Unit-III-Energy Storage Devices

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Unit IIII Energy storage devices
ENERGY STORAGE DEVICES
1. Components of a battery
2. Working of a battery
3. Battery Characteristics
4. Modern batteries : Zinc-air battery, Lithium batteries
5. Reserve Batteries : Magnesium – water activated battery
6. Fuel Cells : Classification of fuel cells
i. H2-O2 Alkaline fuel cells
ii. Direct-methanol fuel cells (DMFCs) or CH3OH-O2 Polymer
electrolyte membrane fuel cells
iii. CO-O2 Solid oxide fuel cells (SOFC)
7. Oxygen Sensor
8. Super Capacitors
9. Ragone plot
1 Department of Science & Humanities (Chemistry) PESU

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Battery is an arrangement of two or more galvanic cells connected in a parallel or series to

increase voltage or Battery is an arrangement of two or more cells usually arranged in
parallel or series to produce necessary voltage or current or both.
The battery was the first practical source of electrical energy developed in man's search for
portable power sources. Although many other technologies have been developed for
supplying electrical power, the battery is the most widely used source of electrical power
when portability is the prime requisite.
Batteries are used in hearing aids, flash lights, clocks, emergency lighting, tape
recorders, toys, calculators, telephone systems, electric bells, space vehicles, military
applications etc.
Battery technology historically considered electrochemical, combines the activities of the
chemist, the chemical engineer, the material specialist, the electrical engineer, the
environmental engineer and instrumental analyst. The individual view points of all these,
cooperate to serve the diversified needs and desires of industries, as well as our daily lives in the
electronic and space age.
Important requirements of Battery components

➢ The electrode reaction must be rapid. For secondary batteries charging must be fast
➢ The two electrodes must have sufficiently different equilibrium half potentials, so that useful
cell voltage can be obtained.
➢ The active components of the cell should only react when the external circuit is closed. There
should be no self-discharge.
➢ The battery should have as large power and energy density as possible
➢ The cell components should be cheap and easily available. They should not be poisonous and
should be disposable without any environmental pollution
Components of a battery
The essential components of battery are as follows.
1. Anode or negative electrode:
It is a negative electrode at which oxidation of the species occur. It releases electrons to
the external circuit by undergoing oxidation during electrochemical reaction.
Example: Lithium metal in Li-MnO2 battery.
+ -
Li Li + e
Cadmium metal in nickel cadmium battery.
2+ -
Cd Cd + 2e

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2. Cathode or Positive electrode:

It is a positive electrode at which reduction of the species occur. It accepts electrons from
the external circuit and reduces active species.
Example: MnO2 is used as cathode in Li-MnO2 battery.
+ -
Li + MnO 2 + e LiMnO 2
3. Electrolyte:
It is an active mass in both the anode and cathode compartments. A solution of an acid, alkali or
salt having ionic conductivity is commonly used as electrolyte. Solid electrolytes with
appreciable ionic conductivity at the operating temperature of the cell are also used.
Example: KOH is used as an electrolyte in nickel cadmium battery.
H2SO4 is used as an electrolyte in lead acid battery.
4. Separator:
It separates the anode and cathode compartments to prevent internal short circuit. It is
permeable to the electrolyte and maintains desired ionic conductivity. It is electronically an
insulator but ionically conductor. The main function of a separator is to transport ions from the
anode compartment to cathode compartment and vice versa.
Example: Micro porous polypropylene or polyethylene, cellophane, nafion membrane
Apart from anode, cathode, electrolyte and separator, other components are
Container or battery housing:
Entire battery is enclosed with a insulating material like wood or paper or plastic to isolate
battery materials from external environment.
Current collector:
A conducting backbone of a electrode in a battery is current collector. It is made up of a
material with high electrical conductance and high surface area to accommodate more
amount of active species on its surface.
Example: Al and Cu current collectors in Li-ion battery
Nickel coated steel mesh in nickel-cadmium battery

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Working of a battery:
Discharging:
During discharge, a battery delivers power. Oxidation takes place at the anode and reduction
takes place at the cathode. The reaction is a spontaneous reaction. Chemical energy is converted
into electrical energy.
Charging:
During charging, reverse reactions take place. The reverse reactions are non-spontaneous
reactions. The battery is connected to an external dc power supply. Electrical energy is
converted in to chemical energy.
Based on working, two types of batteries:

Primary battery
• Electroactive material cannot be regenerated
• Discarded after electroactive species is consumed
• Galvanic cell
• Dry cell, Li-MnO2
Secondary battery
• Electroactive material can be regenerated
• Can be used several times
• Galvanic as well as electrolytic cell
• Storage battery
• Li-ion, Pb-acid, Ni-Cd

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Battery Characteristics
1. Voltage: The voltage available from a battery depends upon the EMF of the cell. The EMF of
the cell depends on change in free energy of overall cell reaction.
According Nernst equation,
2.303RT
Ecell = E o cell − logQ
nF
2.303RT [Products]
Ecell = E o cell − log
nF [Reactants]
E o cell = E o cathode − E o anode

Where Q is the reaction quotient. It is also evident from the equation, EMF of the cell and also the
voltage available from the battery is depending on standard electrode potential difference
between the cathode and anode, temperature and the extent of the cell reaction.
If the difference in the standard electrode potential is more, higher is the EMF of the cell.
As the temperature increases the EMF of the cell decreases.
As the value of Q increases, the EMF of the cell decreases.
To derive a maximum voltage from the cell
✓ The electrode potential difference between cathode and anode must be high
✓ Polarization and over potential must be minimum
✓ Internal resistance must be low
2. Current: It is the measure of the rate at which battery is discharging. To construct efficient
battery large quantity of active materials must be maintained for rapid electron transfer without
any excessive voltage penalty. More the electro active materials packed in the cell more is the
current generated.
It depends on conductivity of electrolyte. With increase in electrolyte concentration,
conductivity of electrolyte increases. The resistance decreases and hence current increases.
It also depends upon distance between the electrodes. By increasing the distance between the
electrodes, the resistance of the electrolyte increases and hence current increases.
3. Capacity :
The capacity is the charge or amount of electricity that may be obtained from the battery and is
given in ampere hours (Ah). Capacity depends on size of the battery and is given by Faraday’s
relation
wnF
C=
M
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where w is the mass and M is the molar mass of active material.

The amount of the active material actually consumed during discharge determines the capacity
of the battery. The capacity also depends on the discharge conditions. It is measured by finding
the time 't' taken for the battery to reach a minimum voltage for a fixed current discharge (i
amperes). The cell is said to be dead at minimum voltage.
A plot of time against voltage at a fixed current discharge is shown in the figure.
The length of the flat portion of the curve is a measure of the capacity of the battery; longer the
flat portion better is the capacity.
The capacity C = it. Where t is the time required by the battery during discharge of fixed
current i amperes to reach a value Emin. Flatter and longer the curve better is the capacity.
4. Power density
It is the power per unit weight of the battery. It is the ratio of the power available from a battery
to its mass (W/kg) or volume (W/L)
Power available from the battery
Power density =
Mass of the battery
i x Ecell
Power density =
W
Where W is mass of the battery, i and Ecell are current and EMF generated in the
cell.
Power density is expressed in Wkg-1

During discharge power density decreases.
5. Energy density
It is the ratio of energy available from the battery to its mass (or volume)
Energy available from the battery
Energy density =
Mass of the battery
i x Ecell
Energy density = xt
W
Where W is mass of the battery, i and Ecell are current and EMF generated in the cell, t is time.
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The unit of energy density is Whkg
A cell with a good energy density is preferred.
6. Energy efficiency:
When secondary batteries are used for energy storage on large scale, the energy efficiency
becomes important.
The energy efficiency of secondary battery is given by
Energy released on discharge
Percentage of Energy efficiency = x 100
Energy required for charging
• Higher the energy efficiency better is the battery
• Depends on efficiency of electrode reactions
7. Cycle life
Primary batteries are designed for single discharge, but a secondary battery is rechargeable.
The cycle life is the number of charge/discharge cycles that are possible before failure occurs.
Why batteries have limited cycle life?
Reasons for failure to achieve high cycle life is,
1. Corrosion at contact points.
2. Shedding of active material from the plates.[Loss of electro active materials from the electrode
due to rapid charging conditions]
3. Shorting between electrodes due to irregular crystal growth and change in morphology.
8. Shelf life
Shelf life is the maximum time for which a given battery can be stored without self-discharge or
corrosion or loss of performance.
Batteries need to be stored for longer time without self-discharge. Shelf life is affected by self
discharge. Self discharge occurs when there is reaction between the anode and cathode active
material or corrosion of current collectors. OR
The duration of storage under specified condition at the end of which a cell or a battery
retains the ability to give specified performance is called the shelf life.
Batteries need to be stored for longer time without self-discharge. Self discharge occurs
when there is reaction n between the anode and cathode active material or corrosion of current
collectors.
9. Electricity storage density
It is the amount of electricity per unit weight which the storer can hold. In other words, it is the
capacity per unit mass of the battery.
The weight of the battery includes, weight of electrodes, electrolyte, terminals, case and current
collectors. To get high electricity storage density, weight of all the elements should be minimum.

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For example, 7 g of lithium is required at anode to give 96500 C of charge where as for the same
charge 65 g of zinc is required.
10. Tolerance to service conditions
The battery has to be tolerant to different service conditions such as variation in temperature,
vibration and shock
Modern batteries
Zinc-air battery
Zinc-air battery is a type of metal-air batteries, which uses oxygen directly from the atmosphere
to produce electrochemical energy. Oxygen diffused into the cell and is used as the cathode
reactant. The air cathode catalytically promotes the reaction of oxygen with an alkaline
electrolyte and is not consumed or changed during discharge. As the cathode can be very
compact, high energy densities are achieved.
Construction:
Anode : Loose powdered zinc with an aqueous alkaline electrolyte and gelling agent (to
immobilize the composite and ensure adequate contact with zinc granules).
Cathode : Amorphous carbon (graphite) blended with MnO2 (catalyst) with a wet proofing agent
coated on nickel wire mesh support and an outer layer of air permeable Teflon layer. Air access holes on
the cathode provide pathway for O2 to enter the battery
Electrolyte : 30 % KOH
Separator : Polypropylene membrane soaked in electrolyte.
Working :
2+ -
Anode : Zn Zn + 2e
2+ -
Zn + 2OH ZnO + H2O
- -
Zn + 2OH ZnO + H2O + 2e
- -
Cathode : 1/2O2 + H2O + 2e 2OH
Ov e rall re action Z
: n + 1/2O2 ZnO
The cell produces an open circuit potential of

1.4 V.
Advantages :
1. High energy density (1000 Whr/kg) : Air does not contribute to the mass of the battery
2. Long shelf life : It can be kept sealed

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3. No ecological problems
4. Low cost
Disadvantages :
1. Limited power output
2. The battery is exposed to atmosphere, therefore CO2 may enter into the battery.
It reacts with KOH forms K2CO3 precipitate, which will reduce the efficiency of the battery.
Applications :
1.Used as power source in hearing aids
2.Used in various medical devices
3. Large zinc-air batteries are used in rail-road signaling
4. In voice transmitters
Lithium batteries
The reasons for the selection of lithium metal as anode is,
1. Lithium is light weight metal with good electrical conductivity.
2.It has very high negative standard electrode potential of -3.05 V. It can be coupled with other
electrodes with high standard electrode potential to get high voltage (about 4 V)
3. The electrochemical equivalence of lithium is high (7 g of Lithium can give 1F of charge)
Advantages :
1. High Voltage up to 4 V depending on the cathode material. This is because of the very negative
electrode potential of Li/Li+.
2. High energy density – Lightest metal
3. High tolerance to service conditions (-40 oC to 70 oC)
4. High electricity storage density
5. Flat discharge characteristics
6. Low self discharge rate
Disadvantages :
1. Safety concerns due to high reactivity of Lithium metal.
2. Poor cycle life – due to dendrite formation.
3. Transportation limit
Classification of Lithium batteries
Primary battery : It is not rechargeable. E.g. : Li-MnO2 battery
Secondary battery : It is rechargeable. E.g.: Li-ion battery
Pure lithium is highly reactive. It reacts vigorously with water to form lithium hydroxide and
hydrogen gas. Thus non-aqueous electrolytes are typically used and a sealed container rigidly
excludes moisture from the battery pack.

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Lithium – ion battery

A lithium battery is a member of a family of rechargeable battery types in which lithium ions
move from the negative electrode to positive electrode during discharge and back when
charging. Lithium ion batteries use an intercalated lithium compound as an electrode material,
compared to the metallic lithium used in a non-rechargeable lithium battery. The electrolyte
which allows for ionic movement, and the two electrodes are the constituent components of a
lithium ion cell.
Construction:
Anode : Lithiated -Carbon (Graphite) coated on copper current collector
Cathode: Lithiated transition metal oxide coated on aluminium current collector.
E.g. : Lithium cobalt oxide.
Electrolyte: The electrolyte is typically a mixture of organic carbonate solvents such as ethylene
carbonate or diethyl carbonate containing lithium salts like LiPF6, LiClO4
Separator: It is a very thin sheet of micro perforated polypropylene membrane.
Working :
During Charging :
At Anode : xLi+ + xe- + xC 6 xLiC6
At Cathode : LiCoO2 Li1-xCoO2 + xLi+ + xe-
LiCoO2 + xC 6 Li1-XCoO2 + xLiC6
During Discharging :
At Anode : xLiC6 xLi+ + xe - + xC 6
At Cathode : Li1-xCoO2 + xLi+ + xe- LiCoO2
Li1-XCoO2 + xLiC6 LiCoO2 + xC 6
Advantages :
1. Lighter than other rechargeable batteries for a given capacity.
2. Li-ion battery delivers a high open-circuit voltage 3.7 V
3. Low self-discharge rate
4. Do not suffer from battery memory effect
5. Good cycle life as the problem of dendrite formation is eliminated (at no point, neither
charging nor discharging, Lithium metal is formed)
Disadvantages :
1. Rising internal resistance with cycling and age
2. Safety concerns if overheated or overcharged

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Applications :
Reserve Batteries
A battery in which one of the key component is kept separated from the rest of the battery to
achieve long shelf life is called reserve battery. Usually the electrolyte is the component that is
isolated. When one of the key components of the cell is separated from the rest of the cell,
chemical reaction between the cell components (self discharge) is prevented and hence reserve
battery has unlimited shelf life.
Classification of Reserve Batteries
1. Water-activated batteries : Activation by fresh or sear water
2. Electrolyte-activated batteries : Activation by the complete electrolyte or with the electrolyte
solvent. The electrolyte solute is contained in or formed in the cell.
3. Gas-activated batteries : Activation by introducing a gas into the cell
4. Heat –activated batteries : A solid salt electrolyte is heated to molten condition and becomes
ionically conductive, thus activating the cell. These are known as thermal batteries.
Magnesium – water activated battery

Construction:
Anode (Negative Plate): Magnesium sheet.
Cathode (Positive Plate): Silver chloride sheets covered with silver on the surface by reduction
to make conducting electrode surface.

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Separators: Woven or nonwoven fabric, absorbent, nonconductive material is utilized for the
dual purpose of separating the electrodes and absorbing the electrolyte.
Electrolyte: water or sea water
Working :
Anode : Mg Mg2+ + 2e -
-
Cathode : 2AgCl + 2e 2Ag + 2Cl -
Overall reaction : Mg + 2AgCl MgCl2 + 2Ag
Advantages:
1. Reliable
2. Safe
3. Instantaneous activation
4. Long shelf life
5. Light weight as electrolyte need not be stored in the battery
Disadvantages:
1. High discharge after activation
2. Once activated must be replaced
Applications:
Sonobuoys, Electric torpedoes, Weather balloons, Air-sea rescue equipment, Pyrotechnic
devices, Marine markers and Emergency lights.
Fuel Cells
The conventional method of utilizing the chemical energy of a fuel involves several steps and can
be depicted as follows :
Chemical energy → Thermal energy → Mechanical energy → Electrical energy
Thermal energy liberated during the combustion of a fuel is used to convert water into steam.
the steam is used to drive turbine that drives the generator to produce electrical energy. There is
a loss of energy in every step and only a maximum of 40% energy of the fuel is converted into
electricity. But in galvanic cell chemical energy is directly converted into electrical energy and
the efficiency of conversion is very high.
A fuel cell is a galvanic cell which converts chemical energy of a fuel oxidant system directly into
electrical energy by means of redox reaction or electrochemical reactions.
A fuel cell consists of the following arrangement
Fuel Electrode Electrolyte Electrode Oxidant
Anode ∶ Fuel → Oxidation product + ne−
Cathode ∶ Oxidant + ne− → Reduction products

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Advantages :
1. High power efficiency. (Theoretical efficiency is 100%, but actually it is about 50 - 80% )
2. Eco-friendly - products of the overall reactions are not toxic.
3. Silent operation.
Disadvantages :
1.Cost of the power is high as a result of the cost of the electrodes.
2. Power output is moderate.
3. Fuels are in the form of gases and oxygen need to be stored in tanks under high pressure.
Applications:
1. Used as auxiliary power generators in space vehicles
2. They are used in vehicles
3. Large scale power generation
How is fuel cell different from a battery?
Battery Fuel cell
These are the energy storage devices These are energy conversion devices
Secondary batteries are rechargeable Fuel cells are not chargeable
The reactants and products form integral In fuel cells, there is a continuous supply of
part of the batteries fuel and oxidant
Products remain in the cell Products are continuously removed from
the cell
May pose pollution problem Eco friendly
Efficiency of a fuel cell

Thermodynamic efficiency is given by the ratio of work output to heat input
Work output is Gibb's free energy ; heat input is enthalpy change of the cell reaction
Gibb's free energy, ∆G - Measure of the electrical work done
Enthalpy change, ∆H- Measure of the heat released during the reaction
∆G
Efficiency η = × 100
∆H
Classification of fuel cells

Based on the type of an electrolyte used in the fuel cells can be classified as follows :
1. H2-O2 Alkaline fuel cells
2. Direct-methanol fuel cells (DMFCs) or CH3OH-O2 Polymer electrolyte membrane fuel cells
3. CO-O2 Solid oxide fuel cells
4. Phosphoric acid fuel cells
5. Carbonate fuel cells

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1. H2-O2 Alkaline fuel cells

Alkaline fuel cells use an aqueous solution of KOH as electrolyte due to the following reasons:
1.Oxygen reduction is more rapid in alkaline electrolytes
than in acid electrolytes
2.The use of non noble metal electro-catalyst is feasible.
Construction :
Anode : Porous carbon impregnated with Pt/Pd catalyst
Cathode : Porous carbon impregnated with Pt/Ag catalyst
Electrolyte : 30-45 % KOH(warm)
Fuel : Hydrogen gas
Oxidant : Oxygen gas
Working : At Anode : H + 2OH- 2H2O + 2e-

2
At Cathode : 1/2O2 + H 2O + 2e- 2OH-
Over all reaction :H2 + 1/2O2 H2O
Emf = 1.23 V
• H2 gas diffuses through anode, gets adsorbed on the electrode surface, reacts with OH- to form
water
• At cathode O2 diffuses through electrode, is adsorbed and reduced to OH-
• Product is water which dilutes the KOH
• Cell operates at 100 oC, so that water from KOH escapes as steam
•The water was used by astronauts for drinking on Apollo spacecraft
Advantages:
1. Operates at low temperature
2. Have minimum corrosion
3. Alkali is used as electrolyte hence non noble metal catalyst can be used
Disadvantages:
1. In this type of cell reactants must be free from CO2, because the alkali reacts with CO2 to form
carbonates which would block the pores of electrodes and reduce efficiency of the cells.
2. Having liquid electrolytes, introducing handling problems.

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2. Direct-methanol fuel cells (DMFCs) or CH3OH-O2 Polymer electrolyte membrane fuel

cells
Direct-methanol fuel cells or DMFCs are a subcategory of proton-exchange fuel cells in
which methanol is used as the fuel. Their main advantage is the ease of transport of methanol
and reasonably stable liquid at all environmental conditions.
Whilst the thermodynamic theoretical energy conversion efficiency of a DMFC is 97 %; the
currently achievable energy conversion efficiency for operational cells attains 30 % - 40 %.
Polymer membrane or proton exchange membrane is used as electrolyte. They are known as
proton exchange membrane fuel cells. They are low temperature fuel cells (60-90 oC), have low
weight and volume.
Construction:
Anode: Porous carbon electrode containing platinum
Cathode : Porous carbon electrode containing platinum
Fuel: Solution of CH3OH
Oxidant: Oxygen gas
Electrolyte: proton conducting polymer membrane
They use a polymer membrane as its electrolyte. This membrane is an electronic insulator but
an excellent conductor of H+ ions. E.g. : Nafion
Nafion: This polymer consists of fluorocarbon backbone (–CF2-CF2-) similar to teflon to which
sulphonic acid groups are attached. The protons on sulphonic acid group are free to migrate
through the hydrated membrane.
• For DMFC Nafion not suitable as it has high permeability for CH3OH, hence methanol crossover
happens
• Methanol crossover - CH3OH diffuses through the membrane to cathode without undergoing
oxidation at anode resulting in low performance
• New membranes are being used - Poly electrolyte membranes e.g., SPEEK - sulphonated
poly(ether ether ketone)
At Anode : CH3OH + H2O 6H+ + 6e- + CO2
At Cathode : 3/2O2 + 6H+ + 6e- 3H2O
Over all reaction :CH3OH + 3/2O2 2H2O + CO2

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Emf = 1.21V
• A aqueous solution of methanol is fed at the anode

• Common operating temperatures are in the range 60 - 90 °C
• Oxidation of methanol on a catalyst layer takes place to form carbon dioxide , protons and
electrons
• Protons (H+) are transported across the proton exchange membrane – to the cathode where
they react with oxygen to produce water
• Water is consumed at the anode and produced at the cathode
• Electrons are forced to travel through an external circuit from anode to cathode, providing
power to connected devices
• Water management is very important for Proton exchange membrane fuel cells
• Temperature has to be maintained constant (60-90 oC)
• Polymer membrane must remain hydrated to maintain H+ conductivity
• Water produced from the reaction must be removed from the cathode
• High temperatures
• may dehydrate the polymer so H+ conductivity cannot take place
• the polymer may degrade and crack resulting in short circuit
• Low temperatures
• will result in flooding of the cell thereby reducing efficiency of the cell
• a higher catalyst loading will be required
Advantages:
1. High energy density : Due to the low weight of the polymer.
2. Long life : Low temperature operation allows them to start quickly and results in less wear on
system components, resulting in better durability.
3. No free corrosive liquid in the cell

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Disadvantages:
1. Noble metal catalysts have to be used (Pt) and electrolyte is expensive so cell cost is high
2. CO , if present, poisons the Pt catalyst , hence pure reactants should be used
3. Management of carbon dioxide created at the anode and water management pose problems
Applications :
1. Used in military applications - since they have low noise and thermal signatures and no toxic
effluent.
3. CO-O2 Solid oxide fuel cells (SOFC)

Solid oxide fuel cells are a class of fuel cells characterized by the use of a solid oxide material as
the electrolyte. The electrolyte is a ceramic material yttria stabilized zirconia (YSZ) i.e. zirconium
oxide doped with yttrium oxide.
SOFCs use a solid oxide electrolyte to conduct negative oxygen ions from the cathode to the
anode. The electrochemical oxidation of the hydrogen, carbon monoxide or other organic
intermediates by oxygen ions thus occurs on the anode side.
This is high temperature fuel cell operates in between 650 - 1000 0C.
Construction:
Anode : Ni-ZrO2 or Co-ZrO2
Cathode : Porous Sr doped with LaMnO3
Fuel: CO
Oxidant : O2
Electrolyte : Solid nonporous metal oxide usually ZrO2 doped with Y2O3 which is commonly
called yttria stabilized zirconia (YSZ). When ZrO2 is doped with Y2O3, oxide ion (O2−) vacancies
are created.
O2− ions can move through the solid oxide membrane.
YSZ shows sufficient ionic conductivity, chemical stability and mechanical strength at high
temperatures.
Working :
At Anode : CO + O2- CO2 + 2e-
At Cathode : 1/2O2 + 2e- O2-
Over all reaction : CO + 1/2O2 CO2
• Oxygen is supplied at the cathode

• Oxygen reacts with the incoming electrons from the external circuit to form oxide ions(O2- )

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• O2− travel through the electrolyte which has oxide ion vacancies and reach the anode
• At the anode the O2− react with the CO to form CO2, liberating electrons
• Electrons flow from anode to cathode through the external circuit thereby generating power
Advantages:
1. No expensive catalyst required since works at a high temp.
2. CO can be used as a fuel - CO is not used in cells where Pt is used as catalyst as CO poisons the
catalyst or in cells which use alkali as electrolyte as CO will form CO2 which reacts with the
alkali and forms carbonates which reduce efficiency of the cell
3. Their high temperatures make them particularly efficient for Combined Heat and Power
(CHP) systems, as waste heat can be put to good use for heating and cooling.
Disadvantages:
1. Very slow start up as high temperature has to be reached.
2. High temperature enhances the corrosion of the components
3. Few materials can operate at high temperature and remains stable at high temperature
Oxygen Sensor
An Oxygen sensor or lambda sensor is an electronic device

that measures the proportion of O2 in the gas or liquid being
analyzed.
A gasoline engine burns gasoline in the presence of oxygen. It

turns out that there is a particular ratio of air and gasoline
that is "perfect," and that ratio is 14.7:1 (different fuels have
different perfect ratios - the ratio depends on the amount of
hydrogen and carbon found in a given amount of fuel). If
there is less air than this perfect ratio, then there will be fuel
left over after combustion. This is called a rich mixture. Rich
mixtures are bad because the unburned fuel creates
pollution. If there is more air than this perfect ratio, then
there is excess oxygen. This is called a lean mixture. A lean mixture tends to produce more
nitrogen-oxide pollutants, and, in some cases, it can cause poor performance and even engine
damage.
The oxygen sensor is positioned in the exhaust pipe and can detect rich and lean mixtures. The
Oxygen sensor detects the amount of oxygen in the exhaust gas and sends a signal to the engine
control unit which adjusts the air fuel mixture to the optimal level. Too much oxygen in the

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exhaust gas indicates a lean mixture, which can cause performance problems, including misfires.
Too little oxygen indicates a rich mixture, which wastes fuel and results in excess exhaust
emissions.
1. An O2 sensor is actually a galvanic cell. The zirconium dioxide or zirconia lambda sensor is
based on a solid-state electrochemical fuel cell. The sensor contains two platinum electrodes
with an electrolyte between them. ZrO2 doped with some Y2O3 is the electrolyte used. Due to
doping some oxygen vacancies are created in the crystal lattice. The mobility of O2- ions is
greatly enhanced and the conductivity is due to oxygen ions.
2. Cell voltage is given by
2.303RT P1
Ecell = log
4F P2
Where P1 and P2 are the partial pressure of O2 in reference air and exhaust gas respectively.
At Anode : 2O2- O2 + 4e-

At Cathode : O2 + 4e- 2O2-
3. Its two electrodes provide an output voltage corresponding to the quantity of oxygen in the
exhaust relative to that in the atmosphere.
4. An output voltage of 0.2 V represents a "lean mixture" of fuel and oxygen, where the amount
of oxygen entering the cylinder is sufficient to fully oxidize the carbon monoxide (CO), produced
in burning the air and fuel into carbon dioxide (CO2).
5. An output voltage of 0.8 V represents a "rich mixture", one which is high in unburned fuel and
low in remaining oxygen. The ideal set point is approximately 0.45 V. This is where the
quantities of air and fuel are in the optimum ratio, such that the exhaust output contains
minimal carbon monoxide.
1. O2 sensors operate at a minimum temperature of 360 oC.

2. The O2 sensor allows fuel management system to maintain the ideal air/fuel ratio across
various engine operation conditions.
3. Leaded gasoline contaminates the O2 sensors and catalytic convertors and results in failure of
the sensor. Other reason for failure could be presence of impurities in gasoline.

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Applications: Most common applications of O2 sensors are:
1. Measure exhaust gas concentrations of O2 in IC engines

2. Divers use to measure partial pressure of O2 in their breathing gas
3. Scientists use as probes to measure respiration or production of O2
4. In O2 analyzers used in medical applications such as anesthesia monitors, respirators etc.
Super Capacitors
The supercapacitor, also known as ultracapacitor or double-layer capacitor, differs from a
regular capacitor in that it has very high capacitance. A capacitor stores energy by means of a
static charge as opposed to an electrochemical reaction. Applying a voltage differential on the
positive and negative plates charges the capacitor. This is similar to the buildup of electrical
charge when walking on a carpet. Touching an object releases the energy through the finger.
A capacitor is a passive electronic component comprising a pair of conducting plates separated
by a dielectric. Capacitors store electrical energy as electrostatic charge with equal quantities of
positive and negative charges on opposite faces of the conducting plates resulting in a voltage
difference between the faces. When the two faces are connected by an external load, current
flows until complete charge balance is attained and the stored energy is released. The capacitor
can then be retrieved to its charged state by applying voltage. Since the charge is stored
physically without any chemical or phase changes, the process is highly reversible and the
charge–discharge cycle can be repeated over and over again, virtually without limit. The
quantity of charge (Q) stored in a capacitor is equal to the device voltage (V) times
proportionality constant (C) called capacitance,
i.e. Q = CV -------------- (1).
In Eq. (1), capacitance C is in Farad, charge Q is in Coulomb and the voltage V is in Volt. In
vacuum, the capacitance of such a capacitor is proportional to the area (A) of the conductors
divided by the thickness (d) of the dielectric separating them as shown in Fig. 1,
Fig. 1. Schematic sketch of a parallel-plate capacitor.
εo A
C= ---------------(2)
d

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In Eq. (2), proportionality constant ε0 = 8.9 × 10 −12 Fm−1 is the permittivity of the free space or
vacuum. With the dielectric material of relative permittivity (εr ), which increases the energy
stored in the device, the capacitance (C) is then expressed as:
εr εo A
C= --------------(3)
d
On substituting Eq. (3) in Eq. (1), we get,
εr εo A
Q= V ---------------(4)
d
Fig. 2. A dielectric medium showing the orientation of charged particles creating polarization
effects.
Electrical double-layer capacitor:
Fig. 3. Schematic sketches for a) Electrostatic, b) Electrolytic and c) Electrochemical

capacitors

2020
Fig. 4. Schematic sketch of an electrical double-layer capacitor
Electrical double-layer capacitor: It has long been accepted that an electrical double-layer
exists at the electrode/electrolyte interface that governs adsorption phenomena and influences
charge transfer reaction rates. As shown in (Fig.3c), the electrical double-layer stretches to
about a few A0 and stores electrostatic energy like a capacitor. It is noteworthy that the
existence of the electrical double-layer has always been inferred from indirect observations of
related properties and quantities, but never directly probed. It was realized only recently that
the energy stored per unit surface area is significant and becomes technologically attractive with
the introduction of materials with high active-surface-areas, such as activated carbons. In the
electrical double-layer, solvated ions are attracted to the solid surface by an equal but opposite
charge in the solid as shown in Fig. 4. These two parallel regions of charge form the source of the
term electrical double-layer where the charge separation as measured in molecular dimensions
is less than 10−9 m. As the surface area of activated carbon is nearly 1000 m2 g−1 of material, this
creates a capacitor cell with very high specific capacitance of nearly 105 Fkg−1 and the
possibility of realizing devices rated at many thousands of Farad. Owing to their appreciably
high capacitance, these capacitors are also referred to as supercapacitors or ultracapacitors.
Electrical-double layer capacitors (EDLCs):
These capacitors rely on carbon-based structures utilizing non-faradaic electrostatic charging of
the electrical double-layer formed at the electrode–electrolyte interface and are hence termed as
electrical-double-layer capacitors.
EDLCs store electrical energy at the electrolyte/carbon interface through reversible ion
adsorption onto the carbon surface, thus charging the electrical double-layer through a non-
faradaic contribution between an electronic conductor, namely the carbon, and a liquid ionic-
2020
conductor, namely the electrolyte. The few nano-meter thick electrical double-layers at the
phase boundary between the electrode and electrolyte can be referred to as a nano-dielectric
similar to a parallel-plate capacitor wherein the current collector of each electrode contacts
high-surface-area-conductive carbon impregnated with an electrolyte. At the negative electrode,
the negative charges received during charge by an external source are balanced by the positive
charges of the electrolyte cations that accumulate on the surface and within the pores of the
carbon particles. The counter electrode charges itself positively against the surrounding
solution.
Because of the formation of the electrical double-layer at each electrode/electrolyte interface, a
complete cell is formed by two capacitors in series and the overall capacitance (CT) is expressed
as: 1 1 1 --------------------------(7)
= +
CT C+ C−
In Eq. (7), C+ is the capacitance of cathode/electrolyte interface and C− is the capacitance of
anode/electrolyte interface. In an ideal electrical-double-layer capacitor, only charge separation
takes place at the electrode and there are no oxidation or reduction reactions. Accordingly,
charge (Q) stored in such a capacitor is related to its capacitance (C) and voltage (V) as: Q = CV.
Consequently, the capacitance is voltage independent but does depend on electrode surface
area, the double-layer thickness and dielectric constant of the electrolyte. Traditionally,
activated carbons have been used in EDLCs. But conducting carbons with graphitic structure
also include template and carbide-derived carbons, nanotubes, nanohorns, onions (multi shell
fullerenes), polyhedral particles, carbon blacks and graphene.
Electrochemical capacitors have limited energy density but are known to exhibit high power
densities. Accordingly, electrochemical capacitors cannot replace batteries but can complement
them in many applications. Applications that can benefit from electrochemical capacitors include
medical, such as X-ray and MRI (magnetic-resonance imaging), spot and contact welding, audio-
line stiffening, actuators, large electric motor starting and power quality such as initial pulse
power for UPS systems.
Advantages:
1. Long life, can be cycled millions of time
2. Low cost per cycle and safe
3. Rapid charging – super capacitors charge in seconds
4. Extremely low internal resistance and extremely low heating rates
Disadvantages:
1. High self discharge - the rate is considerably higher than that of an electrochemical battery.
2. Cells have low voltages - serial connections are needed to obtain higher voltages.
3. Low energy density

2020
Applications of electrochemical capacitors

The major applications of electrochemical capacitors appear to be in high-pulse power and
short-term power hold. Some applications of electrochemical capacitors are discussed below.
1. Memory back-up
Many appliances now incorporate digital components with memory where even a very brief
interruption in the power supply could cause the loss of stored information. In such applications,
the
capacitor can act as a back-up supply for short periods. Batteries are the alternative to the
capacitors for these applications but batteries have a limited lifetime, and therefore need to be
replaced regularly. Electrochemical capacitors are a preferred choice as back-up power supply
due to their long lifetime.
2. Electric and hybrid electric vehicles
Battery-powered electric vehicles have the limitations of low power-density, limited
charge/discharge cycles, high-temperature dependence, and long charging-time.
Electrochemical capacitors are bereft of these limitations albeit they are faced with other
limitations such as low energy-density and high costs. Peak-load requirements that result from
accelerating or climbing up-hills could be met by the high-power device, namely the
electrochemical capacitors bank. An electrochemical capacitor is presently the power supply in
hybrid cars for start/stop application. When a hybrid vehicle stops, its internal combustion
engine (ICE) shuts down which is restarted by the electrical system powered by an
electrochemical capacitor that is recharged when the ICE resumes powering the vehicle. This
helps reducing fuel consumption. Electrochemical capacitors are ideally suited for city-transit
buses with stop-and-go driving, in trash trucks that can experience as many as a thousand
start/stop cycles during a day, and in delivery vans that operate on similar drive cycles. The
primary challenges for any energy storage unit used in heavy duty hybrid vehicles are the long
cycle-life and the need to dissipate the heat generated due to charge/discharge losses.
Electrochemical capacitors are highly efficient and have limited heat dissipation owing to their
low-energy content.
3. Power quality:
Static-synchronous-compensator system injects or absorbs power from a distribution line to
compensate for any voltage fluctuations. Such a system requires a DC energy storage device of
some sort from which energy could be drawn or stored. Since the majority of voltage
perturbations on the distribution bus are short-lived, usually not lasting more than 10 cycles,
electrochemical capacitors are an attractive option for energy storage and delivery to improve
the power quality.

2020
4. Battery improvement
Batteries are being used widely in the portable power appliances, such as UPS, laptops, and
mobile phones. Many such devices draw high-power pulsed currents which result in the
reduction of battery performance. Batteries in parallel with electrochemical capacitors could be
an effective alternative for these applications.
5. Portable power supplies
Most devices presently using battery power supplies have long recharge time and need to be
charged overnight. These need to be replaced with the electrochemical capacitors that can be
quickly charged and discharged. Indeed, for any portable electronic equipment with moderate
energy demands, electrochemical capacitors are ideally suited as rechargeable stand-alone
power sources.
6. Renewable energy applications
In solar photovoltaic applications, batteries need to be replaced every 1–3 years because of
continuous cycling that has a detrimental effect on batteries. But electrochemical capacitors can
be charged and discharged quickly for large number of cycles, and need to be replaced every 20
years only, which is similar to the life-span of the photovoltaic panels. Life-cycle costs are
therefore reduced by eliminating frequent maintenance requirements. Energy efficiency is
always of primary concern in renewable power generation. In this regard electrochemical
capacitors are attractive as they exhibit much higher charging efficiency than batteries.
7. Micro-scale energy scavenging systems
Products and systems can be designed around supercapacitor technology for efficient energy
storage and its retrieval later. The concept is to generate electrical energy at anytime from see-
saw,
swing, health-club equipment, exercising equipment, etc., with little effort and its retrieval on
demand.
Technology challenges
For many applications, relatively higher cost of electrochemical capacitors is currently the
primary reason for not being the energy storage technology of choice. Despite their high-level of
performance, electrochemical capacitors are simply too expensive to compete against the other
available approaches. For some applications, potential users find electrochemical capacitors to
be attractive but find their energy density to be too low. Hence increasing energy density and
lowering cost are the primary challenges facing electrochemical capacitor developers.

2020
Ragone plot
A Ragone plot is a plot used for performance comparison of various energy-storing devices. On
such a plot the values of energy density (in Whr/kg) are plotted versus power density (in W/kg).
Both axes are logarithmic, which allows comparing performance of very different devices (for
example, extremely high and extremely low power). Conceptually, the vertical axis describes
how much energy is available, while the horizontal axis shows how quickly that energy can be
delivered, otherwise known as power, per unit mass.
• Fuel cells have high energy density as the electroactive species can be continuously supplied
but the power density is low due to slow kinetics of redox reactions at electrodes
• Battery systems offer moderate energy density and power density.
• Ultracapacitors (supercapacitors) can deliver very high power density as they can discharge a
large amount of charge quickly (because no redox reaction is involved) but energy density is
very limited because the charge cannot be stored for a long time

2020
References :
1. Engineering Chemistry, by Nityananda Shetty and R V Gadag, Edn 3rd 2014.
2. https://www.matsusada.com/column/secondary-battery.html
3. Ding, Y. et al. Electrochem. Energ. Rev. 2, 1–28 (2019).
4. Vaghari et al. Sustainable Chemical Processes 2013,1:16
5. https://www.doitpoms.ac.uk/tlplib/fuel-cells/high_temp_sofc.php
6. https://en.wikipedia.org/wiki/Oxygen_sensor
7. B.E. Conway, Electrochemical Supercapacitors: Scientific Fundamentals and Technological
Applications, Kluwer-Plenum, New York, 1999.
8. Shukla, a. K., Banerjee, a., Ravikumar, M. K. & Jalajakshi, a. Electrochemical capacitors:
Technical challenges and prognosis for future markets. Electrochim. Acta 84, 165–173
(2012).
9. Gonzalez, A., Goikolea, E., Barrena, J. A. & Mysyk, R. Review on supercapacitors: Technologies
and materials. Renew. Sustain. Energy Rev. 58, 1189–1206 (2016).
10. https://www.electronics-notes.com/articles/electronic_components/battery-
echnology/primer- basics.php
11. http://www.emc2.cornell.edu/content/view/battery-anodes.html
12. https://batteryuniversity.com/learn/archive/understanding_lithium_ion
13. https://www.sciencedirect.com/topics/engineering/electric-double-layer-capacitor
14. https://www.degruyter.com/view/journals/psr/2/8/article-20170018.xml?language=en
15. https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7142913/
16. https://www.semanticscholar.org/paper/Education-on-vehicle-electrification%3A-Battery-
Fuel-Moura-Siegel/7e83f03396b55f2a894461480dda7e9c154f5721/figure/0

Unit-III-Energy Storage Devices

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2020

Unit IIII Energy storage devices

ENERGY STORAGE DEVICES

4. Modern batteries : Zinc-air battery, Lithium batteries

5. Reserve Batteries : Magnesium – water activated battery

6. Fuel Cells : Classification of fuel cells

i. H2-O2 Alkaline fuel cells

ii. Direct-methanol fuel cells (DMFCs) or CH3OH-O2 Polymer

electrolyte membrane fuel cells

iii. CO-O2 Solid oxide fuel cells (SOFC)

1 Department of Science & Humanities (Chemistry) PESU

Unit IIII Energy storage devices

Battery is an arrangement of two or more galvanic cells connected in a parallel or series to

Important requirements of Battery components

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Unit IIII Energy storage devices

2. Cathode or Positive electrode:

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Unit IIII Energy storage devices

Based on working, two types of batteries:

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Unit IIII Energy storage devices

E o cell = E o cathode − E o anode

Unit IIII Energy storage devices

where w is the mass and M is the molar mass of active material.

Power density is expressed in Wkg-1

Unit IIII Energy storage devices

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Unit IIII Energy storage devices

The cell produces an open circuit potential of

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Unit IIII Energy storage devices

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Unit IIII Energy storage devices

Lithium – ion battery

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Unit IIII Energy storage devices

Magnesium – water activated battery

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Unit IIII Energy storage devices

Overall reaction : Mg + 2AgCl MgCl2 + 2Ag

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Unit IIII Energy storage devices

Efficiency of a fuel cell

Classification of fuel cells

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Unit IIII Energy storage devices

1. H2-O2 Alkaline fuel cells

Working : At Anode : H + 2OH- 2H2O + 2e-

At Cathode : 1/2O2 + H 2O + 2e- 2OH-

Over all reaction :H2 + 1/2O2 H2O

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Unit IIII Energy storage devices

2. Direct-methanol fuel cells (DMFCs) or CH3OH-O2 Polymer electrolyte membrane fuel

At Anode : CH3OH + H2O 6H+ + 6e- + CO2

At Cathode : 3/2O2 + 6H+ + 6e- 3H2O

Over all reaction :CH3OH + 3/2O2 2H2O + CO2

15 Department of Science & Humanities (Chemistry) PESU