B.

Conversion and storage of electrochemical energy

Battery Technology
Introduction:
A battery is an arrangement consists of two or more galvanic cells
connected in series. The battery is used as a source of direct electric current
at constant voltage.
Importance of Batteries:
Various types of batteries are used in computers, pace makers,
automobiles, calculators, watches, uninterrupted power supplies, industries,
hospitals and space applications.
In automobiles lead storage battery is used. The advantage of storage
battery is that they can be recharged by reverse electrolysis. Even over
charging does not cause any damage to lead storage battery.
Basic concepts of batteries:
The basic electrochemical unit in a battery is a galvanic cell, the
components of such a cell are shown schematically as shown below

The basic components of a battery are

1. Anode; It is a negative electrode where oxidation takes place. It gives out
electrons to the external circuit by a electro chemical reaction.
2. Cathode; It is a positive electrode where reduction takes place. It accepts
the electrons from the external circuit.
3. The electrolyte (Active mass in the anode and cathode): Is commonly a
solution or slurry of acids, alkalis or salts having high ionic conductivity.
Solid electrolyte with appreciable ionic conductivity is also used at the
operating temperature of the cell.
4. The separator: The material which electronically isolate anodes and
cathodes in a battery to prevent internal short circuiting are referred to as
separator. They are permeable to the electrolyte so as to maintain ionic
conductivity. Their function is to transport ions from one comportment to
other.

Characteristics of Batteries:
1. It should be economically priced.
2. It should be light in weight and compact in size.
3.The voltage of the battery should not change much during its use.
4. It should provide power for longer time.
5. It should be rechargeable.
Characteristic terminologies of a battery;
I. current;
Current is the rate at which the battery is discharging. For an
efficient working of the cell there must be a large quantity of electro active
species which help rapid electron transfer reaction.
II. Voltage:
The voltage available from a battery depends on the e.m.f of the cell which
constitute the battery system. It is given by the Nerns’t equation
E cell = E° cell – 2.303 RT log Q
nF
Q is the ratio of the products of the molar concentrations of product
molecules to that of reactant molecules.
III. Capacity:
The capacity is the amount of electricity that may be obtained from the
battery and is given in ampere hours. (Ah). This depends on the size of the
battery which is determined by the Faraday relation C = wnF
M
Where W is the mass, M is the molar mass of the active material and C is the
capacity in ampere hours.
IV. Energy Density:
The ratio of the energy available from a cell or battery to its weight (volume)
is referred to as energy density. It is expressed as
avg

Energy density = i t E cell

Where t is the time taken at the fixed current i to reach an average voltage E.
It is measured by determining the capacity and recording the average voltage
and the total weight of the battery.

V. Electric Storage Density:

In the measure of charge per unit weight stored in the battery i.e., 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.
VI. Power Density:
The ratio of power available from a battery to its weight (w /kg) or volume
(w/ l) is called the power density.
VII. Energy efficiency:
The energy efficiency for storage batteries is given by
% energy efficiency = energy released on discharge x 100
Energy required for charge
VIII. Cycle life:
Primary batteries are not rechargeable but secondary batteries are
rechargeable and their cycle life must be high
Cycle life = Number of charge
Number of discharge
IX. Shelf life:
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.
Classification of Batteries :
Batteries are classified into three types
a) Primary battery:
These are the batteries in which the cell reaction is irreversible. After
some times cell reaction stops and cell becomes dead. For this reason
primary cells can not be recharged and reused.
Ex; Zn-Hg cell, Zn- MnO2 cell ,etc
b) Secondary batteries:
These are the batteries in which the cell reaction is completely
reversible. The cell can be recharged by passing electric current through
them after every use. As a result a secondary cell can be used again and
again for a long time .
Ex: a) Lead – Acid battery
b) Ni – Cd battery
c) Reserve batteries:
The batteries which may be stored in an inactive state and made ready
for use by activating them prior to the application are referred to as the
reserve batteries.
Ex: Mg-water activated batteries
Zn-Ag2O batteries, etc.
Classical Batteries:
i) Zn-MnO2 Cell (Dry cell):
Construction:
 The dry cell is a primary cell, since various reactions involved can not be
reversed by passing electricity. Which consists of Zn-container acts as
anode. A graphite rod acts is placed in the center but does touch the base acts
as cathode. The space between the anode and cathode is so packed that Zn-
container is filled with the paste of NH4Cl and ZnCl2 and graphite rod is
surrounded by MnO2 powder and carbon. The graphite rod is fitted with a
metal cap and the cylinder is sealed at the top with pitch. Zn container is
covered with cardboard so that the container may be protected from the
atmosphere.
The dry cell is represented as
Zn/Zn2+,NH4+/ MnO 2,C
Cell reactions: The following reactions are takes place in the cell
At anode;
Zn Zn2+ + 2e –
At cathode;

2MnO2(S)+H2O(l)+2e – Mn2O3(s)+2OH -(aq)

2NH4+(aq)+2OH - (aq) 2NH3(g)+2H2O(l)
ZnCl2(S)+2NH3(g) [Zn(NH3)2Cl2]
The net reduction reaction at cathode is
2MnO2(S)+2NH4+(aq)+ZnCl2(s)+2e-
Mn2O3
(s)+H2O(l)+[Zn(NH3)2Cl2]

Net cell reaction;

Zn (s)+2MnO2(s)+2NH4+(aq)+ZnCl2(s)
Mn 2O3
2+
(s)+H2O(l)+Zn (aq)+[Zn(NH3)2Cl2]
The cell potential is in the range of 1.25to1.5V
Application : dry cell finds application in flashlights, transistor radios,
calculators, electronic watches, etc.
ii) Lead – Acid battery (Lead storage battery)

Construction:

It is the most frequently used battery in automobiles. It consists of six

voltaic cells connected in series. In each cell anode is made of spongy lead
and cathode is a grid of lead packed with lead dioxide. The electrolyte is the
aqueous solution of H2SO4 which is 38% by mass. Anode and cathode are
arranged alternatively.
The cell representation is
 Pb(s),PbSO4(s)/H2SO4(38%)/PbO2(s),Pb(s)

Cell reactions:
a. The following reactions take place in lead storage battery during
discharging.
At anode;
Pb (s) Pb2 + (aq)+2e -
Pb2+ (aq) +SO42- (aq) PbSO4(s)
Pb(s) +SO42- (aq) PbSO4(s) +2e -
At cathode;
Pbo2(s) +2e-+4H+ (aq) Pb2+ (aq)+2H2O(aq)
Pb2+ (aq) +SO42-(aq) PbSO4(s)
Pbo2(s) + 4H+(aq) +SO42-(aq) +2e - PbSO4(s)+2H2O(aq)
Net cell reaction;
Pb (s) + PbO2(s) + 4H+(aq) + 2SO42-(aq) 2PbSO4(s) +
2H2O(l)
During the working of the cell, the concentration of H2SO4 decreases
as SO42- ions precipitated as PbSO4. With the decrease in the concentration
of H2SO4, the density of the solution also decreases.
The condition of the battery can easily checked by measuring the
density of the solution when the density falls below 1.20 gm/cm3, the battery
require recharging.
b. The following reactions take place in lead storage battery during
Recharging: The battery can be recharged by connecting it to an external
source of direct current. It would reverse the flow of electrons resulting in
the deposition of Pb on the anode and PbO2 on the cathode.
The charging reaction is as follows.
PbSO4(s) + 2 H2O (l) Pb(s) + PbO 2 (s) + 4H+(aq)+
2SO42-(aq)
Applications: Lead acid storage batteries are used for many purposes such as
automobiles, gas engine ignition, in telephone exchanges, railway trains,
mines, laboratories, hospitals broadcasting stations etc.,
iii) Nickel – Cadmium Battery:
This is also a secondary battery. It consists of Cd anode and metal grid
containing NiO2 as cathode. These electrodes immersed in KOH solution
which acts as electrolyte.
Cell reactions:
At anode:
Cd(s) → Cd+2(aq) + 2e-
Cd+2 (aq)+ 2OH-(aq) → Cd(OH)2 (S)
Cd (S) + 2OH-(aq) → Cd (OH)2(s) + 2e -
At cathode:
NiO2 (s) + 2e- + 2 H2O (l) Ni (OH)2 (s) +2OH-(aq)
The net cell reaction.
Cd(s) +NiO2(s) +2 H2O (l) Cd
(OH)2(s)+Ni(OH)2(s)
The reaction can be readily reversed because the reaction products Ni
(OH) 2 and Cd(OH)2 deposit to the electrode surfaces.
Ni-Cd battery is a portable re-chargeable cell and its cell voltage is
fairly constant of about 1.4 V
Like dry cell it can be packed in a sealed container. No gases are
produced during charging or discharging.

Applications: It is used in electronic calculators, electronic flash unit,

cordless electronic shavers, transistors and other battery powered small
tools.

Modern batteries:
 i) Zn-air battery
Zn battery belongs to the class of air- metal battery, which uses
oxygen from the atmosphere to produce electrochemical energy. It
offers very high energy density because the oxygen does not
contribute to the mass of the battery. This consists of porous carbon
plate as cathode rectangular flat plates of zinc as anode are placed on
either side of the cathode. The electrodes are immersed in 20% NaOH
which acts as electrolyte. The outer container is made up of glass or
ebonite.
The cell is represented as
Zn / NaOH (5M) / air, C
Cell reactions:
At anode;
Zn →Zn2+ +2e-
Zn2+ + 2OH →ZnO+H2O
Zn + 2OH→ZnO+H2O+2e-
At cathode;

½ O2 +H2O+2e-→2OH
The net reaction;
Zn + ½ O2→ ZnO
The cell produces an open circuit potential of 1.4V.
During charging the above reaction is reversed.
Application ;
1. It is used as a power source for hearing aids.
2. used in electronic pagers
3.used in military radio receivers and Railway Station.

ii) Nickel-Metal hydride battery

The active material for anode is a metal hydride such as VH2,ZrH2 and
TiH2 with a hydrogen storage metal alloy such as LaNi5 or TiNi. The active
material for the cathode is NiO(OH). An aqueous solution of KOH acts as
the electrolyte and polypropylene is used as the separator. Anode and
cathode are stacked alternatively in a stainless steel container and connected
in series to get the desired voltage.
The battery is represented as
MH / KOH (5.35M) / Ni(OH)2. Nio(OH)
The reaction during the discharge are given by
At anode: MH + OH → M +H2O + e-
At cathode: NiO (OH) + H2O + e- → Ni (OH)2 + OH
Net reaction MH + NiO (OH) → Ni (OH)2 + M
During the charging the above reaction is reversed. The open circuit
potential of the cell ranges from 1.25 – 1.35 V.
Application:
1) It is used is consumer electronic devices such as cellular phones,
computers other portable devices.
iii) Lithium – MnO2 Battery:
It consists of Lithium anode and manganese dioxide cathode. A solution of
lithium halide in organic solvent served as the electrolyte. The manganese
dioxide palate and lithium anode disc are separated by a no woven poly
propylene separator.
The electrode reaction
At anode: LI → Li+ + e-
At cathode MnO2 + Li + + e - → LiMnO2
Net cell reaction: Li + MnO2 → LiMnO2
Application: It is used in variety of application such as memory backup,
safety and senility devices, watches, calculators, automotive cameras and
many consumer electronic devices.