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Introduction
A battery is a device that converts the chemical energy
contained in its active materials directly into electric energy by
means of an electrochemical oxidation-reduction (redox)
reaction.
In the case of a rechargeable system, the battery is recharged by
a reversal of the process. This type of reaction involves the
transfer of electrons from one material to another through an
electric circuit.
In a nonelectrochemical redox reaction, such as rusting or
burning, the transfer of electrons occurs directly and only heat
is involved.
As the battery electrochemically converts chemical energy into
electric energy, it is not subject, as are combustion or heat
engines, to the limitations of the Carnot cycle dictated by the
second law of thermodynamics.
Batteries, therefore, are capable of having higher energy
conversion efficiencies.
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 While the term battery is often used, the basic electrochemical unit
being referred to is the cell.
A battery consists of one or more of these cells, connected in series or
parallel, or both, depending on the desired output voltage and
capacity.

The cell consists of three major components:

1. The anode or negative electrodethe reducing or fuel

electrodewhich gives up electrons to the external circuit and is
oxidized during the electrochemical reaction.
2. The cathode or positive electrodethe oxidizing electrode
which accepts electrons from the external circuit and is reduced
during the electrochemical reaction.
The electrolytethe ionic conductorwhich provides the
medium for transfer of charge, as ions, inside the cell between the
anode and cathode. The electrolyte is typically a liquid, such as water
or other solvents, with dissolved salts, acids, or alkalis to impart ionic
conductivity. Some batteries use solid electrolytes, which are ionic
conductors at the operating temperature of the cell.
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CLASSIFICATION OF BATTERIES
Electrochemical cells and batteries are identified as primary
(nonrechargeable) or secondary (rechargeable), depending on their
capability of being electrically recharged.
Primary Cells or Batteries
These batteries are not capable of being easily or effectively recharged
electrically and, hence, are discharged once and discarded. Many
primary cells in which the electrolyte is contained by an absorbent or
separator material (there is no free or liquid electrolyte) are termed dry
cells. Ex: Zinc-carbon cells, Alkaline battery, Lithium battery,
Mercury battery, Silver oxide battery
Secondary or Rechargeable Cells or Batteries
These batteries can be recharged electrically, after discharge, to their
original condition by passing current through them in the opposite
direction to that of the discharge current.
They are storage devices for electric energy and are known also as
storage batteries or accumulators. Ex: Lead acid battery, Nickel-
cadmium battery, Lithium ion battery, Nickel metal hydride
battery 4
The applications of secondary batteries
The secondary battery is used as an energy-storage device,
generally being electrically connected to and charged by a prime
energy source and delivering its energy to the load on
demand. Examples are automotive and aircraft systems,
emergency no-fail and standby (UPS) power sources, hybrid
electric vehicles and stationary energy storage (SES) systems for
electric utility load leveling.

The secondary battery is used or discharged essentially as a

primary battery, but recharged after use rather than being
discarded. Secondary batteries are used in this manner as, for
example, in portable consumer electronics, power tools, electric
vehicles, etc., for cost savings (as they can be recharged rather
than replaced), and in applications requiring power drains
beyond the capability of primary batteries.
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 Primary Battery
Zn-Carbon Battery
In the primary batteries, the reaction occurs only once and after use over
a period of time battery becomes dead and cannot be reused again. The
most familiar example of this type is the dry cell which is used
commonly in our transistors and clocks.
The cell consists of a zinc container that acts as anode
and the cathode is a carbon (graphite) rod surrounded by
powdered manganese dioxide and carbon. The space
between the electrodes is filled by a moist paste of
ammonium chloride (NH4Cl) and zinc chloride (ZnCl2).
The electrode reactions as follows :
Anode: Zn(s) Zn2+ + 2e
Cathode: MnO2+ NH4++ e MnO(OH) + NH3

In the reaction at cathode, manganese is reduced from

the + 4 oxidation state to the +3 state. Ammonia
produced in the reaction forms a complex with Zn2+ to
give [Zn(NH3)4]2+. The cell has a potential of nearly 1.5 V. 6
Disadvantages
1) After using for a long time, the chemicals would
leak out of the battery, it is not good for the
environmental protection
2) it cannot be recharged
3) lifetime is short because it continually reacts at a
slow rate
4) current is small (it ceases to function if required
to produce large currents in short time)
5) voltage is not stable
6) resistance is high

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 Mercury cell
Mercury cell, suitable for low current devices like hearing aids,
watches, etc. consists of zinc mercury amalgam as anode
and a paste of HgO and carbon as the cathode.
The electrolyte is a paste of KOH and ZnO. The electrode
reactions for the cell are given below:

Anode: Zn(Hg) + 2OH ZnO(s) + H2O + 2e

Cathode: HgO + H2O + 2e Hg(l ) + 2OH
The overall reaction is represented by

Zn(Hg) + HgO(s) ZnO(s) + Hg(l )

The cell potential is approximately 1.35 V

and remains constant during its life as the
overall reaction does not involve any ion
in solution whose concentration can
change during its life time. 8
 Secondary Batteries (lead acid batteries)
The most important secondary cell is the lead storage battery (Fig. commonly
used in automobiles and invertors.
It consists of a lead anode and a grid of lead packed with lead dioxide (PbO2
) as cathode. A 38% solution of sulphuric acid is used as an electrolyte.
The cell reactions when the battery is in use are given below:
Anode: Pb(s) + SO42(aq) PbSO4(s) + 2e
Cathode: PbO2(s) + SO42(aq) + 4H+(aq) + 2e PbSO4 (s) + 2H2O (l )
i.e., overall cell reaction consisting of cathode and anode reactions is:
Pb(s)+PbO2(s)+2H2SO4(aq) 2PbSO4(s) + 2H2O(l)
On charging the battery the reaction is reversed and PbSO4(s) on
anode and cathode is converted into Pb and PbO2, respectively.

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 LITHIUM-ION BATTERIES
Lithium-ion (Li-ion) batteries are comprised of cells that employ lithium
intercalation compounds as the positive and negative materials. As a
battery is cycled, lithium ions (Li) exchange between the positive
and negative electrodes. They are also referred to as rocking chair
batteries as the lithium ions rock back and forth between the positive
and negative electrodes as the cell is charged and discharged. The
positive electrode material is typically a metal oxide with a layered
structure, such as lithium cobalt oxide (LiCoO2), or a material with
a tunneled structure, such as lithium manganese oxide (LiMn2O4),
on a current collector of aluminum foil. The negative electrode
material is typically a graphitic carbon, also a layered material, on
a copper current collector. In the charge/ discharge process, lithium
ions are inserted or extracted from interstitial space between atomic
layers within the active materials.

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Schematic of the electrochemical process in a Li-ion cell. 11
In this scheme, LiMO2 represents the metal oxide positive material, such as
LiCoO2, and C the carbonaceous negative material, such as graphite. The
reverse happens on discharge. As metallic lithium is not present in the cell, Li-
ion batteries are chemically less reactive, safer, and offer longer cycle life than
possible with rechargeable lithium batteries that employ lithium metal as the
negative electrode material. The charge/discharge process in a Li-ion cell is
further illustrated graphically in Fig. In the figure, the layered active materials
are shown on metallic current collectors.

Electrode and cell reactions in a Li-ion cell. 12

Advantages and Disadvantages of Li-ion Batteries

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 Fuel Cells
Fuel cells, like batteries, are electrochemical galvanic cells that
convert chemical energy directly into electrical energy and are
not subject to the Carnot cycle limitations of heat engines.
Fuel cells are similar to batteries except that the active materials
are not an integral part of the device (as in a battery), but are fed
into the fuel cell from an external source when power is desired.

The fuel cell differs from a battery in that it has the capability of
producing electrical energy as long as the active materials are fed
to the electrodes.
The battery will cease to produce electrical energy when the
limiting reactant stored within the cell is consumed.
The electrode materials of the fuel cell are inert and have
catalytic properties which enhance the electroreduction or
electrooxidation of the reactants (the active materials).
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 The anode active materials used in fuel cells are generally
gaseous or liquid (compared with the metal anodes generally
used in most batteries) and are fed into the anode side of the
fuel cell.
Oxygen or air is the predominant oxidant and is fed into the
cathode side of the fuel cell.

Fuel cell technology can be classified into two categories

Direct systems where fuels, such as hydrogen, methanol and

hydrazine, can react directly in the fuel cell
Indirect systems in which the fuel, such as natural gas or other
fossil fuel, is first converted by reforming to a hydrogen-rich gas
which is then fed into the fuel cell

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 One of the most successful fuel cells uses the reaction of
hydrogen with oxygen to form water. The cell was used for
providing electrical power in the Apollo space programme.
The water vapours produced during the reaction were
condensed and added to the drinking water supply for the
astronauts.
In the cell, hydrogen and oxygen are bubbled through porous
carbon electrodes into concentrated aqueous sodium hydroxide
solution.
Catalysts like finely divided platinum or palladium metal are
incorporated into the electrodes for increasing the rate of
electrode reactions.

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The electrode reactions are given below:
Anode: 2H2 (g) + 4OH(aq) 4H2O(l) + 4e
Cathode: O2(g) + 2H2O(l ) + 4e 4OH(aq)

Overall reaction being:

2H2(g) + O2(g) 2 H2O(l )

The cell runs continuously as long as the reactants are supplied.

Fuel cells produce electricity with an efficiency of about 70 %
compared to thermal plants whose efficiency is about 40%.
There has been tremendous progress in the development of new
electrode materials, better catalysts and electrolytes for
increasing the efficiency of fuel cells.
These have been used in automobiles on an experimental basis.
Fuel cells are pollution free and in view of their future
importance, a variety of fuel cells have been fabricated and tried.
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 Alkaline Fuel Cells
Alkaline fuel cells differ from other types of fuel cells in the chemical
reaction and the operating temperature. Hydrogen and oxygen are
reactants and Potassium hydroxide and electrolyte
The chemical reaction that occurs at the anode is:
2H2 + 4OH 4H2O + 4e
The reaction at the cathode occurs when the electrons pass
around an external circuit and react to form hydroxide ions,
OH, as shown:

O2 + 4e + 2H2O 4OH

Alkaline fuel cells have some major advantages over other types of fuel
cells. The rest is that the activation overvoltage at the cathode is usually
less than with an acid electrolyte fuel cell. The second advantage is that
the electrodes do not have to be made of precious metals.
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Molten Carbonate Fuel Cell
The defining characteristic of a molten carbonate fuel cell (MCFC) is the
material used for the electrolyte. The material is a molten mixture of alkali
metal carbonates. The electrolyte is usually a binary mixture of lithium and
potassium, or lithium and sodium carbonates which is held in a ceramic
matrix of LiAlO2. A highly conductive molten salt is formed by the carbonates
at very high temperatures.

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 Direct Methanol Fuel Cells
The use of pure hydrogen in fuel cells is not the only way to convert
hydrogen into useful electric energy. A variety of reactions can produce
hydrogen indirectly, thus enabling the classic hydrogen fuel cell chemical
reaction to take place.
The fuel is a mixture of water and of methanol; it reacts directly at the
anode according to:
CH3OH + H20 6H+ + 6e +CO2
As mentioned above the boiling point of methanol at atmospheric
pressure is 65oC, thus the cells requires an operating temperature around
70oC (to avoid a too high vapor pressure). The reaction mechanism is
much more complex with the appearance of species adsorbed as well as
with HCOH and HCOOH. If one considers this reaction on a Pt/Ru
catalyst, it can be represented with the following stages.

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The compounds PtCOH and PtCO are poisons for Platinum, and after
research it was found that the addition of Ruthenium makes it possible to
cure the Pt, and prevent poisoning.

The above reactions give the production of the hydrogen, which can in
turn be used by the cathode. The cathode undergoes the typical fuel cell
reaction with hydrogen combining with oxygen. The total DMFC
equation, representing only the initial and final products for both the
cathode and anode is as follows:

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 Difference between a fuel cell and
a battery
Batteries
A battery stores the chemical
reactants, usually metal
compounds like lithium, zinc
or manganese.
Batteries will produce
electricity as long as reactive
materials are present.
Once used up, you must
recharge or throw away the
battery.
Fuel Cell
A fuel cell creates electricity
through reactants (hydrogen
and oxygen) stored externally.
A fuel cell will produce
electricity as long as it has a
fuel supply.
In short, a fuel cell vehicle is
refueled instead of recharged.
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