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UNIT III : ENERGY STORAGE DEVICES

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• Classification - primary, secondary and reserve batteries. Characteristics - cell

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potential, current, capacity, electricity storage density, energy efficiency, cycle life
and shelf life.

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Info Guru

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The fragrance of flowers spreads only in the direction of the wind. But the goodness of
a person spreads in all directions.

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Chanakya
“Batteries are storehouse of electrical energy on demand” They provide well contained

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energy conversion devices which greatly contributed to the needs of mankind. Zero
emission vehicles of future will be battery powered only. Many non-polluting energy
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conversion devices such as photovoltaic systems require the concomitant use of
rechargeable batteries for energy storage.
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Classification - primary, secondary and reserve batteries. Characteristics - cell potential,
current, capacity, electricity storage density, energy efficiency, cycle life and shelf life.

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Construction, working and applications of Zinc Air, Nickel- metal hydride batteries.
Lithium batteries: Introduction, construction, working and applications of Li-ion

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batteries.

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Info Guru
Try to Understand people before Trusting them. Because we are living in such a

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world, where Artificial lemon flavour is used for Welcome drink and Real lemon is
used Finger bowl.

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 Conversion and storage of electrochemical energy

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Introduction
Importance of Batteries

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Ø Various types of batteries are used in computers,

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Ø pace makers,
Ø automobiles,

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Ø calculators,
Ø watches, uninterrupted power supplies, industries, hospitals and space applications.

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Ø In automobiles lead storage battery is used.
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Ø The advantage of storage battery is that they can be recharged by reverse
electrolysis.
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Ø Even over charging does not cause any damage to lead storage battery.
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The basic components of a battery are

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Ø Anode
Ø Cathode

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Ø The electrolyte (Active mass in the anode and cathode)

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Ø The separator

Characteristics of Batteries:

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ü It should be economically priced.

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ü It should be light in weight and compact in size.
ü The voltage of the battery should not change much during its use.
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ü It should provide power for longer time.
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ü It should be rechargeable.

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 Classification of Batteries

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Reserve Battery: One of

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Primary Battery: Secondary Battery:
the key component is
Irreversible Reaction reversible Reaction and
isolated from the rest of
cannot be reused Rechargeable

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the battery, prior to
Ex; Zn-MnO2, Li-MnO2 Ex; Lead acid, Li-ion Ni-MH
activation
etc. etc.

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Ex; Mg-Water activated
battery, Mg-CuCl, Li-V2O5,
S Zn-Ag2O batteries Etc.
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 Characteristic terminologies of a battery

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Ø Current: Current is the rate at which the battery is discharging
Ø Voltage: The voltage of a battery is given by the equation

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Ecell = (EC-EA)-ƞA-ƞC-iRcell
Where EC and EA are the electrode potential of cathode and anode

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ƞA-ƞC are the over potentials at anode and cathode
iRcell is the internal resistance
To derive a maximum voltage from the cell

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ü The electrode potential difference between cathode and anode must be high

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ü Polarization and over potential must be minimum
ü Internal resistance must be low
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ØThe electrochemical cell consists of two half cells where one of the half-cell has a
higher value of reduction potential as compared to the other. As a result of this

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potential difference, there is a flow of electrons from the electrode with a lower
reduction potential (or higher oxidation potential) to the electrode with higher

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reduction potential (or lower oxidation potential).
ØThe difference between the electrode potentials of the two electrodes in the
electrochemical cell is known as electromotive force or cell potential of a cell.

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 !"#
C=
$

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Where W is the mass,
Capacity: Capacity
M is the molar mass of the active material

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is the charge in
C is the capacity in ampere hours. (Ah) that can be
obtained from a

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battery . A good
V Ecell minimum
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battery must have
L higher capacity.

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T Capacity is
A determined by

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G using Faraday
E relation
TIME
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Voltage against time for fixed current discharge
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Capacity depends on the amount of active materials

Consumed during discharge, size and discharge condition
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ØThe simplest capacity is measured in amp-hours and is the result of multiplying the

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discharge current (amps) by the discharge time (hours). If a battery is discharged at 5
amps for 20 hours, it has a capacity of 100 amp-hours.

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ØThe measured capacity (C) is described in terms of the specified time of discharge.
The previous example would have a capacity C20 = 100 amp-hours and the discharge
rate is described as C/20 = 5 amps. If the battery has a rated capacity C20 of 100

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amp-hours and a measured capacity C20 of 105 amp-hours (5 amps x 21 hours), it
would exceed its specification by 5%.

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ØBatteries store energy, hence it is denoted by the power or energy it can supply in an
hour. 90 ampere hour means the battery can provide 90 ampere of current for one

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hour.
ØIf you are looking at 12V battery then the power stored is 12*90 =1080 watts.
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Depending upon your appliances Power requirement, the battery will last before
running out. If your appliance is rated 100 Watt hour then the battery will last for 10
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hours.

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ØPower capacity is how much energy is stored in the battery. This power is often
expressed in Watt-hours (the symbol Wh).

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ØA Watt-hour is the voltage (V) that the battery provides multiplied by how
much current (Amps) the battery can provide for some amount of time (generally in

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hours). Voltage * Amps * hours = Wh.
ØSince voltage is pretty much fixed for a battery type due to its internal chemistry
(alkaline, lithium, lead acid, etc), often only the Amps*hour measurement is printed

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on the side, expressed in Ah or mAh (1000mAh = 1Ah).

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ØTo get Wh, multiply the Ah by the nominal voltage. For example, lets say we have a
3V nominal battery with 1Amp-hour capacity, therefore it has 3 Wh of capacity. 1 Ah
means that in theory we can draw 1 Amp of current for one hour, or 0.1A for 10
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hours, or 0.01A (also known as 10 mA) for 100 hours.
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ØHowever, the amount of current we can really draw (the power capability) from a
battery is often limited. For example, a coin cell that is rated for 1 Ah can't actually
provide 1 Amp of current for an hour, in fact it cant even provide 0.1 Amp without

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overextending itself.
ØIts like saying a human has the capability to travel up to 30 miles: of course running

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30 miles is a lot different than walking! Likewise, a 1Ah coin cell has no problem
providing a 1mA for 1000 hours but if you try to draw 100mA from it, it'll last a lot

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less than 10 hours.

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Electricity storage density :

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Ø Electricity storage density is the amount of electricity stored per unit weight of the
battery

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Ø Here weight refers to the complete weight of the battery
Ø It is the capacity per unit weight. A high storage density depends on a good battery
design and also the appropriate selection of electrode reaction.

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Ø It is given as Ah/kg

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 Energy Density:

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ØEnergy density is defined as the ratio of the energy available from a battery to its mass

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measured in Whr/kg. It is given by

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ØWhere ‘i’ is the current drawn from the battery at fixed voltage ‘E’ for time duration ‘t’ and

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‘w’ weight of battery.
ØFor major applications, a good battery is expected to have good energy density.
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 Power Density:

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• Power density is the ratio of the power available from a battery to its mass. It is measured
in w/kg. The power density is given by

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• Where ‘i’ is the current drawn from the battery and ‘E’ is the voltage and ‘w’ is weight of

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battery.
• If a battery is operated at high power level, then the energy available will be less

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• To obtain maximum amount of energy, battery should be operated at a low power level.
For few applications like ignition starting of an engine, a battery is expected to have very
high power density for a short period.

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ØEnergy density is the amount of energy in a given volume and power density is the
amount of power in a given volume.

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ØThe distinction between the two is similar to the difference between Energy and
power. Batteries have a higher energy density than capacitors, but a capacitor has a

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higher power density than a battery.
Ø This difference comes from batteries being able to store more energy, but capacitors
can give off energy more quickly.

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 Energy efficiency :

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It is the ratio of the output of the battery on the discharge to The input required to restore
it to the initial state of charge under specified Conditions. The energy efficiency for storage
batteries is given by

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Energy released on discharge
% Energy Efficiency = X 100

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Energy required for charge
Cycle life:

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Primary batteries are not rechargeable but secondary batteries are rechargeable and
their cycle life must be high

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Number of charge
Cycle life =
Number of discharge
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1. Sorting of electrodes between electrolyte and changes in morphology.
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2. The cycle life is low due to the corrosion at contacts points.

3. Shedding of electrolytes and irregular crystal growth.
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Shelf life

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The duration of storage under specified condition at the end of which a cell or battery
retains the ability to give specified performance is called the shelf life.

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 Zn-air battery

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ü Zn battery belongs to the class of air- metal battery

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ü Which uses oxygen from the atmosphere to produce electrochemical energy

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ü It offers very high energy density because the oxygen does not contribute to the mass
of the battery

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ü This consists of porous carbon plate as cathode rectangular flat plates of zinc as anode
are placed on either side of the cathode

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ü The electrodes are immersed in 20% or 30% NaOH or KOH which acts as electrolyte
ü The outer container is made up of glass or ebonite.
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 The cell is represented as Zn / NaOH (30%) / air, C

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Cell reactions:

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Ø The cell produces an open circuit potential of 1.4V.

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Ø During charging the above reaction is reversed.
Application
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ü It is used as a power source for hearing aids.
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ü Used in electronic pagers

ü Used in military radio receivers and Railway Station. 23
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Anode Zn granules with gelling agent
Cathode C, air (cathode is a carbon/catalyst mixture with a wet agent
coated on Ni plated steel mesh)

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Net cell Reaction Zn + 1/2O2 ZnO

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Applications Hearing aid, Pagers, railway signalling and other electronic
consumer devices.

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 Lithium Batteries

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Ø High energy density - potential for yet higher capacities.

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Ø Does not need prolonged priming when new. One regular charge is all that's needed.
Ø Relatively low self-discharge - self-discharge is less than half that of nickel-based

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batteries.
Ø Low Maintenance - no periodic discharge is needed; there is no memory.

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Ø Specialty cells can provide very high current to applications such as power tools.

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 Lithium – Ion Battery

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ü Rechargeable Li ion batteries possess many advantages over

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classical rechargeable batteries such as Lead acid,
ü Ni-Cd

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ü High Voltage
ü High energy density
ü High cycle life

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ü Low self discharge

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ü It provides maximum voltage of 3.7V
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 Construction of Li-Ion Battery

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It composed of three parts
Ø Anode

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Ø Cathode
Ø Electrolyte

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ü Anode and cathodes are able to insert lithium ions
into their layered structure

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1) Anode: Graphite carbon
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2) Cathode: Lithium metal oxide (Li-CoO2)
3) Electrolyte: A lithium salt of LiPF6 is dissolved in binary organic solvent like ethylene
carbonate-dimethyl carbonate 28
 Ø Reactions: During discharging battery, Li atoms present in graphite layer are oxidised,

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liberating electrons and Li ions. Electrons flow through external circuit to cathode
and li ions flow through the organic electrolyte towards cathode

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Lix-C6 xLi+ + 6C+ xe

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At cathode, Li atoms are reduced to lithium atoms and are incorporated in to the
layered structure of metal oxide.

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xLi+ + xe + Li 1-xCoO2 Li CoO2

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During charging of battery, Li atoms present in layered structure of metal oxide
are oxidised, liberating electrons and Li+ ions. Electrons flow through external
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circuit and Li+ ions flow through the organic electrolyte towards graphite carbon
electrode.
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Li1-xCoO2 xLi++ xe + CoO2

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At graphite electrode, lithium ions are reduced to lithium atoms and are

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incorporated in to the layered structure of graphite
xLi+ + 6C+ xe Lix-C6

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Applications: They are presently employed for powering portable electronic devices like

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Cell phone, Laptops and also in defence, electrical vehicles, power tools and Aerospace
applications

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Lix-C6 xLi+ + 6C+ xe At Anode

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xLi+ + xe + Li 1-xCoO2 Li CoO2 At Cathode
Discharging
Lix-C6 + Li
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1-xCoO2 6C + Li CoO2 Net cell Reaction
Charging
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Anode Li atoms are intercalated in layered Graphite carbon
Cathode Lithium atoms are incorporated into the layered structure

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metal oxide (Li-CoO2)
Net cell Reaction Lix-C6 + Li 1-xCoO2

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6C + Li CoO2
Applications portable electronic devices like Cell phone, Laptops and also in
defence, electrical vehicles, power tools and Aerospace

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applications

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Electrolyte A lithium salt of LiPF6 is dissolved in binary organic solvent like
ethylene carbonate-dimethyl carbonate
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 RESERVE BATTERIES

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ØBatteries, which use highly active component materials to obtain the required high
energy, high power, and/or low-temperature performance, are often designed in a

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reserve construction to withstand deterioration in storage and to eliminate self-discharge
prior to use.

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ØThese batteries are used primarily to deliver high power for relatively short periods of
time after activation in such applications as radiosondes, fuzes, missiles, torpedoes, and
other weapon systems. The reserve design also is used for batteries required to meet

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extremely long or environmentally severe storage requirements.
ØIn the reserve structure, one of the key components of the cell is separated from the

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remainder of the cell until activation.
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ØIn this inert condition, chemical reaction between the cell components (self-discharge) is

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prevented, and the battery is capable of long-term storage. The electrolyte is the component
that is usually isolated, although in some water-activated batteries the electrolyte solute is
contained in the cell and only water is added.

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ØThe reserve batteries can be classified by the type of activating medium or mechanism that
is involved in the activation:

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ØWater-activated batteries: Activation by fresh- or seawater.
ØElectrolyte-activated batteries: Activation by the complete electrolyte or with the electrolyte

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solvent. The electrolyte solute is contained in or formed in the cell.

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ØGas-activated batteries: Activation by introducing a gas into the cell. The gas can be either
the active cathode material or part of the electrolyte.
ØHeat-activated batteries: A solid salt electrolyte is heated to the molten condition and
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becomes ionically conductive, thus activating the cell. These are known as thermal batteries.
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ØActivation of the reserve battery is accomplished by adding the missing component

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just prior to use.
ØIn the simplest designs, this is done by manually pouring or adding the electrolyte

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into the cell or placing the battery in the electrolyte (as in the case of sea water
activated batteries).

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Ø In more sophisticated applications the electrolyte storage and the activation
mechanism are contained within the overall battery structure, and the electrolyte is
brought automatically to the active electrochemical components by remotely

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activating the activation mechanism.

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 Magnesium Water activated Batteries

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Characteristics

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• These are single use primary cells often called” reserve batteries” with a long shelf
life used mainly for emergency applications.

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• Stored in the dry condition and activated at the time of use by adding or immersing
in water or adding an aqueous electrolyte.
• Seawater-activated types also available.

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• Magnesium is generally used as the anode material with various chlorides being used

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for the cathode cost being traded off for performance, silver chloride having superior
energy and current density while while cuprous chloride has lower costs.
• Aluminium anodes are also widely used with seawater-activated batteries. Very high
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current densities possible.
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 Shortcomings

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Advantages ØHigh self discharge rate after activation
ØReliable ØOnce activated they must be replaced.

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ØRugged Applications
ØMilitary applications
ØSafe

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ØMarine use for sonobuoys, life jackets, air sea
ØLight weight without the need to rescue equipment, emergency lighting,
carry the electrolyte. weather balloons.

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ØHigh power and energy densities ØForced flow types used for powering
ØGood response to pulse loading torpedoes can deliver over 300kW for 10

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ØInstantaneous activation minutes
Costs
ØLong unactivated shelf life
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ØSilver cathode types have high material costs
ØNo maintenance ØNon-silver cathode types have low material
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costs
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ØThe water-activated battery was first developed in the 1940s to meet a need for a
high-energy-density, long-shelf-life battery, with good low-temperature performance,
for military applications.

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ØThe battery is constructed dry, stored in the dry condition, and activated at the time
of use by the addition of water or an aqueous electrolyte.

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Ø Most of the water-activated batteries use magnesium as the anode material. Several
cathode materials have been used successfully in different types of designs and

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applications.
ØThe magnesium / silver chloride seawater-activated battery was developed by Bell

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Tele-phone Laboratories as the power source for electric torpedoes.
ØThis work resulted in the development of small high-energy-density batteries readily
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adaptable for use as power sources for sonobuoys, electric torpedoes, weather
balloons, air-sea rescue equipment, py-rotechnic devices, marine markers, and
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emergency lights.

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 Construction:
ØMg water activated battery consist of an anode, a cathode and a separator.

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ØThe silver chloride-magnesium cell consists of an anode of unalloyed, high purity
magnesium, a cathode system of silver and silver chloride, and an absorbent

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separator of cellulosic material.
ØThe cells are maintained in the inactive state by assembling the dry elements into

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cells or batteries in the absence of electrolyte and immediately packing the cells or
batteries in hermetically sealed containers. At the time the cells or batteries are used,
they are immersed in water to render them active.

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Ø When the cell is discharged, the following reactions take place:

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Mg Mg+2+ 2e At Anode
2AgCl + 2e 2Cl- + 2Ag At Cathode
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Mg + 2AgCl MgCI2 + 2Ag Net Cell Reaction
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Cathode (Positive Plate)

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ØSilver chloride is a special case. Silver chloride can be melted, cast into ingots, and
rolled into sheet stock in thicknesses from about 0.08 mm up. Since this material is

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malleable and ductile, it can be used in almost any configuration. Silver chloride is
nonconductive and is made conductive by superficially reducing the surface to silver

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by immersion in a photographic developing solution. No base grid need be used with
silver chloride.
Separator Separators are nonconductive spacers placed between the electrodes.

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Woven or nonwoven fabric, absorbent, nonconductive material is utilised for the dual
purpose of separating the electrodes and absorbing the electrolyte.

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Electrolyte:
ØThese batteries are activated by pouring the electrolyte into the battery where it is

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absorbed by the separator, can utilize water or seawater when the temperature is
above freezing.

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ØAt lower temperatures special electrolytes can be used. The use of a conducting
aqueous electrolyte will result in faster voltage build up. However the introduction of

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salts in the electrolyte will increase the rate of self-discharging.
ØThese batteries are used in the following types of applications:

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ØLifeboat emergency equipment on commercial airlines Sonobuoys Radio and light
beacons Underwater Ordnance Radiosonde units—balloon transport equipment,
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high altitude low ambient temperature operation.
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Anode Unalloyed, high purity magnesium
Cathode Silver chloride is a special case. Silver chloride can be melted, cast

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into ingots, and rolled into sheet stock in thicknesses from about
0.08 mm up.

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Net cell Reaction Mg + 2AgCl MgCI2 + 2Ag
Applications Military applications, Marine use for sonobuoys, life jackets, air

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sea rescue equipment, emergency lighting, weather balloons.
Forced flow types used for powering torpedoes can deliver over

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300kW for 10 minutes
Electrolyte These batteries are activated by pouring the electrolyte into the
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battery where it is absorbed by the separator, can utilize water or
seawater when the temperature is above freezing.
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 Fuel Cells

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Definition:
ØFuel cells can be defined as a galvanic cell in which the electrical energy is directly

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derived by the combustion of chemical fuels supplied continuously .fuel cells converts
about 75% of the available chemical energy into electrical energy.

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ØA fuel cell differs from conventional battery in the following respects.
ØIn a fuel cell the reactants are fed from out side the cell rather than forming integral

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parts of its construction as in a battery.
ØUnlike batteries fuel cells do not store chemical energy.

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ØReactants are constantly supplied and the products are constantly removed from a fuel
cell.
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 Based on the type of electrolytes used, fuel cells are classified

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into the following types.
Alkaline fuel cell

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ØThese fuel cells are low temperature fuel cells operating at 80° C using relatively
inexpensive material such as hydrogen, oxygen and alkali. The alkali particularly

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aqueous solution potassium hydroxide used as electrolyte and depending on the
system the concentration varies from 30 – 45 % by weight. The reactant must be free

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from CO2because in the alkaline media CO2 forms carbonate which would block
electrolyte path ways and electrode process.

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ØCO2 + 2 OH -→ CO32- + H2O
ØThe alkaline solutions allow the use of a wide range of electrode catalyst and yield
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the highest voltage of all fuel cell system.
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 Phosphoric Acid Fuel Cell:

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Ø These cells used hydrogen and clean reformed fuels such as LPG. Oxygen is used as an oxidant. The
electrolyte constitutes 98% H3PO4. This cell can operate at 190 – 200°c for several hours. At temperature of
about 150°C H3PO4 polymerizes to H4P4O7 which as a considerable higher ionic conductivity. Platinum alloys

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such as
Ø Pt- Co- Cr alloys are used as electro catalyst. These cells are being increasingly used to provide light and

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heat in large buildings.
Molten Carbonate fuel cell:

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Ø In these type of fuel cells molten carbonate are used as electrolyte and cell operates at a temperature
between 600 -650°C. In this type of cells, anode is capable of using either hydrogen or CO as the fuel.

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Ø At anode: H2 + CO32 -→ CO2 + H2O + 2 e –
Ø At Cathode: the reaction is
Ø O2 + 2CO2 + 4 e–→ 2 CO32 –
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Ø The anode is porous nickel or Ni – Cr alloy and the cathode is porous NiO. The electrolyte consisting of 46%
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LiAlO2 28% K2CO3 and 32% Li2CO3in the molten. State is absorbed in a porous inorganic matrix. These cells
find use in chemical industries such as aluminum industries.
Ø The efficiency is greater than 55%. 45
 Polymer electrolyte fuel cell:

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ØThe polymer electrolyte fuel cell used a polymer membrane as its electrolyte. This
membrane is an electronic insulator, but an excellent conductor of hydrogen ions. The

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material used consists of fluoro carbon polymer backbone to which sulphonic acid
groups are attached. The acid group fixed to the polymer and cannot leak out but the

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protons on these groups are free to migrate through the membrane.
ØThe electrodes used in this type of fuel cells are typical gas diffusion electrodes made of
porous carbon and impregnated with platinum catalyst on the anode, hydrogen gas is

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catalytically oxidized accordingly to the reaction.

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Ø2H2→ 4 H + + 4 e –
ØThe hydrogen ion passed through the polymer electrolyte to the cathode. Where they
are combined catalytically with oxygen and electrons to form water.
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ØO2 + 4H+ + 4 e -→ 2H2O
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ØThe cell is generally operated at temperature lower than 100°C. Higher
temperature will caused the evaporation of water faster than its production,
causing dehydration of the membrane. The reactant gases should be free from

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CO, as it is a catalytic poison.
Solid Oxide fuel cell:

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ØThe electrolyte in these fuel cells is a solid, non porous metal oxide usually ZrO2
stabilized by Y2O3. The cell operates at 650 – 1000°C where ionic conduction

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takes place by the migration O2- across the electrons through the vacant lattice
sides. The anode is Co – ZrO2 and the cathode is Cr doped LaMnO3.

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ØThe cell can be operated by using H2 or mixture of CO and H2
ØAnode reaction: H2 + O2-→ H2O + 2e –
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ØCO + O2 -→ CO2 + 2e-
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ØCathode reaction ½ O2 + 2 e-→ O2 –

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 Advantages

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ü Fuel cell produces electrical energy continuously as long as the fuel and the oxidants
are supplied

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ü Energy conversion efficiency is high
ü They are eco friendly

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ü Silent operation: No moving parts and there is no wear and tear
ü They produce direct current for long periods at low cost

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ü No need of charging

Limitations

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ü Cost of the power is high as a result of cost of electrodes
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ü Fuel and oxidant need to be stored under high pressure
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ü Voltage obtained by a single unit is moderate
ü These are only energy conversion devices and not energy storage devices
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 Difference between conventional cell and fuel cell

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Sl No Fuel cell Conventional Battery
1 Fuel cell produces electrical energy Battery produces electrical energy until the
continuously as long as the fuel and materials are present in the cell

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the oxidants are fed into the respective
electrodes.

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2 Reactants are fed from outside to the Reactants are the integral part of the
electrode of the fuel cell construction of the cell

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3 Fuel cell do not require charging Battery needs charging

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4 High efficiency of production of Low efficiency of production of electrical
electrical energy energy
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5 Fuel cell need less attention Battery needs more attention
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6 Fuel cell do not store chemical energy Batteries store chemical energy
7 Eco friendly May pose pollution problem 49
 H2 –O2 Alkaline fuel cell:

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Fuel/Electrode/Electrolyte/Electrode/Oxidant
At anode: Fuel Oxidation product + ne-
At Cathode: Oxidant + ne- Reduction product 50
ØThe cell consists of a porous carbon electrodes impregnated with catalyst Pt or Pd as

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anode.
ØThe cathode is also a porous carbon electrode impregnated with Pt or Ag as catalyst.

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ØThe electrolyte is an aqueous solution of KOH.
ØH2and O2gases are bubbled through the anode and cathode compartments respectively.

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The gas diffuses in to the electrode pores and also the electrolyte solution.
ØThe cell runs continuously as long as gases H2 and O2 are supplied

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Ø The emf of the cell is 1.23V.
ØThe product discharged by the cell is water it should be removed at the same rate.

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Therefore the electrolyte is kept hot so that the water evaporates as fast as it formed. A
wick placed in side the electrolyte also helps to remove the water.
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ØUsually a large number of these cells are attached together in series to make a battery
called fuel cell battery or fuel battery.
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Anode material: H2
Cathode Material: O2

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Anode : Porous carbon electrodes impregnated with catalyst Pt or Pd
Cathode: Porous carbon electrode impregnated with Pt or

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Ag as catalyst
Electrolyte: KOH

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H2 (g) + 2OH– (aq) H2O (l) + 2e- At anode

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O2 (g) + H2O (l) +2e – 2OH- (aq ) At cathode
2H2 (g) + O2 (g) 2H2O (l) Net reaction
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Applications:
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Ø H2 – O2 are used as auxiliary energy source in space vehicles like Apollo space craft,
submarines and other military vehicles.
52
 Solid oxide Fuel

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Anode material: H2
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Cathode Material: O2
Anode : NiZrO2
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Cathode: Sr-doped LaMnO3

Electrolyte: ZrO2 doped with Y2O3 53
ØIt consists of three components - a cathode, an anode, and an electrolyte

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sandwiched between the two.
ØOxygen from the air flows through the cathode

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ØThe electrolyte in these fuel cells is a solid, non porous metal oxide usually ZrO2

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stabilized by Y2O3. The cell operates at 650 – 1000°C where ionic conduction takes
place by the migration O2- across the electrons through the vacant lattice sides. The
anode is Ni – ZrO2 and the cathode is Sr doped La-MnO3.

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ØThe cell can be operated by using H2
H2 + O2-→ H2O + 2e- At Anode

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½ O2 + 2 e-→ O2 –Cathode reaction
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H2+1/2O2 H2O Net Cell Reaction
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54
• Justify the use of same electrolyte in an oxygen sensor.

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• In an oxygen sensor, O2 undergoes reduction at cathode producing O2- ions which have to
move through the electrolyte towards anode the O2- gets oxidised. ZrO2 doped with Y2O3

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has O2- ion vacancies. So the ions O2- formed at cathode can move through these vacant
sites towards the anode, since it facilitates movement of O2- ions from one electrode to
another ZrO2 doped with Y2O3 is suitable electrolyte for O2.

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PE
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 Proton-Exchange Membrane Cell

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ØHow a fuel cell works: In the polymer electrolyte membrane (PEM) fuel cell, also

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known as a proton-exchange membrane cell, a catalyst in the anode separates
hydrogen atoms into protons and electrons. The membrane in the center transports

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the protons to the cathode, leaving the electrons behind.
Ø The electrons flow through a circuit to the cathode, forming an electric current to do

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useful work.
Ø In the cathode, another catalyst helps the electrons, hydrogen nuclei and oxygen
from the air recombine. When the input is pure hydrogen, the exhaust consists of

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water vapor.

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ØIn fuel cells using hydrocarbon fuels the exhaust is water and carbon dioxide.
Cornell's new research is aimed at finding lighter, cheaper and more efficient
materials for the catalysts and membranes.
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PE

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 ity
• Tomorrow, hydrogen's use as a fuel for fuel cells will grow dramatically-for

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transportation, stationary and portable applications. (PlugPower 5-kW fuel cell (large
cell), H2ECOnomy 25-W fuel cell (small silver cell), and Avista Labs 30-W fuel cell).

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PE
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 Super Capacitor

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ØSupercapacitor, Ultracapacitor or electrochemical double-layer capacitor are

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devices that can be used as energy storage systems, that have high energy density
and high power densities, a high efficiency, nearly 95% and a large life expectancy.

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ØThe 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.

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Applying a voltage differential on the positive and negative plates charges the
capacitor. This is similar to the build-up of electrical charge when walking on a

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carpet. Touching an object releases the energy through the finger.
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PE

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 ity
ØA capacitor is a passive electronic component comprising a pair of conducting plates
separated by a dielectric. Capacitors store electrical energy as electrostatic charge

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with equal quantities of positive and negative charges on opposite faces of the
conducting plates resulting in a voltage difference between the faces.

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ØWhen 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.

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ØSince the charge is stored physically without any chemical or phase changes, the

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process is highly reversible and the charge–discharge cycle can be repeated over and
over again, virtually without limit.
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PE

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 ity
ØThe quantity of charge (Q) stored in a capacitor is equal to the device voltage (V)
times proportionality constant (C) called capacitance, i.e.

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Ø Q = CV ---------(1).
ØWhere C= Capacitance in Farad,

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Ø Q=charge in Coulomb
Ø V= Voltage in Volt.

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ØIn 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

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Figure. S
PE

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 ity
.....(2)

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In the above equation proportionality constant ε0 = 8.9 × 10 −12 F m −1 is the permittivity
of the free space or vacuum. Permittivity is the measure of the resistance that is

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encountered whilst forming an electric field in a medium. Permittivity is determined by
the ability of a material to polarize in response to the field that reduces the total field
inside the material.
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 ity
ØAccordingly, permittivity relates to a material’s ability to transmit or permit an
electric field.
ØThe permittivity of a medium describes how much electric field or more correctly

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electric flux is generated per unit charge.

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ØLess electric flux exists in a medium with a high permittivity per unit charge due to
polarization effects. A dielectric medium showing orientation of charged particles
creating polarization effects is represented in Figure.

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ØSuch a medium can have a higher ratio of electric flux to charge (permittivity) than
empty space.

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ØWhen the region between the plates is filled with a dielectric material of relative
permittivity (εr ), which increases the energy stored in the device, the capacitance (C)
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is then expressed as:
PE

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 On substituting Eq. (3) in Eq. (1), we get,

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C= ........(3)

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Q= V ........(4)

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Schematic sketch of an electrical double-layer capacitor

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ØThe total charge stored in a capacitor is directly proportional to the dielectric constant of

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the dielectric (εr ) and area of the electrode (A), and inversely proportional to the
thickness (d) of the dielectric. Accordingly, to achieve a high energy density capacitor, the
dielectric should have high dielectric constant, large surface area and thin dielectric

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medium. The electrical energy (E) stored in a charged capacitor is:

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• As the voltage of the capacitor increases from 0 to V, the charge accumulated on the
electrode increases from 0 to q and accordingly, the stored energy E is expressed as:

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..........................(5)

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..........................(6)
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 There are three types of capacitors.

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(a) Electrostatic,

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(b) Electrolytic and
(c) Electrochemical capacitors

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1. Transition metal oxides
2. Metal oxide – carbon composites

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3. Conducting polymers
4. Electrolytes used are salt solutions in

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aqueous or nonaqueous medium. Special
salt Bases such as fluorborate salt and
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barium titanate are being used as
electrolytes.
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 Advantages of Super capacitors

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• Charging time is very less; almost instantly.
• No danger of overcharge and hence no full charge detection is required.

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• Cycle life virtually unlimited.
• Indefinite life span since no chemical reactions involved.

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• Improved safety, no corrosive electrolyte and low toxicity of materials.
Disadvantages of super capacitors:

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1. Energy density is low which is just 1/5th to 1/10th that of the batteries.
2. Super capacitors with sufficient charge capacity requires large space.

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3. Rate of self – discharge is considerably high compared to battery.
Applications
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Ø In electric cars, memory backup to bridge short power interruptions.
Ø Super capacitors are used in storing solar and wind energies.
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ØPhotographic flash, portable media players and automated meter reading equipment.
ØMedical applications, power handheld, laser – based breast cancer detector
69
 Comparison between Super capacitor and Batteries

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Super capacitor Batteries

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Energy density is low Energy density is high

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Discharge is linear and voltage Delivers steady for long time
Does not require full charge detection unit Requires full charge detection unit

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Unlimited cycle life Low cycle life (few hundreds)

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Low charging time High charging time
Very high self discaharge Very low self discharge
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 Oxygen Sensor

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ØAn Oxygen sensor or lambda sensor is an electronic device that measures the
proportion of O2 in the gas or liquid being analyzed.

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ØA gasoline engine burns gasoline in the presence of oxygen.
ØIt turns out that there is a particular ratio of air and gasoline that is "perfect," and that

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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).
ØIf there is less air than this perfect ratio, then there will be fuel left over after

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combustion.
ØThis is called a rich mixture.

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ØRich mixtures are bad because the unburned fuel creates pollution. If there is more air
than this perfect ratio, then there is excess oxygen.
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Ø This is called a lean mixture.
ØA lean mixture tends to produce more nitrogen-oxide pollutants, and, in some cases, it
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can cause poor performance and even engine damage.

71
ØThe oxygen sensor is positioned in the exhaust pipe and can detect rich and lean

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mixtures.
Ø The Oxygen Sensor detects the amount of oxygen in the exhaust gas and sends a

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signal to the engine control unit which adjusts the air fuel mixture to the optimal
level.

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ØToo much oxygen in the exhaust gas indicates a lean mixture, which can cause
performance problems, including misfires.

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ØToo little oxygen indicates a rich mixture, which wastes fuel and results in excess
exhaust emissions.

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 Construction and operation:
ØAn O2 sensor is actually a galvanic cell.

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ØThe zirconium dioxide, or zirconia, lambda sensor is
based on a solid-state electrochemical fuel cell called

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the Nernst cell. The sensor contains two platinum
electrodes with an electrolyte between them.

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ØZrO2 doped with some Y2O3 is the electrolyte used.
Due to doping some oxygen vacancies are created in
the crystal lattice.

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ØThe mobility of O2- ions is greatly enhanced and the
conductivity is due to oxygen ions.

U Cell voltage is given by =

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where p1 and p2 are the partial pressure of O2 in reference air and exhaust gas respectively.

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• Its two electrodes provide an output voltage corresponding to the quantity of oxygen

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in the exhaust relative to that in the atmosphere.
• 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

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monoxide (CO), produced in burning the air and fuel, into carbon dioxide (CO2).
• An output voltage of 0.8 V represents a "rich mixture", one which is high in unburned

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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.

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• O2 sensors operate at a minimum temperature of 360oC.
• The O2 sensor allows fuel management system to maintain the ideal air/fuel ratio

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across various engine operation conditions.
• Automobiles using a 3-way catalyst are equipped with O2 sensors.
• Leaded gasoline contaminates the O2 sensors and catalytic convertors and results in
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failure of the sensor. Other reason for failure could be presence of impurities in
gasoline.
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 Applications

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• Most common applications of O2
sensors are:
• Measure exhaust gas concentrations of

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O2 in IC engines
• Divers use to measure partial pressure

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of O2 in their breathing gas
• Scientists use as probes to measure
respiration or production of O2

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• In O2 analyzers used in medical
applications such as anesthesia

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monitors, respirators etc.
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 Ragone Plot of Electrochemical Devices

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A Ragone plot is a plot used for performance comparison of various energy storing devices
in which the values of energy density are plotted versus power density. 76
ØThe Ragone plot below compares the performance of a range of electrochemical

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devices. It shows that ultra capacitors (super capacitors) can deliver very high power
but the storage capacity is very limited.

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ØOn the other hand Fuel Cells can store large amounts of energy but have a relatively
low power output.

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ØThe sloping lines on the Ragone plots indicate the relative time to get the charge in
or out of the device.
ØAt one extreme, power can be pumped into, or extracted from, capacitors in

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microseconds. This makes them ideal for capturing regenerative braking energy in EV
applications.

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ØAt the other extreme, fuel cells have a very poor dynamic performance taking hours
to generate and deliver their energy. This limits their application in EV applications
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where they are often used in conjunction with batteries or capacitors to overcome
this problem.
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ØLithium batteries are somewhere in between and provide a reasonable compromise

between the two. 77
• Is a plot used for performance comparison of various energy-storing devices. On such a

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chart the values of specific energy (Wh/Kg) are plotted versus specific power W/Kg). Both
axes are logarithemic, which allows comparing performance of very different devices (for
example, extremely high and extremely low power).

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• 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

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power, per unit mass.
• A point in a Ragone plot thus represents the amount of time during which the energy (per

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mass) on the Y-axis can be delivered at the power (per mass) on the X-axis, and that time
(in hours) is given as the ratio between the energy and the power densities.

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• Consequently, the iso curves in a Ragone plot are straight lines with unity slope. For
example, powering a small light bulb may require low amounts of power, but the power
should be delivered steadily enough to operate a flashlight for minutes or hours of use.
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• Conversely, a high-speed electronic switch inside a computer may require very little
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energy to activate; yet it must be delivered rapidly enough to complete the transaction in
mere microseconds. These two types of loads would be represented at opposite corners
of the Ragone plot. 78