MODULE 2

Energy conversion and storage

Batteries: Introduction, classification of batteries, components, construction, working and
applications of modern batteries: Na-ion battery, solid state battery (Li-polymer battery)
and flow battery (Vanadium redox flow battery).
Fuel cells: Introduction, construction, working and applications of methanol–oxygen and
polymer electrolyte fuel cell.
Solar energy: Introduction, importance of solar PV cell, construction and working solar PV
cell, advantages and disadvantages.
Self-Study Components: Electrodes for electrostatic double layer capacitors, pseudo
capacitors, and hybrid capacitor.

Introduction
“A battery is a compact device consisting of two or more galvanic cells
connected in series or parallel or both. It stores chemical energy in the form of
active materials and on demand converts it into electrical energy through
redox reactions”.
Thus, a battery acts as portable source of electrical energy. Battery technology has
acquired importance in view of development in microelectronics and increased demand
for portable gadgets. The trend of miniaturization has been challenge to the battery
manufacturers.
Classification of Batteries
Batteries are classified as (1) primary batteries (2) secondary batteries and (3)
reserve batteries
1. Primary batteries: a battery which cannot be recharged (because the cell
reactions are irreversible) and discarded when the battery has delivered all its
electrical energy is called as a primary battery. The electrical current available
depends on the quantity of active materials present. They have limited shelf life
and are discharged continuously with fairly high efficiencies.
Ex: Leclanche dry battery, Zinc-air battery, Zn – MnO2 battery, etc.
2. Secondary batteries: a battery which after discharging, can be recharged (as the
cell reactions are reversible) again by passing the electric current through it in the
opposite direction to that of the discharge is known as the secondary battery.
Secondary batteries are also known as rechargeable batteries or accumulators or
storage battery. The charge-discharge cycle (cycle life) can be repeated several
hundred times and these batteries can be built into giant generators with high
capacities.
 Ex: Lead storage battery, Nickel-Cadmium battery, etc.
3. Reserve batteries: in the reserve batteries, one of the components is stored
separately and is incorporated into the battery when required. Usually, the
electrolyte is stored separately. Example: Magnesium batteries activated by water
(Mg – AgCl and Mg – CuCl); Zn – Ag2O batteries. The advantage of reserve
batteries are long shelf life, high performance reliability and variety of design
options. Reserve batteries use highly active component materials for low
temperature performance. They are designed to meet long and environmentally
severe storage requirements. Reserve batteries are primarily used to deliver high
power for relatively short periods of time in application such as radiosonodes (air
borne instrument to send Meteorological information back to earth by radio),
missiles, trajectory, mid-ocean disasters and crisis in space.

Components of a battery
The basic electrochemical unit in a battery is the galvanic cell. The major
components of a battery are described below:
1. Anode or negative electrode: It releases electrons to the external circuit by
undergoing oxidation during electrochemical reaction.
M Mn+ + ne-
2. Cathode or positive electrode: It accepts electrons from the external circuit and
reduction of an active species occurs.
Mn+ + ne- M
3. Electrolyte: It is the active mass in the anode and cathode compartments. It
provides the medium for transfer of ions inside the cell between the anode and
cathode. A solution of an acid, alkali or salt having high ionic conductivity is
commonly used as an electrolyte.
4. Separator: It is used to separate anode and cathode compartments in a battery to
prevent internal short circuiting. A separator allows transport of ions from anode
to cathode and vice versa to maintain the electrical neutrality. It is an electrolytic
conductor but an electronic insulator. Fibrous forms of regenerated cellulose, vinyl
polymers and polyolefins, cellophane and nafion membranes are used as
separators.
Working of a battery
Working of a battery involves discharging (delivering power) and recharging
(charging).
Discharge (generation of electricity or conversion of chemical energy into electrical
energy) occurs when anode and cathode are externally connected and hence the circuit is
closed. During discharge anode undergoes oxidation by releasing the electrons and thus,
metal atoms from anode move into the solution as metal ions (cations). Hence, cationic
concentration increases in the anodic compartment. The released electrons flow from the
anode to the cathode through the external circuit and thus constitute flow of current.
At anode M1 M1n+ + ne-
At cathode, electrons are accepted for the reduction of the metal ions (cations) to
metal atoms (which get deposited on cathode) and hence anionic concentration becomes
more in the cathodic compartment.
At cathode M2n+ + ne- M2

The anions and cations formed at the respective electrodes move across the
separator to maintain electro neutrality and to complete the electric circuit. Thus, during
discharge, concentration of active species at anode gradually decreases and hence the
EMF of the battery decreases. The battery stops to deliver power after EMF drops beyond
certain limits.
During recharge, the current flow is reversed with the aid of a DC power supply.
The negative terminal of the power supply is connected to the anode of the battery and
positive terminal to the cathode of the battery. Under this condition, metal ions are
reduced to metal atoms (which get deposited on anode) at anode and anionic
concentration increases in anodic compartment.
At anode M1n+ + ne- M1
At cathode, oxidation occurs by releasing electrons and hence, cationic
concentration increases in cathodic compartment.
At cathode M2 M2n+ + ne-

During recharge, the positive electrode acts as anode and the negative electrode acts
as cathode. That is, electrode reactions are reversed and hence electro active materials are
restored. Hence original EMF of the battery will be restored.
Sodium-ion battery:
Sodium-ion batteries (SIBs) are energy conversion and storage devices that use sodium-
ions to shuttle positive charge between the anode & cathode in order to convert electrical energy
to chemical energy and vice versa.
SIBs generally contain two electrodes, one anode and one cathode, both consisting of the
respective active materials coated on an aluminum foil current collector. A thin liquid-permeable
sheet called the separator is placed between the two electrodes to keep them electrically insulated
from each other, while allowing sodium ions to move freely between the electrodes. The anode
or negative electrode, is where the sodium is stored when the cell is in the charged state, while
the cathode or positive electrode, hosts the sodium-ions in the discharged state. The transport of
positively charged sodium ions between the electrodes is enabled by a solvent salt solution called
the electrolyte, while electrons move between the current collectors through an external circuit.
The electrochemical cell reactions in a Na-S battery are as follows:
Anode: 2Na 2Na+ + 2e-
Cathode: nS + 2Na+ + 2e- Na2Sn
Overall cell reaction: nS + 2Na  Na2Sn

Anode: Hard carbon is used as the “standard” anode material in SIB that stores sodium-ions at a
low potential.

Cathode: cathode material is layered oxides (FePO4, CoO2, Fe[Fe(CN)6] and polyanionic
compounds i.e., Na2Fe2(SO4)3

Electrolyte: Electrolytes can be solids or liquids. The solid electrolytes are either polymeric or
ceramic. Liquid electrolytes primarily consist of mixtures of carbonate solvents such as ethylene
carbonate (EC), diethyl carbonate (DEC) or ethers such as dimethoxyethane (DME), or
tetraethylene glycol dimethyl ether (TEGDME).

Separator: polymer separators such as Solupor or Celgard, or fiber-based separators such as

Dreamweaver or glass fiber.

Cell Potential: 1.85 to 3.45 V

Advantage:
1) Low-cost and environmentally-friendly.
2) Slightly lower energy density and high efficiency.
3) Better safety characteristics.
4) These are high rate batteries and operation at lower temperature
Disadvantage:
1) Batteries are less powerful.
2) Anode graphite absorbs too little sodium.
3) Large ionic size Na+ which require more power to keep energy flowing.
4) It takes seven days to charge in case you forget to charge it.
5) Lower operating voltage.
6) Need high temperature for optimal work.

Applications:
1) Used in cellular phones and laptops.
2) In electric vehicles and power tools.
3) Sodium-ion batteries have shown great promise for large scale storage of renewable
energy.
4) Sodium-ion batteries are cheaper and last longer than cell currently used in gadgets.
5) These factors price, abundance and size, make sodium-ion batteries particularly
interesting for large scale grid storage application.

Solid state battery (Li-polymer battery)

Introduction to lithium polymer battery technology
The flexibility of dimension, the high energy density and the electrical data have led to a
diversity of cell design. The following designs are particularly interesting in market.
 Gel-polymer cell with improved cell cycle stability
 High energy cells with charging voltage of 4.35/4.4V
 High temperature cells for (intermittent) use up to 80˚C
 Low temperature cells that can be discharged at temperature down to 40˚ C

Working principle
 The principle of operation and construction of Li-polymer batteries are identical to those
of Li-ion batteries.
 These batteries operate on the principle of de-intercalation and intercalation of lithium
ions from positive electrode materials to negative electrode materials Electrode set:
 In Li-polymer batteries the electrode set comprises a carbon-based substance
(graphite+additives) pasted onto a metallic substrate.
 The cathode consists of three-dimensional, lithiated cobalt oxides or
nickel/manganese/cobalt (NMC) mixed oxides, also pasted into a metallic substrate.
During Discharging: During Charging:
At Anode At Anode
Li-C6 → Li+ + 6C + e- Li – MO2 → Li+ + e- + MO2
At Cathode At Cathode
Li+ + e- + MO2 → Li – MO2 Li+ + 6C + e- → Li-C6

Net Cell Reaction:

Li-C6 + MO2 → Li-MO2 + 6C

Applications
 Solid-state batteries are used in medical devices such as pacemakers, defibrillators, etc.
 A number of gardening tools and equipment such as a lawnmower, etc., make use of solid-
state batteries.
 Automobile industry employs solid-state batteries to power various electric vehicles.
 They are used in telecommunication equipment, instruments, portable radios and TVs, pagers
 They are used to operate laptop computers and mobile phones and aerospace application

Advantages of solid state battery

Solid-state batteries promise advantage given below.
(a) Greater energy density,
(b) Longer life
(c) Greater safety,
(d) All in a smaller size.
(e) Fast charging is possible.

Disadvantages of Solid-State Battery

1. The mass production and manufacturing of solid-state batteries are quite complex.
2. Research regarding solid-state batteries is still in progress and the perfect material for the
electrolyte with an ideal ionic conductivity is yet to be found.
Flow battery (Vanadium redox flow battery).
The fundamentals of an all-vanadium RFB
(a) In an all-vanadium RFB (VRFB) system, vanadyl sulphate in sulphuric acid
solution is employed as initial electrolyte at both sides. The same element at
different oxidation states can be converted to one another at the electrodes.
Figure shows a basic schematic of vanadium redox flow battery (VRFBs).

Electrode reactions
At the positive electrode, V(IV)/V(V) redox couple are generally VO2+ and VO2+:
VO2++H2O→VO2++ 2H++ e− (charging)
VO2++2H++e−→VO2++H2O (discharging)
E0 = + 1.00 V versus SHE
At the negative electrode, V(II)/V(III) redox couples are either the vanadium(II) ion or the
vanadium(III) ion:
V3++ e− →V2+ (charging)
2+ 3+ −
V →V + e (discharging)
0
E = − 0.26 V versus SHE
The standard open circuit potential of all-vanadium systems is 1.26 V, but the practical
open circuit potential depends on the operation temperature, the concentration of active species,
and the state of charge. Usually, sulphuric acid is employed as the supporting electrolyte, and
hydrogen ions maintain the current by passing through the membrane.
Due to relatively fast kinetics and high reversibility of these two vanadium redox
reactions, a high coulombic and voltage efficiency at a large current density can be expected.
A VRFB can be overcharged and over discharged within the limits of the capacity of
electrolytes, and it also eliminates the gassing issue during the rapidly charging cycles.

What are the advantages of redox flow batteries?

 Independently scalable performance and storage capacity.
 High efficiency (70 -90%)
 Long life (approximately 20 years) and unlimited number of cycles.
 Resistant to deep discharge, low self-discharge.
 Quick response.
 Electrolyte not flammable or explosive.
 No harmful emissions

What are the disadvantages of redox flow batteries?

 Low energy density
 Low charge/discharge rates.
 To achieve significant capacity, the electrolyte tanks have to be large enough.
 Due to their heavy weight heavy, suitable only for stationary applications.

Applications
Vanadium Redox Flow Batteries work with sustainable energy applications
 Including Utility/Micro-grid,
 Commercial & Industrial, Electric Vehicle charging,
 Telecommunications, Off-Grid Solutions,
 Solar, Wind and Residential.
 Fuel cells
Introduction
Definition:
“A fuel cell is a device that converts chemical energy of fuel into
electric current by direct oxidation of fuel at anode and reduction of
oxidant at cathode”.
Difference between conventional cell and fuel cell
1) Battery stores electricity produced elsewhere and supplies it whenever required. But, fuel
cell produces electricity on the spot.
2) In a fuel cell, the reactants (fuel and oxidant) are not part of cell, they are supplied from
outside. But, in a battery all reactants are integral parts of it.
3) Fuel cells do not store chemical energy but batteries do.
4) The products are continuously removed from a fuel cell, whereas in a battery the products
are not removed.
5) Batteries require recharging from external source of electric current but fuel cells produce
current on their own.
Limitations of fuel cells
 Fuels in the form of gases and oxygen need to be stored in tanks under high pressure.
 Presently fuel cells are bit more expensive than the conventional power generation
sources. Capital cost is also high.
 Electro catalysts used in anode and cathode contain costly noble metal-platinum.
 For continuous supply of electricity, fuel and oxidants to be supplied continuously.
Advantages of fuel cells
 Fuel cell can convert chemical energy of fuel into electricity with very high efficiency.
 Fuel cell converts a fuel to electrical energy with minimum emission of pollutants; hence,
it is ecofriendly.
 Space required for fuel cell is less.
 No moving parts and there is no wear and tear of cell parts.
Methanol-oxygen fuel cell
Methanol is an efficient electro active organic fuels at low temperatures. The advantages of
methanol are
i) It has low carbon content
ii) It has readily oxidizable OH group
iii) It has high solubility in aqueous electrolytes.
Construction
In methanol-oxygen fuel cell, methanol is used as the fuel and oxygen gas is used as an
oxidant. It consists of electrodes made of porous nickel sheets impregnated with electro-
catalysts. Pt/Ru catalyst is deposited on anode and platinum on cathode. Wet sulphuric acid is
used as an electrolyte. A solid ion exchange membrane (fluorinated sulphonic acid polymer)
which is good conductor for proton is used as a separator.
Methanol is circulated through the anode chamber. Pure oxygen is passed through the
cathode chamber and two chambers are separated by a sulphonic acid polymer membrane, placed
in the central compartment. This membrane allows conduction of protons between two
electrodes and also minimizes diffusion of methanol into the cathode. In the absence of the
membrane, methanol crosses over to the cathode compartment and undergoes oxidation there
itself.

Working
At anode : CH3OH + H2O CO2 + 6H+ + 6e-
At cathode : 3/2O2 + 6H+ + 6e- 3H2O
Over all reaction: CH3OH + 3/2O2 CO2 + 3H2O

Polymer electrolyte fuel cell

 It is relatively new and fast-growing technology.
 These cells operate at low temperature.
 Solid polymer membranes capable of H+ migration used.
 Teflon-based ion-exchanger membranes containing sulphonic acid group (-SO3H) are
frequently used.
 The cell is compact as the membrane can be very thin.
 Porous carbon electrodes impregnated with Pt. are used as electrode.
 H2 and O2 are normally used as fuel and oxidant, respectively.

The cell reactions are
At the anode (oxidation): H2→2H++2e-
At the cathode (reduction): 1/2O2+2H++2e-→H2O
The overall cell reaction:
H2+1/2O2→H2O
The membrane serves two important purposes
(a) Provides ionic migration
(b) Separates anodic and the cathodic compartment so that the species do not mixed.

What are the applications of PEM fuel cell

Proton-exchange membrane fuel cells (PEMFC), also known as polymer electrolyte membrane
(PEM) fuel cells, are a type of fuel cell being developed mainly for
 Transport applications
 Stationary fuel-cell applications
 Portable fuel-cell applications.

What are the advantages of PEFC?

The advantage of PEFC is
 its fast startup,
 flexibility in input fuel,
 compact design,
 lightweight,
 Low cost, and solidity of electrolyte.
 It can take pure hydrogen, methanol, as well as formic acid as input. It is ideal for
portable and motile as well as stationary applications.
 Solar Energy
Introduction
Solar radiation is believed to be the only realistic alternative to fossil fuel. It is a clean
and renewable source of energy available in abundance. As per an estimate, if solar energy
received by earth surface per day is converted into electrical energy, it is sufficient to meet the
energy requirements of whole world for 16 years. Solar photovoltaic energy doesn't emit
greenhouse gases that cause global warming in energy generation processes, making them the
cleanest, most viable solution to prevent environmental degradation.

Photovoltaic (PV) cells

Photovoltaic cells or solar cells are often referred to as semiconductor devices that
convert sunlight into direct current electricity.

Principle:
When electromagnetic radiation (sunlight) is incident normal to the plane of the solar cell, the
photons, which possess energy (photons carry certain amount of energy given by Plank’s
quantum equation, E = hc/λ, where h is Plank’s constant, c is the velocity of the light and λ is the
wavelength of the radiation) sufficient to overcome the barrier potential are absorbed and
electron-hole pairs are formed. Electrons are driven into the external circuit and used for various
appliances.

Construction:

 A typical silicon photovoltaic cell is composed of a thin wafer consisting of an ultra-thin

layer of phosphorous doped (n-type) silicon on top of boron doped (p-type) silicon.
Hence, a p-n junction formed between the two.
 A metallic grid on the top of n-type silicon forms one of the electrical contacts of the
diode.
  An antireflective layer (coating of silicon nitride or titanium dioxide) is coated between
the metallic grids to prevent the reflection of solar light.
 The cell’s other electrical contact is formed by a layer of silver metal at the back of p-
type semiconductor.
 The two metallic ends are electrically connected through the external circuit.
 A conventional solar cell structure is shown below:
Working:
 Electrical energy obtained from PV cell is directly proportional to area of cell exposed to
light radiation and intensity of light radiation which can eject electrons.
 When a photon from sunlight carrying energy E = hc/λ (which is enough to cross the
barrier potential) falls on the p-n diode through the antireflective layer, electrons are
ejected from p-type semiconductor creating an electron-hole pair.
 These ejected electrons move to n-side through p-n junction.
 Since, p-n junctions allows only one way movement of electrons, these electrons must
flow through the external circuit to recombine with holes present in p-side of
semiconductor.
 This movement of electrons from n-side to p-side through the external circuit generates
an electric current.

Disadvantages of photovoltaic systems

1. High startup cost
Each PV installation should be economically evaluated and compared to existing alternatives. At
present, the construction cost of photovoltaic systems is relatively high, but with the reduction of
photovoltaic system construction costs and the rise of traditional energy prices, photovoltaic
systems will have strong economic competitiveness.
2. Available solar radiation instability
For any solar system, weather changes will greatly affect the amount of electrical energy output.
Therefore, the system design needs to be adjusted according to changes in climate and location.
3. Have energy storage requirements
Some photovoltaic systems use batteries as energy storage devices. This increases the footprint,
cost and complexity of the system.
4. Efficiency needs to be improved
In order for PV systems to reflect cost-effectiveness, we need to use an efficient method to
distribute the energy generated during use. However, they are now often used to power
alternative inefficient appliances.
5. Lack of knowledge and skills
Photovoltaic technology is an emerging technology. The lack of relevant information limits the
development of its markets and technologies.
Advantages of photovoltaic systems
1. High reliability
Photovoltaic systems are still highly reliable even under harsh conditions. Photovoltaic arrays
ensure continuous, uninterrupted operation of critical power supplies.
2. Strong persistence
Most modules in a PV system have a warranty period of up to 25 years and remain operational
even after many years.
3. Low maintenance costs
Photovoltaic systems require only regular inspections and occasional repairs, which are
extremely low cost compared to conventional fuel systems.
4. Zero fuel consumption
Photovoltaic systems do not require fuel and can eliminate associated procurement, storage and
transportation costs.
5. Noise pollution is small
The photovoltaic system can operate quietly with minimal mechanical movement.
6. There is photovoltaic supervision
In order to improve energy efficiency, photovoltaic systems may need to add some modules.
7. Strong security
Photovoltaic systems do not require fuel and can be safely operated after proper design and
installation.
8. Strong independence
The reason for adopting this new technology in many residential areas is that photovoltaic
systems maintain the independence of energy production and are therefore unaffected by
utilities.

Application
 For producing electricity using solar power plants
 To provide electricity to satellites.
 In remote sensing techniques from space using satellites with objectives.
 To provide reliable weather monitoring and forecasting, there by monitoring the climatic
factors.