MODULE-2
Syllabus:
[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.]
Battery: A battery is a compact device consisting of two or more cells connected in series or
parallel. It stores chemical energy in the form of active materials and on demand converts it into
electrical energy through redox reactions.
Components of battery: The basic unit in battery is electrochemical cell. It consists of four major
components.
1. Anode: electrode undergoes oxidation by releasing the electrons to the external circuit.
2. Cathode: the electrode undergoes reduction by accepting electrons from the external circuit.
3. Electrolyte: it is present in both cathode and anode compartments, the solution of acid, alkali
and high conductivity ionic salts are commonly used as electrolytes.
4. Separator: it is used to avoid the internal short circuiting and also helps to transfer the ions
from anode to cathode or vice versa. Usually separators are organic polymers. Ex: cellulose,
polyolefin and nafion membranes.
Classification: Batteries are classified into three types
1) Primary batteries: In theses batteries, the chemical reactions are not reversible. So these
are not rechargeable. Ex:Zn-MnO2, Li-MnO2 batteries.
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2) Secondarybatteries: In these batteries, the chemical reactions are reversible. So these
are rechargeable. Charging and discharging can be done many times before their failure.
Ex. Lead-acid, Ni-Cd batteries, Lithium ion battery.
3) Reserve batteries: In these batteries, one of the components is stored outside the battery
and incorporated into the battery whenever energy required. Usually electrolyte is stored
separately. These are used for long term storage.
Ex. Ag-MnO2
Lithium-Polymer battery:
Lithium polymer batteries work on the principle of intercalation and de-intercalation of lithium
ions between positive and negative electrode materials with polymer electrolyte instead of a liquid
electrolyte.
Construction:
Anode: Lithium incorporated graphite layer with polyvinylidene fluoride (PVDF) as the binder
coated on copper current collector.
Cathode: Lithium incorporated transition metal oxide like LiCoO2 with conductive material and
binder, coated on aluminium current collector.
Electrolyte: Solid polymer electrolyte (Polyacrylonitrile, PMMA) gelled with lithium salt
(LiPF6).
Separator: Micro porous polypropylene film.
Battery Representation: LixC6 / Li+. C / LiPF6 in PAN / LiCoO2
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Working:
➢ During discharging, Li+ ions generate at anode by oxidation diffuse to cathode, convert into
atoms and insert into the layers of metal oxide.
➢ During charging, Li+ ions generate at cathode diffuse to anode, convert into atoms and insert
into the layers of graphite.
➢ Thus in lithium ion battery, the cell reaction is merely the transfer of Li+ ions between the
electrodes through polymer electrolyte.
➢ The movement of free electrons from anode to cathode via external circuit creates a charge
at the positive current collector (cathode). The electrical current then flows through a device
being powered (cell phone, computer, etc.) to the negative current collector (anode).
➢ Each cell produces a potential of 3.6 – 3.7 v.
Advantages: The main advantages of Li-Po batteries are that they have high energy density,
high voltage, greater life span (300-500 cycles), less weight, more resistance to overcharge and
fast charging rate and can be made to almost any size or shape. They can be banged around,
punctured, dropped or run over with a car and still not explode, making them more resistant to
physical trauma than most batteries.
Applications: Li-polymer batteries are used in cameras, calculators, pacemakers,
telecommunication equipments, portable radios and TVs, laptops, computers, mobile phones and
aerospace applications.
Sodium-ion battery (SIB):
Sodium-ion battery (SIB) is a type of rechargeable battery analogous to the lithium-ion battery
(LIB), but uses sodium ions (Na+) as the charge carriers. Its working principle and cell
constructions are almost identical with those of commercially well-known lithium-ion battery
types. SIBs are currently evolving as a viable substitute for LIBs because of the abundant
availability and reasonable cost of sodium.
In SIBs, graphite electrodes cannot be used due to the bigger ionic radius of sodium ions compared
with that of lithium ions. Hence, suitable anode must be used for better performance. Usually, HC
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electrodes are being used for that purpose.
Construction:
Anode: Sodium intercalated disordered carbon material consisting of amorphous structure (hard
carbon) with polyvinylidene fluoride (PVDF) as the binder coated on aluminium current
collector.
Cathode: Sodium incorporated transition metal oxide like NaMnO2 with conductive material and
binder, coated on aluminium current collector.
Electrolyte: Non-aqueous/aqueous solvents (ethylene carbonate, propylene carbonate) with
sodium salt (NaPF6).
Separator: Fiber-based separators such as glass fiber.
Battery Representation: NaxC6 / Na+. C / NaPF6 in PC/EC / NaMnO2
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Working
➢ During discharging, Na+ ions generate at anode by oxidation and diffuse to cathode, where
they convert into atoms and insert into the layers of metal oxide.
➢ During charging, Na+ ions generate at cathode and diffuse to anode, where they convert into
atoms and insert into the layers of hard carbon.
➢ Thus, in sodium ion battery, the cell reaction is merely the transfer of Na+ ions between the
electrodes through the electrolyte.
➢ The movement of free electrons from anode to cathode via external circuit creates a charge
at the positive current collector (cathode). The electrical current then flows through a device
being powered (cell phone, computer, etc.) to the negative current collector (anode).
➢ Each cell produces a potential of 1.85 – 3.45 v.
Advantages:
SIBs have the advantage of high stability, relatively high density with up to 240 Wh/kg, long life
span of 10–15 years, high efficiency (75%–90%), high natural abundance of sodium, low cost, fast
recharging.
Applications: They can be used in cellular phones, laptops, electric vehicles and power tools.
Redox flow battery:
A redox flow battery is an electrochemical energy storage device that converts chemical energy
into electrical energy through reversible oxidation and reduction of working fluids. The oxidation
and reduction reactions happen between two electrolytes, rather than between electrolyte and
electrode inside the flow battery cell. Therefore, there is no electro-deposition or loss of electro-
active substances. Also, electrolytes are stored in external storage tanks and are circulated through
the cell. Conventional redox flow batteries have two divided electrolytereservoirs, catholyte and
anolyte that are separated by a membrane, which permits ions to pass through it. Among various
kinds of redox flow batteries (RFBs), the Vanadium Redox Flow Battery (VRB) was the first one
introduced into commercial energy storage applications by Sumitomo Electric Industries in 1996.
Vanadium redox flow battery (VRB)
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Vanadium redox flow battery is a type of rechargeable flow battery. It employs vanadium ions
as charge carriers.
Construction:
Electrodes: Both the electrodes are made of carbon felt with large surface area, high electrical
conductivity and high chemical stability.
Electrolyte: Both electrolytes are vanadium-based. The electrolyte in cathode compartment
contains VO2+ and VO2+ ions, while the electrolyte in anode compartment consists of V3+ and V2+
ions. The electrolytes can be prepared by dissolving vanadium pentoxide (V2O5) in H2SO4.
Membrane: Hydrogen permeable polymer membrane like perfluorinated sulfonic acid (Nafion)
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Cell reactions:
Anode: V2+ ↔ V3+ + e−
Cathode: VO2+ + 2H+ + e− ↔ VO2+ + H2O
Overall reaction: V2+ + VO2++2H+↔VO2++V3++H2O
Working:
➢ Circulate the electrolytes in both the external storage tanks through the cell by a pumping
loop, refreshing active ions to the positive and negative half-cells.
➢ During discharging, V2+ is oxidized to V3+ in the negative half-cell and an electron is
released to do work in the external circuit. In the positive half-cell, V5+ in the form of VO2+
accepts an electron from external circuit and reduced to V4+ in the form of VO2+.H+ ions
are transported through the membrane from anode to cathode and maintain electrical
neutrality.
➢ During charging, the cell is continuously charged until it reaches fully charged state (2V),
confirmed by the color change of electrolytes. Vanadium electrolyte color changes from
green (V3+) to purple (V2+ ) at anode and blue VO2+ (V4+) to yellow VO2+ (V5+) at cathode.
H+ ions are transported through the membrane from cathode to anode.
➢ The standard cell voltage of VRB is 1.4 to 1.6 V.
At a given temperature, pH value and given concentrations of vanadium species, the cell voltage
can be calculated based on the Nernst equation:
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RT [VO2+ ][V 3+ ]
E = 1.26 − ln
F [VO2 + ].[H + ]2.[V 2+ ]
where R, T and F are the universal gas constant, absolute temperature and Faraday constant,
respectively.
Advantages:
✓ They require low maintenance
✓ High energy efficiency
✓ Wide operating temperature range including passive cooling
✓ Long charge/discharge cycle lives (15,000-20,000 cycles)
✓ Long shelf-life
✓ Independent of weather and temperature fluctuations
✓ Eco-friendly and recyclable
✓ High level of safety, non-flammable, non-explosive
Applications: Battery can be used in utility-scale energy storage projects, micro grids, grid
smoothing, backup power and in remote and off-grid power applications.
FUEL CELL:
A device that converts chemical energy of a fuel into electrical energy by the direct oxidation of
fuel and reduction of oxidant.
Here, Fuel is H2, CH3OH, natural gas, etc. Oxidant is air or O2.
Fuel cell can be represented as, Fuel/Anode/Electrolyte/Cathode/Oxidant
Reaction: Anode: Fuel → oxidized product + ne-
Cathode: oxidant + ne- → reduced product
Advantages of fuel cell:
1. Fuel cells have high energy efficiency (97%).
2. They are eco-friendly, minimum emission of pollutants.
3. They provide direct current for long period of time.
4. They do not require recharging.
5. They require less space.
6. Fuels used are not expensive,
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Limitations of Fuel cell: Power output is moderate, Electrodes are costly and fuels are to be stored
in tanks under high pressure.
Classification of fuel cells: Classification is based on the type of electrolyte used in the cell and
the temperature at which the cell operates.
1. Low temperature fuel cell: They operate below 100oC.
Ex. a) Acid-fuel cell: methanol – O2 fuel cell.
Fuel: methanol
Oxidant: O2
Electrolyte: H2SO4
Electrode: Both are made of porous carbon
b) Alkaline fuel cell: H2-O2 fuel cell
Fuel: H2
Oxidant: O2
Electrolyte: KOH
Electrode: made of platinum.
2. Medium temperature fuel cell: They operate at 100 oC to 600 oC.
Ex. Phosphoric acid fuel cell (PAFC), operates at 200 oC
Fuel: H2 / LPG / CNG
Oxidant: O2
Electrolyte: Orthophosphoric acid
Electrode: Both are made of platinum
3. High temperature fuel cell: They operate at 600 oC to 1000 oC.
Ex. a) Molten carbonate fuel cell (MCFC), operates at 600 oC
Fuel: H2 / CNG
Oxidant: O2
Electrolyte: molten carbonate- Li2CO3 or K2CO3 with the base of LiAlO2
Electrode: Anode:- Nickel with chromium, Cathode: NiO-Cobalt.
b) Solid-oxide fuel cell (SOFC), operates at 900 oC.
Fuel: H2 / H2+CO / CNG
Oxidant: pure O2
Electrolyte: Solid metal oxide
Electrode: Ni-ZrO2, Cathode: Sr doped LaMnO3.
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Methanol oxygen fuel cell with H2SO4 as electrolyte:
It consists of two porous carbon electrodes. Anode is coated with platinum catalyst and cathode
i s with silver catalyst. The electrolyte is an aqueous solution of H2SO4. Methanol is
continuously supplied at the anode and oxygen is supplied at the cathode. Methanol adsorbed
on anode electrode surface and undergoes oxidation giving CO2 and H+ ions. Electrons release
at anode, move externally to cathode. H+ ions diffuse through the electrolyte and reacts with
oxygen at cathode to produce water. A membrane is placed adjacent to cathode to prevent the
diffusion of methanol to cathode or else methanol diffuses to cathode and undergoes oxidation
itself.
Reactions:
Anode: CH3OH + H2O → CO2 + 6H+ + 6e-
Cathode: 3/2O2 + 6H+ + 6e- → 3H2O
Overall: CH3OH + 3/2O2 → CO2 + H2O
Applications: Methanol-O2 fuel cell is used in military applications and in large scale power
production.
Note: 1. An advantage of acid electrolyte is that CO2 can be easily removed.
2. Ecell is 1.21 v.
3. KOH cannot be used as it reacts with CO2 to form K2CO.
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Polymer electrolyte membrane fuel cell
Polymer electrolyte membrane fuel cells convert the chemical energy stored in hydrogen fuel directly and
efficiently to electrical energy. They are developed mainly for transport applications, as well as
for stationary fuel-cell applications.
They employ a polymer membrane with acid side groups to conduct protons from the anode to cathode.
Water management in the fuel cell is critical for PEM fuel cell operation. Sufficient water must be absorbed
into the membrane to ionize the acid groups.
Construction:
Fuel: Pure hydrogen, methanol, ethanol, etc.
Oxidant: Pure air or O2
Electrodes: Both the electrodes are carbon based, coated with platinum catalyst
Electrolyte: Proton exchange membrane is used like Perfluorinated sulfonic acid (Nafion)
Cell representation:- H2. H+ /anode / PEM / cathode / O2
Cell reactions:
Anode: H2 → 2 H+ + 2e-
Cathode: ½O2 + 2H+ + 2e- → H2O
Overall: H2 + ½O2 → H2O
Working:
At anode, platinum catalyst causes hydrogen molecule to split into positively charged hydrogen ions
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(protons) and electrons. Electrons travel through the external circuit and go to cathode generating the
electrical output of cell. Protons diffuse through the PEM under an electrochemical gradient to the cathode.
Oxygen molecules adsorb at the cathode, are reduced and react with protons and electrons to produce water.
The product water is absorbed into the PEM or flows out.
Advantages: They have high energy efficiency and environmentally friendly
Applications: They can be used as power sources in vehicles, portable and stationary
applications.
SOLAR ENERGY
Photovoltaic cell: Photovoltaic cell or Solar cell is a semiconductor device which converts solar
energy into electrical energy.
Solar cells harness the energy from the sun and transform this into electricity which can be used
in residential and commercial sectors.
Construction and working of photovoltaic cell
Photovoltaic cell is made of semiconductors which have the capacity to absorb light. When n- type
and p-type semiconductor are bought together, a semiconductor diode is formed. The
semiconductor diode separates and collects the charge carriers and conducts electrical energy
preferentially in a specific direction.
A typical silicon photovoltaic cell is composed of a thin poly crystalline silicon wafer. It consists
of an ultra-thin layer of phosphorus doped (n-type) silicon on top of boron doped (p-type) silicon
to form a p-n junction diode. It has two electrical contacts, one of which is in the form of metallic
grid and the other is a layer of noble metal like silver on the back of the solar cell. Light
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radiations are allowed to fall perpendicular on the semiconductor between
the grid lines. An antireflective layer between the grid lines increases the
amount of light transmitted to thesemiconductor.
When sun light falls on the solar panel, the plate absorbs it and reaches the
p-n junction. The photons present in sun radiation possess sufficient energy
(E= hγ) to overcome the barrier potential, generates electron – hole pairs and
causes the electrons drifted to and collected at the n-type end and holes at
the p-type end. When these two ends are electrically connected through a
conductor, electricity generates.
Advantages of PV cell:
1. Electricity can be provided to individual families located in remote areas like
mountains.
2. No emissions, no combustion or radioactive residues for disposal.
3. Does not contribute to global warming or pollution.
4. Low operating cost and high reliability.
5. No moving parts and so no wear and tear.
6. No recharging is required.
7. They do not corrode.
Disadvantages of PV cell:
1. Sunlight is relatively low density energy.
2. High installation cost.
3. Energy can be produced only during daytime.
