟𝑒𝑛𝑡) 𝑥 𝑡 (𝑡𝑖𝑚𝑒) 𝑥 𝑉 (𝑉𝑜𝑙𝑡𝑎𝑔𝑒 𝑜𝑓 𝑎 𝑏𝑎𝑡𝑡𝑒𝑟𝑦)
𝐸𝑛𝑒𝑟𝑔𝑦 𝑑𝑒𝑛𝑠𝑖𝑡𝑦 =
𝑤𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝑏𝑎𝑡𝑡𝑒𝑟𝑦

⮚ Power density (W / Kg): The ratio of the power available from a battery to its weight or
its volume (W / V) is called power density. The power density will decrease during
discharge and while recharge it will increase.
𝐼 (𝑐𝑢𝑟𝑟𝑒𝑛𝑡 )𝑥 𝑉(𝐸𝑀𝐹 𝑜𝑓 𝑏𝑎𝑡𝑡𝑒𝑟𝑦)
𝑃𝑜𝑤𝑒𝑟 𝑑𝑒𝑛𝑠𝑖𝑡𝑦 =
𝑀𝑎𝑠𝑠 𝑜𝑓 𝑒𝑙𝑒𝑐𝑡𝑟𝑜𝑎𝑐𝑡𝑖𝑣𝑒 𝑚𝑎𝑡𝑒𝑟𝑖𝑎𝑙

⮚ Energy efficiency: it is the ratio of energy released during discharge to energy consumed
during charging. The energy efficiency of a rechargeable battery is given by
𝐸𝑛𝑒𝑟𝑔𝑦 𝑟𝑒𝑙𝑒𝑎𝑠𝑒𝑑 𝑑𝑢𝑟𝑖𝑛𝑔 𝑐ℎ𝑎𝑟𝑔𝑖𝑛𝑔
𝐸𝑛𝑒𝑟𝑔𝑦 𝐸𝑓𝑓𝑖𝑐𝑖𝑒𝑛𝑐𝑦 = 𝑥100
𝐸𝑛𝑒𝑟𝑔𝑦 𝑠𝑢𝑝𝑝𝑙𝑖𝑒𝑑 𝑑𝑢𝑟𝑖𝑛𝑔 𝑐ℎ𝑎𝑟𝑔𝑖𝑛𝑔

⮚ Cycle life: The number of recharges per discharge cycle that are possible before the failure
of a secondary battery is called cycle life. In a secondary battery it is essential for the
discharge per recharge cycle to perform the active material in a suitable state for further
discharge reaction. The discharge per recharge cycle depends on the correct chemical
composition, morphology and proper distribution of active material in the battery.

⮚ Shelf life: The duration of storage under specific conditions at the end of which battery
still retains the ability to give specific performance is called shelf life. Shelf life for most
of the storage must be good. Good shelf life for a battery is possible when there is no self-
discharge or corrosion in current collectors.

Lithium-ion batteries:

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A Lithium-ion battery is a rechargeable battery which stores the energy by reversible reduction
of lithium ions. This battery is widely used in the portable electronic gadgets, e vehicles and
all medical equipment because of their energy density and compactness. This type of battery is
more advanced when compared to other types of battery such as lead acid and nickel cadmium
battery. Further these types of batteries are majorly classified as primary and secondary
batteries.
Criteria of selection of anode materials for lithium-ion battery
Desired characteristics of anode materials

⮚ Large capability of Lithium adsorption: porous anodes

⮚ High efficiency of charge/discharge

⮚ Excellent cyclability: high cycle life

⮚ Low reactivity against electrolyte: Chemical stability

⮚ Fast reaction rate

⮚ Low cost

⮚ Environmental -friendly, non-toxic

Commercial anode materials used in lithium batteries: Hard Carbon, Graphite
Criteria of selection of Cathode materials for lithium-ion battery
Desired characteristics of Cathode materials

⮚ High discharge voltage

⮚ High energy capacity

⮚ Long cycle life

⮚ High power density

⮚ Light weight

⮚ Low self-discharge

⮚ Absence of environmentally hazardous elements

Commercial cathode materials for lithium-ion battery: LiCoO2, LiMn2O4, LiNiO2, LiFePO4
Electrolytes used in the lithium-ion battery
Electrolyte is one of the important components of the battery ecosystem. In general
ether-based electrolytes along with lithium salts are used as electrolytes.

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The electrolyte should have following Characteristics in order to employ them in battery
technology

⮚ Inert: solvent stability

⮚ High ionic conductivity, low viscosity

⮚ low melting point & high dielectric constant (ε)

⮚ Appropriate concentration of Lithium salt

⮚ Chemical/thermal stability, High flash point (Tf), nontoxic,

⮚ Low cost

⮚ Environmental -friendly, non-toxic

Commercial electrolytes: LiPF6 in Carbonate solvent, propylene carbonate, 1,2

dimethoxyethane

Role of electrolyte in battery technology

⮚ Ion conductor between cathode and anode

⮚ Generally, Lithium salt dissolved in organic solvent

⮚ Solid electrolyte is also possible if the ion conductivity is high at operating temperature.
Separators: Separator is a membrane placed between a battery electrode. The main function
of a separator is to keep the two electrodes apart to prevent electrical short circuits while also
allowing the transport of ionic charge carriers that are needed to close the circuit during the
passage of current in an electrochemical cell.

Fig. 2.2: Separator in battery technology

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Primary lithium batteries: These are batteries in which redox reactions proceed only in the
one direction. The reactants in these batteries are consumed after a certain period of time,
rendering them dead. A primary battery cannot be used once the chemicals inside it are
exhausted. An example of a primary battery is the dry cell – the household battery that
commonly used to power TV remotes, clocks, and other devices. Best example for this battery
is the lithium-ion battery.
Secondary lithium-ion batteries: These are the rechargeable lithium-ion batteries. Here
electroactive materials are converted into electro inactive materials during discharge and during
charging again this electro inactive material can be converted into electroactive materials with
the help of external electricity. Examples: Lithium cobalt oxide battery, Lithium Nickel Cobalt
Aluminium Oxide, Lithium iron phosphate etc…
Lithium cobalt oxide battery
Lithium Cobalt is a mature, proven, industry-standard battery technology that provides
long cycle life and very high energy density[1]. The polymer design makes the cells inherently
safer than "canned" construction cells that can leak acidic electrolyte fluid under abusive
conditions. The cell voltage is typically 3.7 Volts.
Construction of LiCoO2 battery

⮚ Positive electrode: Lithiated form of a transition metal oxide (lithium cobalt oxide-LiCoO2
or lithium manganese oxide LiMn2O4)

⮚ Negative electrode: Lithiated Carbon (C) usually graphite (C6)

⮚ Electrolyte: solid lithium-salt electrolytes (LiPF6, LiBF4, or LiClO4) and organic solvents

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 Fig. 2.3: Structure of lithium-ion battery
Solid electrolyte interphase (SEI) layer: A passivation layer called the solid electrolyte
interphase (SEI) is formed on electrode surfaces from decomposition products of electrolytes.
The SEI allows Li+ transport and blocks electrons in order to prevent further electrolyte
decomposition and ensure continued electrochemical reactions.

Fig. 2.4: Role of solid electrolyte interphase

Mechanism of working: in lithium cobalt oxide batteries, generally lithium salts are used as
electrolytes along with 1, 2 dimethoxy ethane and propylene carbonate. The main reason
behind the selection of this solvent is its density and high boiling inert nature. During the
discharging reaction the lithium metal in the anode compartment converts into lithium ion and
it moves through SEI and separator towards cobalt cathode. In the cathode it reacts with Cobalt
oxide and the electron to form LiCoO2. And this process is reversible during charging. During
discharging movement of lithium ions takes place from anode to cathode and it moves from
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cathode to anode when connected to an external power supply. The chemical reaction that takes
place inside the battery is as follows, during charge and discharge operation:

Reactions during discharge

At anode

LiXC6 Li+ + xe- + 6C

At cathode

Li 1-X CoO2 + xLi+ + xe- LiCoO2

Overall reaction

LiXC6 + Li 1-X CoO2 LiCoO2 + 6C

Similarly reverse reactions will happen during charging when the battery is connected to
external power source. In the above reaction x can be 1 or 0, With discharge the Co is oxidized
from Co3+ to Co4+.
The reverse process occurs when the battery is being charged.

Advantages and limitations of lithium-ion batteries

When compared to other type of commercial batteries such as lead acid and nickel metal
hydride batteries lithium batteries have several advantages. Few of them listed below
Advantages of lithium-ion batteries:

⮚ Lightweight compared to other batteries

⮚ Higher theoretical energy density than other types of batteries

⮚ Rate of loss of charge is very less

⮚ Operates at higher voltages than other batteries

⮚ High adaptability to several applications

⮚ As there is no memory effect, no need to completely drain the battery

⮚ Low self-discharge compared to lead acid battery

⮚ Easy maintenance
Limitations of lithium-ion batteries:

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 ⮚ Sourcing of lithium is difficult

⮚ As lithium is not abundant, extraction of it doesn’t meet global need

⮚ Expensive than the other commercially available battery

⮚ This battery is temperature sensitive; at higher temperature it may degrade with

explosion

⮚ Extra protection is required if want to employ them in large scale application

⮚ Disposal may a problem because of heavy metal cathodes

Metal air batteries

Metal air battery is one of the most advanced batteries in which metal incorporated in a carbon
matrix acts as anodes and air itself-acts as cathode. Amongst all the studied metal air batteries,
lithium air batteries are more attractive because of its high energy density along with light
weight[2].
In general lithium ions move between the anode and the cathode across the electrolyte.
Under discharge conditions, electrons follow from the external circuit to do electric work and
the lithium ions migrate to the cathode. During charging the lithium metal in the anode, freeing
O2 at the cathode. In the case of non-aqueous lithium air batteries Li2O2 or LiO2 are the
byproducts. Similarly in aqueous lithium air battery LiOH is the byproduct. Further aqueous
lithium air battery requires a protective layer to protect the lithium metal in the anode.

Components and working of lithium air battery

Generally, lithium air batteries consist of lithium anode and porous cathode which will
allow air from it. Then air itself-acts as a cathode. Also, these lithium air batteries can have
different electrolyte systems such as aqueous and non-aqueous. The chemical reaction in these
types of batteries is given below.
Non aqueous lithium air battery Aqueous lithium air battery
Anode: lithium metal Acidic electrolyte
Cathode: Oxygen (air) 2Li + ½O2 + 2H+  2Li++ H2O
Anodic reactions: Li  Li+ + e- Alkaline aqueous electrolyte
Cathodic reactions: 2Li + ½O2 + H2O  2LiOH
Li+ + e− +O2 +  LiO2*
Li+ + e− +LiO2*  Li2O2*

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 Fig. 2.5: lithium air battery
The electrical energy is provided by the chemical reaction between the lithium metal and O2
from the air. The oxygen electrode has to be porous in order to allow the transport of gasses.
The lithium electrode will be protected by a solid electrolyte interphase (SEI), which can be
artificially prepared or spontaneously formed by the reaction of lithium with the electrolyte.
Lithium–air batteries can also be built in the full solid state by using a solid electrolyte.
The main advantages of lithium air batteries are

● High theoretical specific energy of lithium

● Light weight of lithium

● Use of light weight oxygen

● High theorical capacity of lithium metal

In the case of non-aqueous lithium air batteries, two main discharge products have been
proposed: Li2O2 and Li2O. In the case of aqueous lithium–oxygen batteries, the theoretical
specific energies are lower, due to the presence of hydrating water molecules in some of the
species involved in the reactions. The main byproduct in the aqueous lithium air battery is
LiOH. Limitations of lithium air battery are as follows

● Poor reversibility

● Inferior long term cyclability

● Electrolyte evaporation

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2.2. Supercapacitor
Supercapacitors, also known as electrochemical capacitors, utilize high surface area
electrode materials and thin electrolytic dielectrics to achieve capacitances several orders of
magnitude larger than conventional capacitors [3]. In doing so, supercapacitors are able to
attain greater energy densities while still maintaining the characteristic high-power density of
conventional capacitors. A supercapacitor (SC), also called an ultracapacitor, is a high-
capacity capacitor with a capacitance value much higher than other capacitors, but with lower
voltage limits, that bridges the gap between electrolytic capacitors and rechargeable batteries.
It typically stores 10 to 100 times more energy per unit volume or mass than electrolytic
capacitors, can accept and deliver charge much faster than batteries, and tolerates many more
charge and discharge cycles than rechargeable batteries.
Definition: A supercapacitor is a double-layer electrolytic capacitor that can store large
amounts of energy nearly 10 to 100 times more energy when compared to the electrolytic
capacitors. It is widely preferred over batteries because of its faster charging capacity and faster
delivery of energy. It has more charging and discharging cycles than rechargeable batteries.
The capacitance of this capacitor is also measured in Farad’s (F). The main advantage of this
capacitor is its efficiency and high-energy storage capacity.
Principles of Energy storage
The supercapacitor has the self-discharging capacity and unlimited charging-
discharging cycles. These types of capacitors can work with low voltages (2-3 volts) and can
be connected in series to produce high voltage, which is used in powerful equipment. It can
store more energy and releases instantly and more quickly when compared to batteries. When
this capacitor is connected to the circuit or DC voltage source, the plates are charges and
opposite charges are formed on both sides of the separator, which forms a double-layer
electrolytic capacitor. To charge a supercapacitor, connect the positive side of the voltage
source to the positive terminal of the supercapacitor and the negative side of the voltage source
is connected to the negative terminal of the supercapacitor. If the supercapacitor is connected
to a 15 volts voltage source, then it charges up to 15 volts. As the voltage is increased beyond
the applied voltage source, the supercapacitor may get damaged. So, the resistor is connected
in series with the voltage source and capacitor to decrease the amount of current flowing
through the capacitor and it doesn’t get damaged. The constant current supply and limited
voltage supply is suitable for the supercapacitor. When the voltage is increased gradually, the

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amount of current flowing through the capacitor changes. In the fully charged mode, the current
drops by default.
Classification of super capacitor
Supercapacitors majorly classified as follows
Electrostatic double-layer capacitors (EDLCs): EDLCs use carbon-based materials as
electrodes with higher electrostatic double-layer capacitance, achieving separation of charge in
a Helmholtz double layer at the interface between the surface of a conductive electrode and an
electrolyte.
Electrochemical pseudo-capacitors: Use metal oxide or conducting polymer electrodes with
a high amount of electrochemical pseudo capacitance additional to the double-layer
capacitance. Pseudo capacitance is achieved by Faradaic electron charge-transfer with redox
reactions, intercalation or electro sorption.
Hybrid capacitors: Hybrid capacitors are lithium-ion capacitors, use electrodes with differing
characteristics. In this type of supercapacitor, principles of both battery and supercapacitors are
involved to increase energy density and power density.

Fig. 2.6: super capacitors classification

Electrostatic double-layer capacitors (EDLCs)
Electrochemical double-layer capacitors (EDLCs) are constructed from two similar
carbon-based electrodes, an electrolyte, and a separator. These types of super capacitors store

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the energy very similarly to conventional capacitors. These EDLCs store charge
electrostatically, or non-Faradaic Ally, and there is no transfer of charge between electrode and
electrolyte. These EDLCs store the charge using an electrochemical double-layer. As voltage
is applied, charge accumulates on the surface of both the electrodes. This is followed by the
natural attraction of unlike charges, ions in the electrolyte solution diffuse across the separator
into the pores of the electrode of opposite charge. In this architecture electrodes are designed
to avoid recombination of ions. Due to this a double-layer of charge is produced at each
electrode. These double-layers, coupled with an increase in surface area and a decrease in the
distance between electrodes, allow EDLCs to achieve higher energy densities than
conventional capacitors. Due to the non-transferring of charges between electrolyte and
electrode, there are no chemical or composition changes associated with non-Faradaic
processes. For this reason, charge storage in EDLCs is highly reversible, which allows them to
achieve very high cycling stabilities. The performance characteristics of an EDLC can be
adjusted by changing the nature of its electrolyte.
An EDLC can utilize either an aqueous or organic electrolyte. Aqueous electrolytes,
such as H2SO4 and KOH, generally have lower minimum pore size requirements compared to
organic electrolytes, such as acetonitrile. In these EDLCs generally carbon-based materials are
used because of their higher surface area, lower cost, and more established fabrication
techniques than other materials, such as conducting polymers and metal oxides. Different forms
of carbon materials that can be used to store charge in EDLC electrodes are activated carbons,
carbon aerogels. and carbon nanotubes.

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 Fig. 2.7: Electrolytic double layer capacitor
Electrochemical Pseudo capacitance:
Applying a voltage at the electrochemical capacitor terminals moves electrolyte ions to
the opposite polarized electrode and forms a double-layer in which a single layer of solvent
molecules acts as a separator. Pseudo capacitance can originate when specifically adsorbed
ions out of the electrolyte pervade the double-layer[4]. This pseudo capacitance stores electrical
energy by means of reversible redox reactions on the surface of suitable electrodes in an
electrochemical capacitor with an electric double-layer. Pseudo capacitance is accompanied
with an electron charge-transfer between electrolyte and electrode coming from a de-solvated
and adsorbed ion whereby only one electron per charge unit is participating. This faradaic
charge transfer originates by a very fast sequence of reversible redox, intercalation or electro
sorption processes. The adsorbed ion has no chemical reaction with the atoms of the. electrode
since only a charge-transfer takes place. The electrons involved in the faradaic processes are
transferred to or from valence electron states (orbitals) of the redox electrode reagent. They
enter the negative electrode and flow through the external circuit to the positive electrode where
a second double-layer with an equal number of anions has formed. The electrons reaching the
positive electrode are not transferred to the anions forming the double-layer, instead they
remain in the strongly ionized and "electron hungry" transition-metal ions of the electrode's
surface. As such, the storage capacity of faradaic pseudo capacitance is limited by the finite
quantity of reagent in the available surface.

Fig. 2.8: Electrochemical pseudo capacitance

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 Hybrid Capacitors
Hybrid supercapacitors have higher operating voltage (3.8 V maximum) and much
higher capacitance and energy density (up to 10 times) than symmetric supercapacitors. They
also have much lower self-discharge and standby current. They can be discharged to zero volts
for safety; hybrid supercapacitors cannot be discharged fully. From a construction standpoint,
they are very similar, but a hybrid supercapacitor uses an anode made from graphite laced with
lithium and a different electrolyte. Utilizing both Faradaic and non-Faradaic processes to store
charge, hybrid capacitors have achieved energy and power densities greater than EDLCs
without the sacrifices in cycling stability and affordability that have limited the success of
pseudo capacitors. The schematic representations of hybrid capacitors are given below.

Fig. 2.9: Schematics representation of hybrid capacitor

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 Importance of Electrolytes in supercapacitors
Characteristics of electrolyte used in supercapacitors

⮚ Wide potential window

⮚ High ionic conductivity

⮚ High chemical and electrochemical stability

⮚ High chemical and electrochemical inertness to ES components

⮚ Wide operating temperature range

⮚ Well-matched with the electrolyte materials

⮚ Low volatility and flammability

⮚ Environmentally friendly

⮚ Low cost
Advantages and limitations of super capacitor
These super capacitors are having advantages as well as limitations, some of them highlighted
below. Advantages of supercapacitor are as follows

⮚ High energy storage.

⮚ Wide operating temperature (-40 oC to 60 oC).

⮚ Eco-friendly.

⮚ Quick charging time.

⮚ Maximum life cycle.

⮚ High cycle efficiency (95%).

⮚ High specific power up to 17 kW/kg.

⮚ Extremely low internal resistance and Safe

Limitations of super capacitors are as follows

⮚ Low energy density; usually holds 1/5 – 1/10 of a battery.

⮚ Cannot use the full energy spectrum for some applications.

⮚ The voltage varies with the energy stored.

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 ⮚ Have a high self-discharge rate.

⮚ Individual cells have low voltages, and so serial connections are needed to obtain higher
voltages.

⮚ Requires expert electronic control.

⮚ Cannot be used in AC and high frequency circuits.

⮚ High cost.
Applications of supercapacitor

⮚ In the startup mechanism for Automobiles.

⮚ Used in Diesel engine start up in submarines & tanks.

⮚ In quickly recharged electric bus

⮚ Backup power system in missiles.

⮚ Power source for laptops, flash in cameras.

⮚ Voltage stabilizer.

⮚ To deliver high power and bridge power gaps

⮚ Industrial and electronic applications

⮚ Used in wind turbines, electric and hybrid vehicles

⮚ Regenerative braking to release the power in acceleration

⮚ To start power in start-stop systems

⮚ Regulate voltage in the energy grid

⮚ To capture and assist the power in lower loads and lifted loads
Super battery
Superbattery is an innovative technology that combines the advantages of batteries and
supercapacitors. In less than 60 seconds, charged. Up to 30 minutes of driving can be
accomplished with 60 seconds of charge, therefore lengthy charging stops are eliminated.
Super battery is a unique combination of materials that allows for 100x faster charging
compared to standard lithium-ion batteries while offering excellent safety.
Hybrid battery called a superbattery combines ultracapacitor cells with regular lithium-
ion cells. The Curved Graphene material utilized to create the ultracapacitors is the primary

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characteristic that sets the Superbattery apart from comparable devices. The Superbattery does
not have the energy density to completely replace lithium-ion batteries, like other
ultracapacitors.
Although lithium batteries have a high energy storage capacity, they have a low power
density, which results in lengthy charge and discharge cycles. In contrast to batteries, which
are charged by a chemical reaction, ultracapacitors are charged and discharged via static
electricity. Because of this, ultracapacitors have a far longer lifespan without deterioration than
chemical batteries and can charge and discharge at much higher rates. Ultracapacitors, on the
other hand, have a very low energy density. A storage device composed of ultracapacitors
would need to be significantly larger than a lithium-ion battery to hold the same amount of
energy. The advantages of lithium battery and ultracapacitor are combined in a super battery.
The Super battery might be a good fit for hybrids, plug-in vehicles, or vehicles that run on
hydrogen fuel despite having a far lower energy density than normal electric vehicle batteries.
In all-electric vehicles, it might supplement the main battery during acceleration or other
strenuous circumstances. Structure of a typical super battery manufactured by Skeleton
company is depicted in the figure.

Fig. 2.10: Schematic representation of super battery

2.3. Fuel cells

A fuel cell is an electrochemical device, which can continuously convert the chemical
energy of a reducing agent and an oxidant fuel stored externally by a process involving an
essentially invariant electrode electrolyte system. A fuel cell consists of two electrodes and an
electrolyte. However, the fuel and the oxidizing agents are continuously and separately
supplied to the two electrodes of the cell, at which they undergo reactions. These cells are
capable of supplying current as long as they are supplied with the reactants.
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A fuel cell may be represented as: Fuel/electrode/electrolyte/electrode/oxidant At the anode
fuel undergoes oxidation and at the cathode oxidant undergoes reduction. Fuel cell is an
energy conversion device the main difference between fuel cell and battery are as follows.
Sl Battery Fuel cell
No
1 These are the energy storage devices These are energy conversion devices
2 Secondary batteries are rechargeable Fuel cells are not chargeable.
3 The reactants and products form integral In fuel cells, there is a continuous
part of the batteries supply of fuel, oxidant
4 Products remain in the cell Products are continuously removed
from the cell
Advantages of fuel cells

● Savings in fossil fuels due to the high efficiency of electrochemical energy conversion.

● Low pollution level, no noxious exhaust gasses formed.

● Low noise level.

● Low maintenance, exchangeable parts.

● No need for charging.

● Theoretically, the efficiency can be 100%. In practice, the efficiency is 50-80% which is high
compared to conventional methods

● Have few moving parts and thus require minimal maintenance, reducing life cycle costs of
energy production.

● Modular in design, offering flexibility in size and efficiencies in manufacturing

● Can be utilized for combined heat and power purposes, further increasing the efficiency
of energy production
Limitations of fuel cell

● The electrodes used are Pt, Ag or alloys of noble metal which are costly.

● High price of clean hydrogen.

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 Hydrogen oxygen fuel cell

The Hydrogen oxygen fuel cell is categorized under alkaline fuel cells (AFC). The alkaline fuel
cell uses an alkaline electrolyte such as 40% aqueous potassium hydroxide. In alkaline fuel
cells, negative ions travel through the electrolyte to the anode where they combine with
hydrogen to generate water and electrons.

These fuel cells can use a variety of metals as a catalyst at the anode and cathode and
use a solution of potassium hydroxide in water as the electrolyte. Low-temperature AFCs
function between 23°C and 70°C, while high-temperature AFCs run between 100° and 250°C.
AFCs are high-performance fuel cells because of how quickly chemical processes occur inside
the cell. They are also incredibly effective, with space applications achieving efficiency of
60%. This fuel cell type's drawback is that carbon dioxide (CO2) can poison it readily. It is vital
to purify both the hydrogen and oxygen used in the cell because even a small amount of CO 2
in the air can have an impact on how the cell functions. This fuel cell type's drawback is that
carbon dioxide (CO2) can poison it readily. It is vital to purify both the hydrogen and oxygen
used in the cell because even a small amount of CO2 in the air can have an impact on how the
cell functions. Potassium carbonate, which is created when CO2 and KOH mix, will improve
resistance. More than 8,000 working hours of AFC stacks have been demonstrated to sustain
adequately steady operation.

Construction and working of Hydrogen oxygen fuel cells

Construction: It is made up of two inert porous carbon plates that serve as the cathode and the
anode. A 25% solution of NaOH or KOH positioned between the two electrodes serves as the
electrolyte. While oxygen gas constantly bubbles at the cathode, hydrogen gas continuously
bubbles at the anode. Generally, platinum is used as anode catalyst and silver is used as cathode
catalyst.

Working:

When Hydrogen gas pumped at the anode surface the following oxidation reaction occurs:

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 H2(g) + 4 OH-(aq) 4H2O(l)+ 4e-

The liberated electrons from anode then passes through the external circuit where work is
performed, & then finally to the cathode where following chemical reaction takes place

O2 (g) + 2H2O(l) )+ 4e-  4 OH- (aq)

Hence Net reaction:

H2 (g) + 2O2 (g) 2H2O(l)

Fuel: Hydrogen
Oxidant: Oxygen
Anode: porous carbon with Pt
Cathode: porous carbon with
Ag
Electrolyte: KOH

Fig.: 2.11: Hydrogen oxygen fuel cell

Advantages:

● Zero emissions: The only byproduct of a fuel cell car is water vapor. As a result, there
is no air pollution.

● High efficiency: Without using combustion, fuel cells transform chemical energy
directly into electricity. Fuel cells can thus reach significant energy conversion
efficiency.

● High power density: Fuel cells can be used in applications where space is limited
because of their high-power density

● No Pollution: Fuel cell generators don't produce any thermal, vibrational, or acoustic

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 pollution.

● Replaceable: Because fuel cell systems are modular, it is simple to swap out individual
pieces.

● Water is produced by a hydrogen oxygen fuel cell and is of portable quality

● Fuel cell systems: no recharging

Limitations

● It is difficult to manufacture and stores a high pure hydrogen

● High cost of pure hydrogen

● Life span of the cells are not accurately known

● Lack of infrastructure for distributing hydrogen.

● Liquefaction of hydrogen requires 30% of the stored energy

Construction and working of Direct Methanol- Oxygen Fuel Cell

Methanol is used as the fuel in direct-methanol fuel cells, which are a type of proton-
exchange fuel cell. Their key benefit is the simplicity of transporting methanol, an
environmentally stable and energy-dense liquid.

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 Fig. 2.12: Direct methanol fuel cell (DMFC)

Construction: In this type of fuel cell, Methanol is used as fuel and oxygen is used as oxidant.
Here Porous nickel impregnated with pt/pd used as anode and Porous nickel impregnated with
Ag used as cathode. H2SO4 is used as an electrolyte. The cell will offer an EMF of 1.186V.

Working mechanism
Fuel cell is fed with methanol and water at anode site. After the injection of methanol,
it passes through anode catalyst (Pt/Rh) and membrane, then splits into carbon dioxide and
proton with the liberation of electrons. Carbon dioxide escapes from the system and the electron
will move in the external circuit. This electron reacts with oxygen at cathode in presence of
cathode catalyst (Ag) to produce water as a useful byproduct.

Anodic reactions

Cathodic reactions

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Overall reaction is
CH3OH + 3/2 O2 → CO2 + 2H2O

Alkali electrolytes are not preferred in advanced methanol fuel cells because, liberated CO 2
during reaction is converted into carbonate in presence of an alkali and would have an adverse
effect on working of the cell. Hence, design of methanol-oxygen fuel cell in acid medium is
attempted; electrodes made of Pt-Ru-Ni and Pt-Ru-Ni alloys are used. Energy density of
DMFC (15 times higher than Lithium-ion batteries) and power density are high, Energy
efficiency is low. DMFC is Sensitive to CO2 – if alkali is used this leads to the formation of
carbonates spoiling the quality of electrodes, hence sulphuric acid is used.
CO2 formed blocks the porosities as carbonates and efficiency of the cell is decreased.

CO2 + 2OH-  CO3-2 + H2O

2.4. Photovoltaics
Introduction:
Solar energy is a renewable energy and it is inexhaustible. The earth is receiving
approximately 1.8×1011 MW of energy which is thousands of times larger than the requirement
of energy for present consumption. Thus, solar energy is the only energy that fulfills all our
present and future energy needs if we utilize it properly. Solar energy can be directly converted
into heat energy or electricity. A solar cell, or photovoltaic cell, is an electrical device that
converts the energy of light directly into electricity by the photovoltaic effect.

Advantages of Solar Cells

⮚ Solar cell is renewable energy which can be continuously drawn from the sun.

⮚ It is economic friendly energy because once it is installed there will be minimum

maintenance charges for small usage.

⮚ Solar energy is environmentally friendly and green energy because it doesn’t produce
any greenhouse gasses and no pollutants.

⮚ It doesn’t involve any combustion reaction or radioactive residue hence no pollution

⮚ Disadvantages of Solar Cells

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 ⮚ Space utilization: Solar cells required large area for installation

⮚ It requires high investment cost for a big power plant

⮚ During the rainy season power production is less hence grid maintenance will be
difficult.

⮚ Solar energy is produced only in the day time hence storage will be a big challenge
Classification of solar cells
The solar cells are broadly classified as i) Inorganic solar cells and ii) Organic/polymer
solar cells. Amongst them inorganic solar cells are currently in the global market. The
amorphous silicon solar cells are classified under inorganic solar cells. There are three types of
PV cell technologies that dominate the world market: monocrystalline silicon, polycrystalline
silicon, and thin film. Higher efficiency PV technologies, including gallium arsenide and multi-
junction cells, are less common due to their high cost, but are ideal for use in concentrated
photovoltaic systems and space applications [6]. There is also an assortment of emerging PV
cell technologies which include Perovskite cells, organic solar cells, dye-sensitized solar cells
and quantum dots solar cells.

Fig. 2.13: Classification of solar cells

Quantum dot sensitized solar cells

Quantum dots (QDs)

27
 Quantum dots are tiny particles or nanocrystals of a semiconducting material with
diameters in the range of 2-10 nanometers. When they are illuminated by UV light, an electron
in the quantum dot can be excited to a state of higher energy. In the case of a semiconducting
quantum dot, this process corresponds to the transition of an electron from the valence band to
the conductance band. The excited electron can drop back into the valence band releasing its
energy as light. The color of that light depends on the energy difference between the
conductance band and the valence band. Potential applications of these quantum dots include
solar cells, LEDs, lasers, quantum computing, cell biology research and medical imaging.
Examples for QD sensitizers such as CdS, CdSe, PbS, PbSe,CdTe etc.
It consists of two electrodes cathode and anode, generally cathode, is made of graphite
or platinum. Anode is made of transparent conducting oxide such as Indium tin oxide. Anode
is coated with a layer of nano porous materials (TiO2 of ZnO). Further these nano porous
materials are coated with CdSe quantum dots as light absorbing materials. Here the nano porous
materials act as semiconductors and also provide a way for electrons. The quantum dots with
suitable energy levels help in the electron transfer process. A triiodide electrolyte system is
employed in between the electrodes, which helps in electron transfer process[7].

Fig. 2.14. Construction and working of quantum dye sensitized solar cells.

Mechanism of Working
When a light photon strikes the solar cell, it passes through the ITO layer and it reaches
the quantum dots. Once the photon hits the quantum dots, it undergoes excitation with the
liberation of electrons, which travels through the network TiO 2 nanoparticles (because of

28
matching in energy levels) and finally it reaches the cathode. The cell is completely filled with
Triiodide electrolyte. The electron from the cathode directly reduces the triiodide molecule to
three iodide molecules. Further this iodide molecule oxidizes to form triiodide again with the
liberation of electrons, which can be easily absorbed by quantum dots. And a similar cycle
continues whenever sunlight falls on the solar cells.

References/supporting materials

[1] K. Wang et al., “Recent advances and historical developments of high voltage lithium
cobalt oxide materials for rechargeable Li-ion batteries,” J. Power Sources, vol. 460, p.
228062, Jun. 2020, doi: 10.1016/j.jpowsour.2020.228062.
[2] N. Imanishi and O. Yamamoto, “Perspectives and challenges of rechargeable lithium–air
batteries,” Mater. Today Adv., vol. 4, p. 100031, Dec. 2019, doi:
10.1016/j.mtadv.2019.100031.
[3] M. S. Halper, “Supercapacitors: A Brief Overview,” 2006.
[4] T. Prasankumar et al., “Pseudocapacitors,” in Supercapacitors for the Next Generation,
IntechOpen, 2021. doi: 10.5772/intechopen.98600.
[5] L. Fan, Z. Tu, and S. H. Chan, “Recent development of hydrogen and fuel cell
technologies: A review,” Energy Rep., vol. 7, pp. 8421–8446, Nov. 2021, doi:
10.1016/j.egyr.2021.08.003.
[6] “RECENT PROGRESS OF AMORPHOUS SILICON SOLAR CELLS,” in Energy and
the Environment, Pergamon, 1990, pp. 39–48. doi: 10.1016/B978-0-08-037539-7.50008-
9.
[7] A. J. Nozik, “Quantum dot solar cells,” Phys. E Low-Dimens. Syst. Nanostructures, vol.
14, no. 1, pp. 115–120, Apr. 2002, doi: 10.1016/S1386-9477(02)00374-0.

Video links

Topics Links QR Code

1 Battery https://drive.google.com/file/d/1rFOYQWvf31Tb
technology mRM3Ok_-aVb0PrJqDHQF/view?usp=sharing

2 Fuel cell https://drive.google.com/file/d/1bTvfVJM3Oacu

technology 7Y0Vdmwz6T4pkIF8wE75/view?usp=sharing

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3 Photovoltaics https://drive.google.com/file/d/1Z8yMvYZVuh
Wx_jmATGR2PGnRn4D3yYdh/view?usp=shari
ng

4 Supercapacitor https://www.youtube.com/watch?v=iFVVv23Zz
GE

5 Introduction to https://www.youtube.com/watch?v=nh2xbyOaE
battery Rw
technology

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