BATTERIES

It is a device where chemical energy is converted into electrical energy or in other words a
battery is an electrochemical cell or series of cells that produces an electric current. Batteries
consist of cells.

Cell - single unit consisting of two electrode , electrolyte and current collectors.

 A spontaneous redox reaction occurs producing electrical energy.

 The half cell reactions occur separately at the electrodes – oxidation at anode and
reduction at cathode.

 A voltage is generated because of the difference in the potentials between the two
electrodes.

Battery - Several cells connected together form a battery. The connection can be made in series
or parallel.

Connections in parallel: Cells are said to be connected in parallel when they are joined
positive to positive and negative to negative such that current is divided between the cells. The
final voltage of the battery remains unchanged while the capacity is increased.

Parallel connection of four 3.6 V Li-ion cells

The emf of the battery is the same as that of a single cell.The current in the external circuit is
divided equally among the cells.

Connections in series : Cells are connected in series when they are joined end to end so that
the same quantity of electricity must flow through each cell. The final voltage is the sum of all
battery voltages added together while the capacity remains unchanged.

1
 Series connection of four 3.6 V Li-ion cells

Adding cells in a string increases the voltage; the capacity(A/Hr) remains the same.

The emf of the battery is the sum of the individual emfs. The current in each cell is the same
and is identical with the current in the entire arrangement.

Types: Primary and secondary batteries.

Primary batteries Secondary batteries

Chemical reactions are irreversible Chemical reactions are reversible
Reaction product cannot come back to original Reaction product come back to original form
form
Once use battery Recharged and reused
Ex: Lechlanche cell or drycell, lithium primary Ex: Lead acid, Ni-Cd, Ni-metal hydride
battery battery, lithium ion battery.

BATTERY CHARACTERISTICS

Batteries are designed and manufactured for a particular duty. For e.g., to power a torch, for
starting a car or bike, or for an uninterrupted power supply (UPS). For each application the
requirement is different.

Requirements of a car traction battery::

 Voltage : 90-400V
 Size : 0.1 to 0.5m3
 Rechargeable – should be able to withstand at least 1000 charge discharge cycles and
also overcharging.
Requirement for SLI (start – lighting- Ignition) automobile batteries
 Voltage 12V
 Usage may be intermittent of prolonged use with uneven demand
 Enough capacity to power head lights, AC, music system.

2
Requirement of battery for computer volatile memory:
 Voltage – 1-3V
 Size – few cm3
 Need not be rechargeable.

In order to judge whether a battery is suitable for a particular application or to design a

battery for a specific purpose, there are a set of defined characteristics which can be measured
and specified.
BATTERY PERFOMANCE CHARACTERISTICS

1. Voltage - The terminal voltage of a cell depends on the free energy change of the cell
reaction, and therefore on the electrodes used, kinetics of electrode reactions and cell
internal resistance.
Ecell = E0 C – E0A - ƞA - ƞC - iRcell

Where the ηA and ηc are over potentials for anode and cathode reactions. And iR cell is the
internal resistance of the cell. EOC and EOA are the standard electrode potentials of anode and
cathode.

The overpotentials for the cathode and anode reactions are caused by:

 Concentration overpotential – due to depletion of electroactive species at the

electrodes, this in turn is due slow diffusion of ions in the electrolyte. Current withdrawn
at a faster rate causes concentration over potential. This is cab be minimized by (i) by
using electrolytes containing ions with high transport number, (ii) by avoiding withdrawal
of higher currents than prescribed for the given battery system.

 Activation overpotential – due to slow electron transfer between the electrodes and
active species. By making right choice of electrode materials this can be minimised.
Internal resistance in the cell can be minimised by using highly conducting current
collectors, electrolytes and reducing the interelectrode gap.

Cut-off Voltage – The minimum allowable voltage. It is this voltage that generally
defines the “empty” state of the battery.

2. Capacity or Nominal Capacity (Ah for a specific C-rate) – It is the charge that can be
obtained from a battery. It depends upon size of the battery.
The coulometric capacity, the total Amp-hours available when the battery is discharged at a
certain discharge current (specified as a C-rate) from 100 percent state-of-charge to the cut-off
voltage. Capacity is calculated by multiplying the discharge current (in Amps) by the discharge
time (in hours) and decreases with increasing C-rate.

3
C- and E- rates – In describing batteries, discharge current is often expressed as a C-rate in
order to normalize against battery capacity, which is often very different between batteries.
 A C-rate is a measure of the rate at which a battery is discharged relative to its
maximum capacity.
 A 1C rate means that the discharge current will discharge the entire battery in 1 hour.
For a battery with a capacity of 100 Amp-hrs, this equates to a discharge current of 100
Amps.
 A 5C rate for this battery would be 500 Amps, and a C/2 rate would be 50 Amps.
Similarly, an E-rate describes the discharge power.
 A 1E rate is the discharge power to discharge the entire battery in 1 hour.

C = i x t Ampere hour.

If the capacity of a battery is 10 Ah it signifies that if a load connected to the battery withdraws
1A current, the battery will last for 10 hrs.

If the load withdraws 0.5A current, the battery will last for 20 hrs.

3. Specific Energy (Wh/kg) – The nominal battery energy per unit mass, sometimes referred
to as the gravimetric energy density. Specific energy is a characteristic of the battery chemistry
and packaging. Along with the energy consumption of the vehicle, it determines the battery
weight required to achieve a given electric range.

4. Specific Power (W/kg) – The maximum available power per unit mass. Specific power is a
characteristic of the battery chemistry and packaging. It determines the battery weight
required to achieve a given performance target.

5. Energy Density (Wh/L) – The nominal battery energy per unit volume, sometimes referred
to as the volumetric energy density. Specific energy is a characteristic of the battery
chemistry and packaging. Along with the energy consumption of the vehicle, it determines
the battery size required to achieve a given electric range.

6. Power Density (W/L) – The maximum available power per unit volume. Specific power is a
characteristic of the battery chemistry and packaging. It determines the battery size required
to achieve a given performance target.

7. Cycle life:
A secondary battery is expected to be capable of repetitive charge and discharge cycles. The
cycle life is the number of charge and discharge cycles that are possible before failure
occurs.
In a charge discharge cycle it is essential that the active material is reformed in the correct
chemical composition, morphology and distribution on the electrodes for further discharge.
The cycle life strongly depends on the depth of discharge. Complete discharge of a battery
are damaging to the electrodes. The common causes of failure are (i) Corrosion of current

4
 collectors and plates (ii) Shedding of active material from the plates (iii) Shorting due to
dendritic growth between the electrodes (iv) Changes in morphology.

8. Shelf life:
Applies to primary batteries. This denotes the period of storage before its usage. Shelf life of
a battery is reduced due to self discharge.

PRIMARY BATTERIES

Batteries that are designed for one use.

ZINC - CARBON BATTERIES

Have been in use for more than 100 years. Widely used for low power applications: flash lights,
clocks, remote control, toys, shavers etc. The batteries utiliseZn-MnO2 chemistry for
generating electrical energy Their open circuit voltage is 1.5V.

The zinc carbon battery is marketed as general purpose (lechlanche cell) or also called dry
cell.Other variants of lechlanche cell that are based on the Zn-MnO2 chemistry are the heavy
duty or super heavy duty (Zinc Chloride cells) and the alkaline batteries

They are available in various sizes and hence with different capacities.

5
LECHLANCHE CELL

CONSTRUCTION

 The zinc serves as both the container and the anode.

 The manganese dioxide/carbon mixture is wetted with electrolyte and shaped into a
cylinder (bobbin shape) which has a hollow at the centre.
The electrolyte is a solution with the following composition:
NH4Cl 26.0%

ZnCl2 8.8 %

H2O 65.2 %

Corrosion inhibitor 0.25 - 1.0 %

 A carbon rod is inserted into the centre of the bobbin, which serves as a current collector.
It is also porous to allow gases to escape, and provides structural support.
 The separator is either cereal paste or treated absorbent kraft paper. The paste is in a gel
form which holds the electrolyte.

6
LECHLANCHE CELL COMPONENTS AND ROLES

Components Roles

Zinc can Anode

Carbon rod Cathode current collector

Bobbin shaped MnO2 Cathode material also called cathode

cathode material depolariser. Without MnO2, the cathode
Natural ore – 70-85% reaction would be evolution of H2 gas
Synthetic - 90-95% which is undesirable as it will get
adsorbed on the carbon cathode and
Electrolytic MnO2 increase its resistance. It may also lead
to pressure buildup in the battery.
Hence MnO2 is called the cathode
depolariser.

Graphite powder Added to improve conductivity of

MnO2(poor conductor)

Electrolyte NH4Cl - 26% Increases the conductivity of the

electrolyte.

ZnCl2 - 8% The product of the cell reaction is

alkaline. ZnCl2 being acidic helps in
maintaining the pH which is necessary
to maintain the gel structure of the
electrolyte.

H2O - 65%

Dichromate, chromate Zinc undergoes self corrosion and

salts 1% hence reduces the shelf life of the
battery. The dichromate salts act as
corrosion inhibitors by forming a
passive oxide film on Zinc.

Separator Kraft paper coated with Holds the electrolyte in a gel form and
cereal paste( wheat flour acts as an electronic insulator between
and starch) the anode and cathode.

7
 Gelled paste cereal paste

Electrical contacts

The terminals of the battery, are tin plated steel or brass. They aid in conductivity and
prevent external exposure of the zinc.

Seal

The battery is sealed using asphalt pitch, wax/resin mix, or plastic (usually
polyethylene or polypropylene) An airspace is usually left between the seal and the
cathode to allow for expansion. The function of the seal is to prevent evaporation of
the electrolyte, and to prevent oxygen entering the cell and corroding the zinc.

CELL CHEMISTRY

The probable half-cell reactions are:

Anode: Zn → Zn2+ + 2e–
Cathode: 2MnO2 +2H2O + 2e– → 2MnO(OH) + 2OH-
The OH- ions generated at the cathode migrate to the anode and combine with the Zn2+
ions and form Zn(OH)2 which increases the pH. The acidic ZnCl2 combine with the
hydroxide to form a neutral complex.
Zn(OH)2 + ZnCl2 → neutral complex
2MnO(OH) + Zn(OH)2 → ZnO + Mn2O3 + 2H2O
Sometimes the ammonium ions react with the hydroxide to give free ammonia. This
happens especially when high current is withdrawn.,
NH4+ + OH- → NH3 + H2O
The ammonia combines with the ZnCl2 to form a complex.
ZnCl2 + 2NH3 → Zn(NH3)2Cl2
The overall reaction in the cell is:

Zn + 2MnO2 → ZnO + Mn2O3

8
 BATTERY CHARACTERISTICS
 Open circuit voltage – 1.5V.

Electrode potential of zinc is – 0.76 V and that of manganese dioxide is 1.23V.

Therefore, theoretical voltage of each cell Ecell= 1.23-(-0.76) = 1.99 V but due to
polarisation the actual voltage of a standard zinc carbon battery is not more than 1.5
V.

 Low energy density

 Voltage falls steadily with discharge.
 Low efficiency under high current drain.
 Service Life: 110 min (if used continuously). But, it is designed for intermittent
use. For best capacity it should be used intermittently and removed from the
device when not required.
 Comparitively poor shelf life: ~ 1 – 2 years (at room temperature). Shelf life
can be improved it refrigerated.

SECONDARY BATTERIES

Secondary batteries are those which are rechargeable.

LEAD ACID BATTERY

The lead acid battery is the most used battery in the world. The most common is the SLI
battery used for motor vehicles for engine Starting, vehicle Lighting and engine Ignition,
however it has many other applications (such as communications devices, emergency lighting
systems and power tools) due to its cheapness and good performance.

It was first developed in 1860 by Raymond Gaston Planté. Strips of lead foil with coarse
cloth in between were rolled into a spiral and immersed in a 10% solution of sulphuric acid. The
cell was further developed by initially coating the lead with oxides, then by forming plates of lead
oxide by coating an oxide paste onto grids. The electrodes were also changed to a tubular
design.

Fabrication:

Lead grids (plates) are coated with a paste of lead monoxide (PbO) and dilute sulphuric acid
and dried. Alternate plates are attached to two common terminals. Microporous PVC sheets are
placed between the plates to separate them from each other. (The separator are usually
cellulose, PVC, rubber, microporous polyethylene or non-woven polypropylene). This assembly
is housed in a PVC container and the top is closed with a PVC lid and sealed using pitch.
Suitable vents are provided for filling up of the electrolyte. The vents are closed with plastic caps
having small holes. Sulphuric acid of specific gravity 1.2 – 1.4 is filled up in the container.

9
Several such assemblies can be connected in series to increase the voltage to suit the
requirement. In practice, most cells contain upto 30 plates with separators between.

First Charging:

The common terminal of one set of plates is attached to positive and the other set to the
negative terminal of a DC power source. The PbO coating on the plates, connected to positive
terminal is oxidised to spongy porous electroactive lead dioxide (PbO2) while the PbO on the
other set of plates, connected to negative terminal, is reduced to spongy electroactive lead.

PbO2
+
(O)
Pb PbO
(R)

Pb

The physical state of these coatings is entirely different from that of lead or lead dioxide which
are not electroactive. The conversions occur only during the first charge of the battery. Actually
the battery plates are formed only during first charge.

– +
The cell notation is Pb/H2SO4/PbO2 . These plates are now ready for discharge.
10
Reactions during discharge:

At anode: This is the negative plate and hence lead undergoes oxidation as:

Pb Pb2+ + 2e-

Pb2+ + SO42- PbSO4

Pb + SO42- PbSO4 + 2e- ………….. (1)

At cathode: This is the positive plate and lead dioxide undergoes reduction as:

PbO2 + 4H+ + 2e- Pb2+ + 2H2O

Pb2+ + SO42- PbSO4

PbO2 + 4H+ + SO42- + 2e- PbSO4 + 2H2O ………….. (2)

The total cell reaction is: [(1)+(2)]

Pb + PbO2 + 4H+ + 2SO42- 2PbSO4 + 2H2O

(Pb + PbO2 + 2H2SO4 2 PbSO4 + 2H2O)

All these reactions are exactly reversed during charging

2PbSO4 + 2H2O Pb + PbO2 + 2H2SO4

11
Thus the overall process can be represented as:

+
PbO2
+ (R)
(O)
Pb PbO PbSO4
(R)

Pb (O)

Charging Discharging

Functioning :
1. Quantity of materials required: According to the overall cell reaction, one mole of lead,
one mole of PbO2 and two moles of sulphuric acid are required to generate two faradays of
electricity. But if theoretical quantities are taken, the specified Ampere hour cannot be
withdrawn because (i) The products PbSO4 and water are poor conductors of electricity (ii) The
acid gets progressively diluted. Therefore the internal resistance often cell increases
enormously. Similarly, when the entire quantity of lead and PbO2 are converted to PbSO4,
recharging becomes almost impossible. Hence when 60-65% of the current is withdrawn from
the battery, the recharging should be done or excess quantity of the material over the theoretical
quantity should be taken. In practice, 1.6-1.7 times higher than the theoretical amount is taken
in the battery. Virtually, an 80 Ah battery has materials theoretically required for a 130 Ah
battery.
2. Discharge: Lead acid battery is designed for heavy current output. Two kinds of
coatings are given in these batteries depending on the end use. A thin coating over a large area
is given for a very high current output in unit time. These become possible because the acid can
percolate easily through a thin coating and react with a large surface area underneath producing
a high current. A battery of this type is necessary for starting automobile engines, aviation
engines and railway engines. On the other hand, a thick coating over a smaller area gives
sustained low or medium current for a long duration. A battery of this type is mainly used in
laboratory work. Batteries which are used in UPS back-up power supply employ moderately
thick coatings because the power demand and the frequency of demand are quite uncertain.
Accordingly, the battery manufacturers specify the optimal discharge rate on the battery
depending upon the type of coating employed. For example, an 80 Ah battery may have an
efficiency between 85 – 90% when its discharge does not exceed 8A. If a higher current is
withdrawn, the efficiency decreases exponentially. If too low a current is drawn, it also results in
a loss of efficiency because the self discharge rate becomes a significant part of the low ampere
output.
Open circuit voltage is 2V whenever a load is attached, irrespective of its magnitude. Voltage
decreases to 1.98 and then gradually decreases to 1.7V and thereafter the decreases to steep.
Hence there is no useful current can be taken from the battery below 1.7V. The battery has to
be then recharged. Therefore the working voltage range of the battery is 1.7 – 1.98V.
12
3. Performance

 The charging rate should be preferably 25-30% of the discharge rate specified or the
charging voltage should be between 2.1-2.3V.
 Overcharging amounts to charging at a higher voltage or charging for a higher period
than specified. This leads to scouring i.e., continuous evolution of hydrogen gas at
cathode damaging the porous coating.
 Undercharging leads to accumulation of PbSO4 on the plates, increasing the internal
resistance and makes it difficult to recharge.

4. Wrong polarity connection : During charging, the PbSO4 must be oxidised back to PbO2 on
the cathode and plates and PbSO4 must be reduced to Pb on the anode grids. During
discharge only 60-65% of active coating gets converted to PbSO4. The remaining 35% PbO2
will be present on the cathode plates and 35% Pb on the anode plates. If a wrong polarity
connection is given during charging, the lead sulphate will be reduced to Pb at the cathode
(instead of being oxidised to PbO2) gets mixed up with PbO2 present. Similarly, PbSO4 will be
oxidised to PbO2 at the anode gets mixed up with Pb already present.ie mix up of PbO 2 and
Pb occurs in both the electrodes. This gives rise to innumerous local cell formation and
heavy short circuiting results. Self discharge is heavy and the battery becomes dead in no
time.

13