Secondary Batteries

The batteries may be classified in many ways depending on their use, material, manufacturing
technology and power rating etc., however, they are broadly categorized as:
a) Lead Acid Batteries
b) Alkaline Batteries
- Nickel-iron battery
- Nickel-cadmium battery
Lead Acid Battery - Construction
A battery consists of a number of cells and each cell of the battery consists of positive and negative
plates, separated by separators, immersed in the electrolyte held in a container. The individual cells
are then placed in a battery container.

Parts of a Lead Acid Battery

i) Plates - A plate consists of a grid made of cast antimonial lead alloy which is covered with active
material. The grid not only serves as a support for the fragile active material but also conducts the
electric current. Active material on +ve plate is Lead Peroxide (PbO2) and on the -ve plate it is Pure
Lead (Pb) in sponge or porous condition. An individual cell has many plates joined by connector straps
to make separate groups (combs) of +ve and -ve plates which are then interlaced to reduce the
electrolytic path between them while the grouping of plates increases the effective area or the amount
of active material in contact with the electrolyte. The effect of this arrangement is equivalent to joining
many smaller cells in parallel resulting in decrease of internal resistance and increase in the cell
capacity. The number of -ve plates is one more than the +ve plates for better mechanical strength and to
ensure that both sides of a positive plate are used in the chemical reaction.
Positive plates are generally Plante type whereas the negative plates are generally Faure type. In the
Plante process the active material on the plates is formed electrochemically i.e. through repeated
electrolysis process while in making of Faure plates the active material paste is mechanically pressed
into the grid palettes.
ii) Separators - These are thin sheets of porous insulating material placed between the positive and
negative plates for preventing contact between them and thus avoiding internal short-circuiting of the
battery. These are made of especially treated cedar wood, glass wool mat, microporous rubber (mipor),
microporous plastic (miplast) and perforated PVC. In addition to good porosity to allow enough
diffusion & circulation of electrolyte, a separator must have high electrical resistance and mechanical
strength.
iii) Electrolyte - It is dilute sulphuric acid (H2SO4) which fills the cell compartment to immerse the
plates completely. It provides the media for flow of charges from one plate to another.
iv) Connecting Straps - The connecting straps in a cell, join together all +ve and the -ve plates to form
separate groups of +ve and -ve plates.
v) Post or Pillar - It is the upward extension from each connecting bar which provides for
series/parallel connections of individual cells to form the battery.
vi) Cell Container - It houses the electrolyte and the plates. Parts of the container are:
a) Bottom Grooved Support - These are raised ribs at the bottom of the container to support the
plates and hold them in position and at the same time protect them from short-circuiting that would
otherwise occur as a result of fall of active material from the plates on to the bottom of the container.
b) Vent Plugs or Filler Caps - These are made of polystyrene or rubber and are usually screwed
in the cell cover. Their function is to prevent escape of electrolyte but allow the free exit of the gas.
These can be easily removed for topping-up or taking hydrometer readings.
vii) Battery Container - It houses the cells and is generally made of thick walled GRP (Glass
Reinforced Plastic) or Vulcanized rubber, moulded hard rubber (ebonite), moulded plastic, ceramics or
celluloid. The container should have a good mechanical strength to withstand heavy shock & vibration
and the electrical insulation resistance to resist leakage currents.
viii) Connecting Bars - These are the antimonial lead alloy flat bars which joins the individual cells
together in series by connecting the positive pillar of one cell to the negative of the next one across the
top of the cell covers. These bars are of very solid construction especially in starting batteries because
they have to carry very heavy currents.
ix) Battery Terminals – The +ve and –ve terminals of a battery provide for cable connections to the
outside circuits. For easy identification, the negative terminal post is smaller in diameter than the positive
terminal post.
Chemical Changes

i) Discharging - The cell sends the current

through the external load, H2SO4 dissociates
into positive H2 and negative SO4 (sulphate)
ions. H2 ions move to anode and SO4 ions
move to the cathode and the following changes take place:
At cathode: Pb + SO4 = PbSO4
At anode : PbO2 + H2 + H2SO4 = PbSO4 + 2H2O
a) Both, anode and cathode become PbSO4 which is somewhat whitish in colour.
b) Due to formation of water(2H2O), specific gravity of acid decreases.
c) Voltage of the cell decreases.
d) The cell gives out energy.
ii) Charging - The electrical current (charging current) is passed in a direction reverse of discharge
current i.e. anode to cathode inside the cell. H2 ions move to cathode and SO4 ion move to the anode
and the following changes take place:
At cathode: PbSO4 + H2 = Pb + H2SO4
At anode : PbSO4 + SO4 + 2H2O = PbO2 + 2H2SO4
a) The anode becomes (PbO2) dark chocolate in colour and cathode becomes (Pb) grey
metallic lead (sulphate ions 'SO4' leave the plates and move back to the electrolyte).
b) Due to consumption of water, specific gravity of acid increases.
c) Voltage of the cell rises.
d) The cell stores energy.
Charging / discharging of the cell can be represented by a single reversible equation given below:
+Plate -Plate Discharge->> +Plate -Plate
PbO2 + 2H2SO4 + Pb = PbSO4 + 2H2O + PbSO4
<<-Charge
Alkaline Batteries - the two types of alkaline batteries in general use are:
a) Nickel-cadmium type
b) Nickel-iron type (Edison type)
Construction - The electrodes or plates of alkaline
cells are designed to be either of enclosed-pocket
type or open-pocket type. In the case of enclosed-
pocket type plates the active material is inside
perforated metal envelopes whereas in the other type
the active material is outside, directly in contact with
the electrolyte.
a) Nickel-cadmium Batteries
Active Materials:
i) Positive Plate is Nickel hydroxide Ni(OH)4 with
about 17% of graphite added to increase
conductivity and about 2% barium hydroxide added to increase the service life of the plates.
ii) Negative Plate is a mixture of cadmium or cadmium oxide and iron to which is added about 3% of
solar oil for stabilizing the electrode capacity. The use cadmium results in reduced internal resistance
of the cell.
iii) The electrolyte is 21% solution of caustic potash KOH (potassium hydroxide) to which is added a
small quantity of lithium hydrate LiOH for increasing the capacity of the cell.
Plates of the same polarity with their pockets filled are assembled into cells groups for which purpose
they are welded to a common strap having threaded post.
The number of positive plates is one more than the negative plates. Ebonite separating sticks are
placed between the positive and negative plates to prevent any internal short-circuiting.
The steel containers of the batteries are press-formed from steel and the joints are welded. The body
and the cover are nickel-plated and have a dull finish.
Chemical Changes

a) During Discharge - the electrolyte (KOH) splits into positive K ions and negative OH ions. K ions
go to anode and reduce Ni(OH)4 to Ni(OH)2. The OH ions travel towards the cathode and oxidize iron.
b) During Charge - just the opposite reactions take place i.e. K ions go to cathode and OH ions go to
anode.
Chemical changes can be written thus:

Potassium hydroxide Hydroxyl ions

KOH -> K+ + OH-

Nickel Hydrate
During Discharge
Positive Plate : Ni(OH)4 + 2K -> Ni(OH)2 + 2KOH
Negative Plate : Cd + 2OH -> Cd(OH)2
Cd hydroxide
During Charging Nickel Hydroxide

Positive Plate : Ni(OH)2 + 2OH -> Ni(OH)4

Negative Plate : Cd(OH)2 + 2K -> Cd + 2KOH
Charging / discharging of the cell can be represented by a single reversible equation given below:
+Plate -Plate Discharge->> +Plate -Plate
Ni(OH)4 + KOH + Cd = Ni(OH)2 + KOH + Cd(OH)2
<<-Charge
(hydroxyl ions (OH-), the charge carriers, move from one set of plates to another leaving the
electrolyte unchanged. SG, therefore, does not change appreciably)
Since there is no formation of water during the chemical action, therefore, there is no significant
change in SG of the electrolyte during charge/discharge of cells. Hence, the state of charge in the cell
cannot be ascertained by using a hydrometer.
New alkaline cells have a SG of 1190 which reduces to 1140 over the period 5-10 yrs depending upon
the duty cycle. The electrolyte is then changed completely or the battery is replaced.