Battery: Battery is an electrochemical device which transforms chemical energy to

electrical energy. In general battery consists of two or more electrochemical cells

connected in series. In general batteries are three types
(I) Primary batteries and (II) Secondary batteries (III) Fuel cells

1. Primary cells: In Primary cells the electrochemical reactions at the

electrodes are not reversible. Thus, when most of the reactants converted as
products, no more electricity can be released and the battery become dead
2. Secondary batteries: The cell reactions can be reversed by passing the
electric current in opposite direction. Secondary battery may be used
through large number of cycles of charging and discharging.
3. Fuel Cells: In the fuel cells, the materials such as fuel and oxidant are
passed separately and continuously to the electrode at which the
electrochemical reaction occur are called as fuel cells or flow batteries.
(I) Dry cell or Leclanche cell:
It consists of Zn anode which is shaped in the form of container for the elctrolyte.
Electrolyte consists of NH4Cl, ZnCl2 and MnO2 and to this starch is added to make
paste. The cell is encased in polypropylene cylinder. A carbon rod serves as cathode,
which is immersed in the electrolyte in the center of cell.
At Anode,

𝑍𝑛(𝑠) 𝑍𝑛+2 (𝑎𝑞) + 2𝑒 −

The reaction at cathode is complex, it involves the reduction of MnO2 to Mn2O3

2𝑀𝑛𝑂2 (𝑠) + 𝐻2 𝑂 + 2𝑒 − 𝑀𝑛2 𝑂3 (𝑠) + 2𝑂𝐻 − (𝑎𝑞)

The acid - base reaction from NH+4 (from NH4Cl) and OH- evolves NH3 and it
disrupts current flow.
𝑁𝐻4+ (𝑎𝑞) + 𝑂𝐻 − (𝑎𝑞) 𝑁𝐻3 (𝑔) + 𝐻2 𝑂(𝑙)

This can be prevented by the reacting NH3 (g) with ZnCl2 to form complex
[Zn(NH3)2]Cl2(s)
Hence the electrode reactions can be written as:
𝑍𝑛(𝑠) + 2𝑁𝐻4+ (𝑎𝑞) + 2𝐶𝑙 − (𝑎𝑞) + 2𝑀𝑛𝑂2 𝑀𝑛2 𝑂3 (𝑠) + [𝑍𝑛(𝑁𝐻3 )]2𝐶𝑙2 (𝑠) + 2𝐻2 𝑂

Figure: Leclanche cell or dry cell

The voltage of the dry cell is about 1.5 V.

Disadvantages: (I) drop in voltage (ii) dissolution of Zn metal in acidic electrolyte.
The electrolyte in NH4Cl if it is replaced by KOH then it is called as alkaline battery
which is improved form of the dry cell.
Uses: (i) Transistor radios (ii) flash lights
Secondary Battery: Secondary battery is electrochemical cell in which the cell
reaction can be reversed by passing electrical current in reverse direction. Thus the
secondary battery can be used through the large number of cycles of discharging
and charging.

Ni-Cd Battery: It consists of Cd anode and cathode consists of a paste of NiO(OH)

Anode: 𝐶𝑑(𝑠) + 2𝑂𝐻 − (𝑎𝑞) 𝐶𝑑(𝑂𝐻)2 (s)+2𝑒 −
Cathode: 2𝑁𝑖𝑂(𝑂𝐻)(𝑠) + 2𝐻2 O(l)+2𝑒 − 2𝑁𝑖(𝑂𝐻)2 (𝑠) + 2𝑂𝐻 − (𝑎𝑞)

Net: 2𝑁𝑖𝑂(𝑂𝐻)(𝑠) + 2𝐻2 𝑂 + 𝐶𝑑(𝑠) 2𝑁𝑖(𝑂𝐻)2 (𝑠) + 𝐶𝑑(𝑂𝐻)2

The cell reaction can be easily reversed. Ni-Cd cell is portable and rechargeable cell
with constant voltage of 1.4 V.
Uses: It is used in electronic calculators, electronic flash units, cordless electronic
shavers, transistors and other battery powered small tools.

Lead Acid Cell or Lead acid Cell:

A storage cell is which can work both as voltaic cell as well as electrical cell. During
its operation (at the time of discharge) it works as voltaic cell i.e. electrical energy
produced during the chemical reaction. At the time of charging it works as
electrolytic cell i.e. Chemical is produced by the supply of electrical energy. Lead
acid cell is one of such example for the storage cell. Hence it is also named as lead
storage cell.
It consists of Lead dioxide as cathode and lead as anode. The electrolyte is
20 % solution of H2SO4. The voltage of the cell is around 2.0 V at 25 C. Lead acid
cell consisting 6 cells in series is capable of delivering 12 V.
Discharge:
At the time of discharge lead acid cell acts as voltaic cell and the reactions at anode
and cathode are
Anode:
𝑃𝑏 𝑃𝑏 2+ + 2𝑒 −
𝑃𝑏 2+ + 𝑆𝑂42− 𝑃𝑏𝑆𝑂4
The lead ions formed they combine with SO4 2- from electrolyte and PbSO4 will be
formed.

Cathode:
The released electrons at anode flow to cathode and reduction occurs at cathode.
Here also PbSO4 will be formed.

𝑃𝑏𝑂2 + 4𝐻 + + 2𝑒 − 𝑃𝑏 2+ + 2𝐻2 𝑂
𝑃𝑏 2+ + 𝑆𝑂42− 𝑃𝑏𝑆𝑂4

Hence the Net reaction during the discharge can be written as:
𝑃𝑏 + 𝑃𝑏𝑂2 + 4𝐻 + + 2𝑆𝑂42− 2𝑃𝑏𝑆𝑂4 + 2𝐻2 𝑂 + 𝐸𝑛𝑒𝑟𝑔𝑦

From the equations from which PbSO4 formed, it can be easily realized that PbSO4
precipitates on both the electrodes, when PbSO4 covers the electrodes completely,
cell stops functioning as voltaic cell. Hence it has to be recharged.

Recharge: Recharge of lead acid cell can be done by passing an external e.m.f
greater than 2V and the equations at the time of charging can be expressed as:

Cathode:
𝑃𝑏𝑆𝑂4 + 2𝑒 − 𝑃𝑏 + 𝑆𝑂42−

Anode:
𝑃𝑏𝑆𝑂4 + 2𝐻2 𝑂 𝑃𝑏𝑂2 + 4𝐻 + + 𝑆𝑂42− + 2𝑒 −

The net reaction (during charging) is:

2𝑃𝑏𝑆𝑂4 + 2𝐻2 𝑂 + 𝑒𝑛𝑒𝑟𝑔𝑦 𝑃𝑏 + 𝑃𝑏𝑂2 + 4𝐻 + + 2𝑆𝑂42−

Hence during the charging cycle, the cell electrodes are restored to their original
condition. During the discharge the con. of H2SO4 decreases and it increases during
recharge operation. Charging and discharging of the battery can be checked by
measuring density of H2SO4 using hydrometer.
Applications: It can be used in electrical vehicles, automobiles, power stations and
stand by supplies (UPS) etc.
 Fig: Lead acid battery

Lithium ion batteries:

Li atom is having the highest negative electrode potential (-3.05 V) and light weight
element. Hence it can be found as useful material for battery applications. In
Lithium ion battery anode consists of porous carbon such as graphite and cathode
materials are Li containing crystal structures such as LiCoO2 and LiMn2O4 etc.
Non-aqueous electrolytes containing Lithium salts such as LiPF6 and LiBF4 in
organic solvents can be sued as electrolytes. The cell operation involves the
transport of Li ions through the electrolyte from one electrode to other and charge
balance can be maintained by transport of electrons through the external circuit.

When the cell is discharged, Li ions move back to Cobalt oxide through the
electrolyte. If we represent amount of Li ions transferring by “y” the discharge
reaction is

Applications: In laptops, mobile phones, electric devices

 Fig: Li-ion battery

Fuel Cells:
Fuel cell is an electrochemical cell and it converts chemical energy of fuel-oxidant
system to electrical energy. In the fuel cell chemical energy is supplied by the fuel
and oxidant system which are stored outside the cell. Fuel and oxidant are
continuously and separately supplied to the electrodes, at which they undergo
reaction. Fuel cells are capable of supplying current as long as the reactants are
supplied.

Study H2-O2 fuel cell:

Methanol-Oxygen fuel cell: this is not necessary

It is sub category of proton exchange fuel cell. In this fuel cell Methanol-water
mixture is circulated at anode and Oxygen is circulated at cathode. Pt is used as
catalyst to carryout the electrochemical reactions at cathode and anode. Methanol
undergoes oxidation over catalyst surface (Pt) and forms CO2. The electrons
produced at anode are transported to cathode over external circuit. While the
transport of protons (H+ ions) from anode to cathode is facilitated by proton
exchange membrane, often Naffion used as commercially available proton
exchange membrane. At cathode, protons combine with oxygen and electrons and
produce water. The half cell reactions can be represented as:

From the above cell reactions, which involve the transfer of 6 e- can produce a
standard cell voltage of 1.21 V and energy density of 6 kwh/kg of methanol.

Limitations:
• During the oxidation of methanol over catalytic Pt surface, CO is formed. CO
can adsorb on the Pt surface and decreases the active catalytic surface area.
Hence the catalytic activity of Pt is reduced. This is called as catalyst
poisoning.
• Methanol is toxic and flammable.
• The permeation of methanol through proton exchange membrane leads to
the decrease in efficiency of fuel cell performance. This phenomenon is called
as methanol crossover
Advantages:
• Storage of methanol is much easier than H2 and it does not require high
pressures and low temperatures.
• The energy density of methanol is an order of magnitude greater than H2
Fig: Methanol-Oxygen Fuel cell