What is an Electrochemical cell?

An electrochemical cell is a device which is

used to convert the chemical energy produced in a reduction-oxidation
reaction to electrical energy (during discharging) or a device in which the
electrical energy is converted to chemical energy thereby resulting in a
chemical reaction (during charging).
The electrode where oxidation occurs is called anode while the electrode where
reduction occurs is called cathode.
What is the function of the salt bridge in an electrochemical cell? A salt bridge is a U-
shaped tube filled with conc. solutions of KCl or K2SO4 or solidified solution of agar agar and
gelatin electrolytes. The tube has porous plugs at the ends, and the function of the salt bridge
is to allow the movement of ions from one half-cell to the other without mixing of the two
solutions thereby completing the inner circuit and also to maintain electrical neutrality.
Electrons flowing through the wire from anode to cathode complete the outer circuit of the cell.
Q. Why KCl salt bridge can’t be used for a cell made up of Ag and Pb (chlorides) half-
cells?
Ans.: The KCl-bridge cannot be used when any salt of lead, or silver is used in the cell
because lead chloride and silver chloride are insoluble in water.

Definition: Battery is an electrochemical device that stores chemical energy for latter
release as electricity in the form of direct electric current at a constant voltage.
Classification: Batteries can be classified into three main types : (i) Primary
(ii) Secondary Batteries and (iii) Fuel Cells.
Advanced Primary batteries: Alkaline and Lithium.

Advanced Secondary batteries: Ni-Metal Hydride, Lithium-ion.

Fuel Cells: Hydrogen – oxygen fuel cells (HOFC) or alkaline fuel cells
Solid oxide fuel cell (SOFC)

Mention a few differences between Primary and Secondary Batteries.

Primary battery Secondary battery
electrochemical cell reaction is electrochemical cell reaction is reversible
irreversible
The reactants cannot be The reactants can be regenerated by passing D.C. in
regenerated the opposite direction to the discharging direction
disposable after complete reusable after complete or partial discharge.
discharge; usable for only once.
Cheaper in cost Expensive than primary batteries
Higher charge density Lesser charge density
e.g. carbon-zinc (dry cell), e.g. Lead-acid, Ni-Cd, Ni-MH, Lithium-ion
alkaline and Lithium cells rechargeable cells
(i) Advanced Primary batteries:
(a) Alkaline battery: It is an improved form of the dry cell in which the NH4Cl is
replaced by KOH as the electrolyte.
Basic structure :
Anode (-ve terminal): made up of zinc powder (increased surface area for
increased rate of reaction and hence more electron flow) with the exposed
bottom as the negative (-ve) end of the battery.
Electrolyte: Potassium hydroxide (KOH, electrolyte) mixed at 35 to 50 wt.-%
with the zinc powder and a small quantity of a gelling material to get a thick
paste. A metal pin or a sheet (serving as electron collector) is inserted into the
anode mixture provide contact to the anode electrode.
Cathode (+ve terminal): made up of carbon (graphite) as positive (+ve) end
and mainly surrounded by electrolytically produced manganese (IV) dioxide
(MnO2) (higher purity than naturally available MnO2 used in Dry cell case) and
carbon powder (for increased conductivity).
The natural manganese (IV) dioxide (MnO2) used as a electrolyte in dry cells is
cheaper in cost and present in the form of mineral “insutite”, but its efficiency is
lesser than the electrolytically or chemically produced MnO2 used in alkaline
cells.
This is one of the reasons for higher performance of the alkaline cells
compared to the dry cells.
Separator: The anode and cathode
materials are separated using a non-
woven layer of cellulose or a synthetic
polymer. The role of the separator is
to avoid the mixing of anode and
cathode materials; to conduct ions
and to remain stable in the highly
alkaline electrolyte solution.
For additional safety, the alkaline cells
has a safety valve which opens when
the internal pressure of the cell
exceeds a particular limiting value.

Electrochemical reaction

Anode half – cell reaction : Ox: Zn (s) + 2OH− (aq) → Zn(OH)2 (s) + 2e−

Cathode half – cell reaction : Red: 2MnO2 (s) + H2O (l) + 2e− → Mn2O3 (s) + 2OH− (aq)

Therefore, the net cell reaction is: Zn (s) + 2 MnO2 (s) + H2O (l) → Mn2O3 (s) + Zn(OH)2 (s)

Cell type: Zn|KOH(paste)|MnO2,C

Important characterisitics of the alkaline cell:
The nominal voltage of the alkaline battery cell is 1.5 V. The fully discharged
cell has a remaining voltage in the range of 0.8 to 1.0 V. To prevent gassing of
the cell at the end of its life, excess MnO2 is taken than that required to react
with all the zinc powder present in the cell.
Advantages of the alkaline cell:
Zinc does not dissolve as readily in the basic medium; longer shelf life than
zinc-carbon battery since there is no acid corrosion of zinc; Charge density of
an alkaline battery is larger than similar sized zinc-carbon cell because the
MnO2 in the electrolyte is purer and denser; space taken up by internal
components such as current collectors is less; can provide between 3 to 5
times more operating time than zinc – carbon battery; the space taken up by
other cell components (separator, current collectors) is minimized.
Disadvantages of the alkaline cell:
The efficiency of the alkaline cell decreases with decreasing temperature unlike
dry cells. Over time, alkaline batteries are prone to leaking KOH, a caustic
agent that can cause respiratory, eye and skin irritation; The leaking crystalline
growths of KOH may oxidize the copper traces in the circuit, thereby leading to
permanent circuitry damage.
Applications: In camera flash, calculators, watches, etc.
(ii) Lithium-I2 batteries: are disposable (primary) type, solid-state type
batteries using a dry solid polymer as the electrolyte (like a plastic film) that
does not conduct electricity but allows the exchange of ions.
Basic structure:
Anode (-ve terminal): Lithium;
Solid Electrolyte: Lithium Iodide or poly-2-vinylpyridine (P2VP) as solid
organic charge transfer complex
Cathode (+ve terminal): Iodine
Electrochemical reaction
Anode half – cell reaction : Oxidation: Li (s) → Li+ + e−
Cathode half – cell reaction : Reduction: ½ I2 (s) + e− → I-
Therefore, the net cell reaction is: Li (s) + ½ I2 (s) → Li+ + I-
Cell type: Li|LiI(s)|I2(in polymer)
Important characteristics of the lithium cell:
Lithium is a light weight metal;
Highly polarizing (higher ability to lose its electron); highest electronegativity
value (-3.05 E0/V) in the electrochemical series.
Largest amount of electrical energy per unit weight among all solid elements.
Output voltage = 2.8 volts.
Li cannot be used with the traditional aqueous electrolytes due to the
very vigorous corrosive reaction between Li and water with flammable
hydrogen as the by-product.
Li cells are properly sealed against contact with air and moisture.

Advantages of the lithium cell:

High energy density; provide very high current;
long shelf-life of around 10 years;
though costly, Li cells require low maintenance;
lithium cells can produce voltages more than twice the voltage of an ordinary
zinc-carbon battery or alkaline cell; The higher voltage reduces the number of
cells in a battery pack by a factor of at least 2;
less self-discharge rate compared to Ni-Cd batteries;
Does not generate gas even under short circuit; Operation over a wide
temperature range (-40 to 70oC).
Disadvantages of the lithium cell:
Require protection circuit to maintain voltage and current within safer limits;
Lithium batteries can provide extremely high currents and can discharge very rapidly
which can result in overheating of the battery and even explosion. Hence, lithium
batteries incorporate vents in order to prevent explosion.
transport of lithium batteries by air is restricted.
expensive to manufacture; about 40% higher in cost than Ni-Cd battery;
lithium metal scrapped from the batteries can be illegally used as a reducing
agent in methamphetamine (used as drugs) labs.
Applications:
Used in portable consumer electronic devices, as backup batteries in computers and
communication equipment, and in remote car locks.
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.
Conventional Cells using aqueous (containing water) electrolytes are limited in
voltage to less than 2 Volts but Lithium batteries which use non-aqueous
electrolytes are available in higher voltages between 2.7 and 3.7 Volts. How?
because water dissociates to O2 and H2 in the presence of voltages above 2V.
Lithium batteries which use non-aqueous electrolytes do not have this problem.
(II) Conventional Secondary batteries:

Secondary batteries act as galvanic cell during discharge, and act

as electrolytic cell during charging.

Electrochemical Cell Electrolytic Cell

Discharging Charging
(a) Nickel-Metal hydride (MH) battery

An hydrogen absorbing alloy is used as the negative anode electrode.

The H2 gas adsorbed over the metal alloy yield a metal hydride (MH), thereby
allowing H2 to participate in reversible reactions.

(a) Nickel-Metal hydride batteries consist of:

Anode: Hydrogen adsorbing metal alloys (MH) of AB5 type, where A = La and
Ce; B = Ni, Co, Mn or Al.
Cathode: Nickel oxide hydroxide [NiO(OH)] (Where M = Hydrogen
absorbing alloy and
Separator: fine fibers
H (ab) = adsorbed hydrogen)
Electrolyte: aqueous KOH electrolyte

Electrochemical reaction during discharging and charging:

Anode half-cell reaction:
MH (ab) + OH-(aq) M (s) + H2O (l) + e-

Cathode half-cell reaction:

NiIIIO(OH) (s) + H2O (l) + e- NiII(OH)2 (s) + OH- (aq)

The net cell reaction:

MH (ab) + NiIIIO(OH) (s) M (s) + NiII(OH)2(s)
 Important Characteristics: since the KOH
electrolyte does not take part in the reaction, there
is no change in the volume of the electrolyte;
if excessive heat or pressure builds up, the cells
have a safety vent.
During excessive overcharging of the cathode, O2 is
evolved which is 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 lead 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 or 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: used in all-electric plug-in vehicles, in cell phones and camcorders.
(b) Lithium-TiS2 battery
Anode: Li (s)
Cathode: TiS2
Electrolyte: Poly-2-vinylpyridiene (P2VP) solid electrolyte
Electrochemical reaction during discharge
Anode half – cell reaction : Oxidation: Li (s) ↔ Li+ + e−
Cathode half – cell reaction : Reduction: Ti(II)S2 (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;
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 passivation 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 battery
Anode: Li (s)
Cathode: carbon coated - sulphur (as electron acceptor)
Electrolyte: β - Alumina (NaAl11O17) solid electrolyte
Electrochemical reaction during discharge
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 electro-conductivity that was missing from pure sulfur;
intermediary polysulfides are soluble in the electrolytes which causes
irreversible loss of active sulfur material.
 Discharging Charging Anode: lithium
adsorbed over
the carbon
material

Cathode: MnO2

The following reactions take place during discharging and charging:

• At the anode: Li(0)C6 Li+ + 6C + e-

• At the cathode: Li+ + Mn(IV)O2 +e- Li(I)Mn(III)O2

• Overall: LiC6 + MnO2 LiMnO2 + 6C

Anode: lithium adsorbed over the carbon material
Cathode: lithium in between the layered CoO2
The following reactions take place during discharging and charging:
• At the anode: Li(0)C6 Li+ + 6C + e-

• At the cathode: Li+ + Co(IV)O2 +e- Li(I)Co(III)O2

• Overall: LiC6 + CoO2 LiCoO2 + 6C

Chemistry and Construction

• Anode here is a non-metallic compound, e.g. carbon, which can store and exchange
lithium ions.
• A lithium ion-accepting material, for example MnO2 or CoO2, is then used as the
cathode material, and lithium ions are exchanged back and forth between the two
electrodes (carbon, graphite) during discharging and charging. Hence, these
electrodes are called intercalation electrodes.
• This type of battery is known as a “rocking chair battery” as the ions simply
“rock” back and forth between the two electrodes.
Differences between a battery and a fuel cell:
Battery Fuel Cell
A battery generates electrons from the A fuel cell make electrons from the
electrochemical reaction between the electrochemical reaction only when the
reactants already stored in the cell reactants are supplied from outside the
cell
A battery stores a limited amount of A fuel cell uses the reactants which are
chemical reactants internally inside a metal stored externally and constantly filled
case, which when used up, must be either up. A fuel cell vehicle is refueled instead
recharged or disposed. of recharged
It is a thermodynamically closed system It is a thermodynamically open system

Fuel cell types:

Hydrogen – oxygen fuel cell (HOFC) or alkaline fuel cell
Polymer electrolyte membrane (PEM) fuel cell
Solid oxide fuel cell (SOFC)
(i) Hydrogen – oxygen fuel cells (HOFC) or alkaline fuel cells (AFCs)

Materials used:
Anode: inert and porous graphite
electrode + finely divided Platinum catalyst
Cathode: inert and porous graphite
electrode + finely divided Platinum catalyst
Electrolyte: 25% KOH hot solution
(alkaline).
Chemistry: H2 and pure O2 gases are
bubbled through the anode and cathode
respectively, and the fuel cell produces
power through a red-ox reaction between
H2 and O2.

At anode (-): 2 H2 (g) + 4 OH-(aq) → 4 H2O (l) + 4 e- (oxidation)

The electrons flow through an external circuit and enter the cathode.
At cathode (+): O2 (g) + 2 H2O (l) + 4 e- → 4 OH- (aq) (reduction)
Net reaction: O2 (g) + 2 H2 (g) → 2 H2O (l)
The standard EMF of the cell: Eo = Eo ox + Eo red = 0.83 V + 0.40 V = 1.23 V.
By stacking a number of cells together in as series to make a battery, the
required voltage to drive a motor is achieved.

Electrode specifications:
(i) must be good conductors;
(ii) must be good electron sink;
(iii) must not be consumed or deteriorated by the electrolyte heat or
electrode reactions.

Advantages:
AFCs consume H2 and pure O2 producing water, heat, and electricity.
Efficiency is around 70%, highest among the fuels cells used at present.
Operating temperature are 150 to 200oC suitable for automobile
applications.
For low-temperature (-54oC to 72oC) operation, potassium
thiocyanate (KSCN) dissolved in liq. NH3 is used.

Disadvantages:
Require pure H2 and O2 fuel;
Platinum electrodes used as catalyst are expensive;
As the electrolyte is aqueous medium, it may leak.
Applications:
Compared to conventional energy generators, fuels cells occupy less
space and weight and hence used as auxiliary energy source in space
vehicles, submarines, etc;
In case of H2/O2 fuel cells, the water obtained as product is a
valuable source of fresh water for the astronauts.

Fuel cell poisoning:

AFCs can become poisoned if the oxygen is contaminated with
CO2 resulting in the conversion of aq. KOH into K2CO3.
Hence, AFCs require the supply of pure O2 thereby increasing the
cost.

The main mechanisms of poisoning is the change in electrolyte

composition from aq. KOH to aq. K2CO3 leading to subsequent
decrease in ionic conductivity of the electrolyte.

The poisoning effect can be reversed by replacing the poisoned

electrolyte with aq. KOH which returns the cell back to its original
output.
 Polymer - membrane fuel cell
Anode: inert and porous graphite
electrode + finely divided Platinum
catalyst
Cathode: inert and porous graphite
electrode + finely divided Platinum
catalyst
Electrolyte: proton-conducting
polymer membrane

Anode: 2H2(g) -----> 4H+(aq) + 4e-

Cathode: O2(g) + 4H+(aq) + 4e- ----> 2H2O(l)

Anode (Negative) Cathode (Positive)

PEM
Hydrogen reacts with the Pt
catalyst on the PEM
to form protons and
release electrons
H2 O2 + H+ + e-
The protons combine
H+ + e- H2O with O2 and electrons
to form water
The protons travel This reaction is also
across the PEM H+ catalyzed by Pt
(ii) Solid oxide fuel cell (SOFC) Draw this diagram only
Fuels used:
Lighter fuels: methane, propane and butane;
Heavier fuels: gasoline, diesel, jet fuel or biofuel.
Operating temperature: 500 to 1000oC

Anode or fuel electrode: Nickel mixed with YSZ

(yttria stabilized zirconia); is a porous ceramic
layer to allow the fuel to flow towards electrolyte.

Cathode or Air electrode: lanthanum strontium

manganite (LSM); is a thin porous ceramic layer
coated over the solid electrolyte where oxygen
reduction takes place.

Electrolyte: yttria stabilized zirconia (YSZ) +

gadolinium doped ceria (GDC) or a mixture of
zirconium oxide + calcium oxide; a dense layer
of oxygen ion conducting ceramic.

At anode (oxidation): H2 (g) + CO + 2O2- → H2O + CO2 + 4e- + energy

At cathode (reduction): O2 (g) + 4e- → 2O2-
 Interconnect: . Its purpose is to connect each cell in series, so that the
electricity generated from each cell can be combined.
Can be either a metallic or ceramic layer that sits between each individual cell.
Nickel- and steel-based alloys are used as interconnects in SOFCs operating
at 600-800°C.
The most common intermetallic materials used today are doped lanthanum
chromites as they exhibit high temperature thermal stability and excellent
electrical conductivity.

Function of Anode and Cathode electrodes:

Anode: to use the oxygen ions that diffuse through the electrolyte to oxidize the
hydrogen fuel to produce both water and electricity.
to act as a catalyst for steam reforming the fuel into hydrogen. This reforming
reaction is endothermic, which cools the SOFC cell internally.

Cathode: It is compatible with doped zirconia electrolytes; It has similar coefficient of

thermal expansion to YSZ.
Since LSM is a poor ionic conductor, the electrochemically active reaction is
limited to the triple phase boundary (TPB) where the electrolyte, air and
electrode meet. Composite cathodes consisting of LSM and YSZ have also been
used to increase this triple phase boundary length.
Principle of operation:
SOFC is made up of all-solid four layers among which the anode, cathode
and electrolyte are all made from ceramics, and inter-connect are made up
of metal alloys.
The ceramics used in SOFCs become electrically and ionically active at very
high temperature (500 to 1,000°C).
At high temperatures, reduction of oxygen into oxygen ions occurs at the
cathode (air electrode).
These O2- ions diffuse through the electrolyte to the anode (fuel electrode)
where they electrochemically oxidize the fuel gas containing hydrogen.
In this reaction, a water byproduct is given off as well as electrons. These
electrons then flow through an external circuit creating electricity. The cycle
then repeats as those electrons enter the cathode material again.
Reforming natural gas or water gas (H2 + CO) to extract the necessary
hydrogen can be done within the fuel cell thereby eliminating the need of the
external reformer. In such a fuel cell, reformate gas (H2 + CO) is used as a
fuel and oxygen as the oxidant.
SOFC design: Thermal expansion due to high temperature operation requires
a uniform and well-regulated heating process at startup.
SOFC stacks with planar geometry design require an hour to be heated to
operational temperature. But, micro-tubular fuel cell design requires just a
few minutes for the startup.

Characteristics: They operate at very high temperatures (500 to 1,000°C) and

hence do not require expensive platinum catalyst material for the redox reaction.
SOFCs are not vulnerable to carbon monoxide catalyst poisoning but are
vulnerable to sulfur poisoning. Hence, sulfur must be removed before entering
the cell through the use of adsorbent beds.
Power output = 100 W to 2 MW. Theoretical efficiency of a SOFC device can
exceed 60 %. In applications designed to capture and utilize the system’s waste
heat, the efficiency could reach 80 to 85%.

Advantages: high efficiencies, long term stability, fuel flexibility, low emissions,
and cost. It produces exhaust gases at temperature ideal for combined-cycle
electric power plants.

Disadvantages: high operating temperature (500 to 1,000°C) which results in

longer start up times and mechanical/chemical compatibility issues.