Applications: largely used in high current applications

Chapter – 3: Conventional secondary batteries: Nickel-

Cadmium (alkaline) and Lead-acid secondary batteries such as in power tools and computer power supply units;
used in calculators, electronic flash units, cordless
Secondary batteries act as electrochemical cell during
discharge, and act as electrolytic cell during charging. electronic shavers, etc; NiCd is preferred over NiMH for
TV remote control where the current draw on the battery is
(a) Nickel-Cadmium (NiCd) batteries consist of:
lower than the battery's own self-discharge rate.
Anode: Cadmium
Cathode: Nickel (III) oxide-hydroxide [NiIIIO(OH)]
(b) Lead-acid battery: (i) Structural description:
Separator:
Electrolyte: KOH alkaline electrolyte.
Electrochemical reaction: Anode half-cell reaction
(discharging from left to right and charging from right to
left):
discharging →
Cd (s) + 2 OH - ( a q ) Cd(OH ) 2 (s) + 2 e-
←charging

Cathode half-cell reaction:

discharging →
2 NiIIIO(OH) (s) + 2 H2O (l) + 2 e- ←charging
2NiII(OH)2(s) + OH-(aq) A number of lead (-ve) plates and lead dioxide (+ ve) plates
placed alternately are connected separately in parallel
The net cell reaction:
circuits. The entire combination is then immersed in 20%
discharging →
Cd (s) + 2 NiIIIO(OH) (s) + 2 H2O (l) ←charging
Cd(OH)2(s) dil. H2SO4 corresponding to a density of 1.2 to 1.3.
II
+ 2Ni (OH)2(s)
(ii) Lead-acid batteries consist of:
Cell definition: Cd,Cd(OH)2|KOH|NiO2,Ni(OH)2,Ni Anode: Lead, Pb
Important Characteristics: The discharge reaction can be Cathode: Lead dioxide, PbO2
readily reversed because the reaction products, Cd(OH)2 (s)
and Ni(OH)2 (s) adhere to the electrode surface; cell voltage Separator: rubber or glass fiber
is 1.4V; Self-discharge rate is 10% per month; working Electrolyte: 20% dil. H2SO4
temperature range is −20°C and 45°C; If the anode
electrode is overcharged, hydrogen gas is produced; If the (iii) Electrochemical reaction during discharging:
cathode electrode is overcharged, oxygen gas is produced. PbSO4 is precipitated at both the electrodes during the
Advantages: The NiCd batteries have a safety sealing discharging process.
value to release excess heat and gases produced during the At Anode (-ve) At Cathode (+ve) (reduction):
charging cell reaction; the cell can be re-charged within 15 (oxidation):
PbIVO2 (s) + 4 H+ (aq) + 2 e- →
minutes; can supply high surge currents suitable for power Pb (s) → Pb + 2e
2+ -
Pb2+ + 2H2O (l)
tool applications; energy density is higher than lead-acid
Pb2+ (s) + SO42-(aq)→ PbSO4↓ Pb2+ (s) + SO42-(aq) → PbSO4↓
battery; lasts longer, in terms of number of
charge/discharge cycles (around 2,000 cycles) than other The net cell reaction during discharging:
rechargeable batteries; can be stored in the deep-discharge Pb (s)) + PbIVO2 (s)+ 4 H+ (aq)+ 2 SO42-(aq) → 2 PbIISO4↓ +
state for long time whereas lithium ion batteries will be 2H2O (l) + Energy
permanently damaged if discharged below a minimum (iv) Electrochemical reaction during charging: When
voltage. both anode and cathode are covered with PbSO4
Disadvantages: High cost; Cadmium is toxic to dispose; precipitate, the voltage output decreases. Hence, the
energy density of NiCd battery is lower than Ni-MH and discharged reaction products are reversed back to Pb and
Li-ion batteries. PbO2 by charging the battery with more than 2 volts from
a electron generator (dynamo). The function of the
generator is to force the electrons (generated during the Chapter – 4: Advanced secondary batteries: Nickel-
motion of the car) into the electrochemical cell causing the Metal hydride and Lithium-ion secondary batteries
charging reaction to take place that restores the original (a) Nickel-Metal hydride batteries: The reactions are
reactants of the cell. similar to the nickel-cadmium reactions except that it uses
a hydrogen abosorbing alloy as the negative anode
At Cathode (-ve) At Anode (+ve) (oxidation): electrode. The H2 gas is adsorbed over the metal alloy to
(reduction): yield a metal hydride (MH), therby allowing H2 to
PbSO4↓ + 2H2O (l) – 2e- →
PbSO4↓ + 2 e → Pb (s) + SO42-(aq)
-
PbIVO2 (s) + 4 H+ + SO42- participate in reversible reactions.

The net cell reaction during charging: (a) Nickel-Metal hydride batteries consist of:

2 PbSO4↓+ 2H2O + Energy → Pb (s)) + PbO2(s)+ 4 H+ (aq)+ 2 SO42-(aq) Anode: Hydrogen adsorbing metal alloys (MH) of AB5
type, where A = La and Ce; B = Ni, Co, Mn or Al.
Cell type: Pb,PbSO4|H2SO4(aq)|PbO2,Pb
Cathode: Nickel oxide hydroxide [NiO(OH)]
Advantages: ability to supply high surge currents;
Separator: fine fibers
maintain a relatively large power-to-weight ratio; can be
recharged by being exposed to an external potential Electrolyte: aqueous KOH electrolyte (does not take part
through electrolysis. in the reaction)
Disadvantages: it is heavy, and sulfuric acid is corrosive Electrochemical reaction during discharging and
and can spill. charging:
Applications: mainly used in automobiles, gas engine Anode half-cell reaction:
ignition, emergency lightening, nuclear submarines, etc. discharging →
MH (ab) + OH-(aq) ←charging
M (s) + H2O (l) + e-
Six 2V cells connected in series make up a 12V battery.
Cathode half-cell reaction:
To obtain high current output from the battery, the surface discharging →
area of the electrodes in contact with the electrolyte must NiIIIO(OH) (s) + H2O (l) + e- ←charging
NiII(OH)2(s) + OH-(aq)
be large & the plates close together. The net cell reaction:
Important aspects of the Lead-acid battery: discharging →
MH (ab) + NiIIIO(OH) (s) ←charging
M (s) + NiII(OH)2(s)
Important characteristics: (i) During discharge, the
(Where M = Hydrogen absorbing alloy and H (ab) =
concentration of acid decreases whereas during the
charging process, the concentration of acid increases. adsorbed hydrogen)
Hence, the degree of discharge can be checked by
measuring the density of the fluid in it with a hydrometer.
The density of a fully charged battery should be ≥1.2
g/cm3. Therefore, the amount of charge left is directly
proportional to the sulfuric acid density in the battery.
(ii) People living in cold climates have trouble in starting
their cars. Since, the lowering of temperature causes
insignificant change in the output voltage, the real reason
for battery breakdown in sub-zero conditions is the
increase in viscosity of the electrolyte as the temperature
decreases. As the battery discharges and the concentration
of sulfuric acid decreases, water formed as the byproduct
is more likely to freeze during winter weather. Any Important Characteristics: since the KOH electrolyte
increase in viscosity of the electrolyte is going to affect the does not take part in the reaction, there is no change in the
movement of ions between the electrodes and hence volume of the electrolyte; if excessive heat or pressure
current generation is affected. This situation is avoided by builds up, the cells have a safety vent and hydrogen will be
adding anti-freezing agents or warming the battery to room emitted from the vent in the event of serious overcharging;
temperature in order to deliver normal power. During excessive overcharging of the cathode electrode,
oxygen is evolved which is successfully reduced by the
hydrogen adsorbing metal alloy anode electrode thereby
keeping the internal pressure at constant.
Advantages: The Metal alloys used as anode has the
ability to capture and release hydrogen in volumes up to
1000 times their own volume; Can store about 30 – 40 %
more energy capacity than Ni-Cd; cooler storage
temperatures leading to slower discharge rate and longer
battery life; less toxic than Ni-Cd; Ni-MH can be
repeatedly charged and discharged for about 500 cycles;
Rapid recharge in 1 hour; when the internal pressure rises
due to overcharge, short-circuiting and reverse-charging,
the self-resealing safety vent is activated to prevent battery
damage.
Disadvantages: the rate of self-discharge is faster than Ni-
Cd and Li-ion batteries; Compared to Li-ion, the energy
density is also lower. Repeated recharging at high and low
temperatures causes the battery performance to deteriorate.
Repeated overcharge should be avoided since it will
downgrade the battery performance.
Applications: Ni-MH battery is used in all-electric plug-in
vehicles manufactured by Toyota, Honda, Ford and others;
used in cell phones, camcorders.
(b) Lithium-TiS2 batteries:
Anode: Li (s)
Cathode: TiS2
Electrolyte: Poly-2-vinylpyridiene (P2VP) solid electrolyte
Electrochemical reaction
Anode half – cell reaction : Oxidation: Li (s) → Li+ + e−
Cathode half – cell reaction : Reduction: TiS2 (s) + e− → TiS2-
Therefore, the net cell reaction is: Li (s) + TiS2 (s) → Li+ + TiS2-
Characteristics: P2VP is a solid organic charge transfer
complex which permits transfer of ions but not the transfer of
electrons; cell voltage is 3 V; TiS2/Li battery is
thermodynamically stable; Li is light weight, only 7 g of
Li produces 1 mole of electrons; all the constituents of the
battery are solid and hence no risk of leakage from the
battery; can be made in a variety of shapes and sizes.
Disadvantages: Formation of a passivating layer on the
lithium anode can result in dendrite formation on recharge;
Lithium batteries can provide extremely high currents and
can discharge very rapidly which can result in overheating
of the battery, rupture, and even explosion. Hence, lithium
batteries incorporate safety vents in order to prevent
explosion; Because of the above risks, transport of lithium
batteries by air is restricted; expensive to manufacture.
Applications: used in portable consumer electronic
devices, as backup batteries in computers and
communication equipment, lithium batteries can easily
support the brief, heavy current demands of devices such
as digital cameras, and they maintain a higher voltage for a
longer period than alkaline cells; self-discharge is less than
half compared to Ni-Cd batteries.
(c) Lithium-Sulphur batteries:
Anode: Li (s)
Cathode: carbon rod + sulphur (as electron acceptor)
Electrolyte: β - Alumina (NaAl11O17) solid electrolyte
Electrochemical reaction
Anode half – cell reaction : Oxidation: 2 Li → 2 Li+ + 2 e−
Cathode half – cell reaction : Reduction: S + 2 e− → S2-
Therefore, the net cell reaction is: 2 Li + S → 2 Li+ + S2-
Characteristics: The S2- formed during the cathode reaction
reacts with elemental sulphur to form the polysulphide ion.
S2- + n S → [Sn+1]2-
The function of β - Alumina
electrolyte is to allow only
the Li+ ions to migrate from
anode to cathode through its
lattice but does not allow the
bulky polysulphide ion from
cathode to anode. Therefore
the direct reaction between Li
and S detrimental to current
production is prevented by the intervening alumina in the cell.
Advantages: 2.5 to 1.7 non-linear output voltage; lighter weight
than lead-acid battery; low cost of sulphur; high energy density;
used in electric cars The lithium-sulfur cell can get an electric
car 400 miles for a single charge.
Disadvantages: This battery must be operated at high
temperatures as S and Li must be in their molten states for the
operation of cell reaction. Since sulphur lacks electro
conductivity, the carbon coating on the sulfur then provides the
electroconductivity missing from pure sulfur; intermediary
polysulfides are soluble in the electrolytes which causes
irreversible loss of active sulfur material.