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.
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.

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
(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:
Lithium is a light weight metal, Higher ability to lose its electron; highest
electronegativity value (-3.05 E0/V), Output voltage = 2.8 volts, Largest amount of
electrical energy per unit weight among all solid elements.
Advantages:
High energy density, Less self-discharge rate, Does not generate gas even under short
circuit, Long shelf-life of around 10 years, Though costly, Li cells require low
maintenance, Lithium cells can produce voltages more than twice that of conventional
cells, Operation over a wide temperature range (-40 to 70oC).
Disadvantages:
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.
Lithium and Water reaction: Electrolysis of water into O2 and H2 takes place at 2V.
In conventional cells, output voltage is <1.5 V and hence water used as electrolyte.
In Li battery, water cannot be used since it will easily undergo electrolysis to form
flammable H2 as the by-product.
Hence, Li cells are properly sealed against contact with air and moisture.
Lithium batteries which use non-aqueous electrolytes do not have this problem.
(II) Secondary batteries: Secondary batteries act as galvanic cell during
discharge and act as electrolytic cell during charging.
(a) 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, Li/TiS2 battery is
thermodynamically stable, 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.
Advantages and Disadvantages: Refer to previous slides
(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-
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 Sulphur (m.pt = 116
o
C) and Lithium (m.pt = 181 oC) must be in their molten states for the operation
of cell reaction.
Since sulphur lacks electro-conductivity, carbon coating on sulfur is
required provide the electro-conductivity.
S2- formed during the cathode reaction reacts with elemental sulphur to form
the polysulphide ions which are soluble in electrolytes, thereby causing
irreversible loss of active sulfur material.
S2- + n S → [Sn+1]2-
 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
recharged or disposed. instead 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 aq. soln. (alkaline).

Chemistry: Pure H2 and O2 gases are

bubbled through the anode and cathode
respectively, and the fuel cell produces
power through a redox 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)
Advantages:
Standard EMF of the cell: Eo = Eo ox + Eo red = 0.83 V + 0.40 V = 1.23 V.
Efficiency is around 70%, highest among the fuels cells used at present.
Operating temperature: 150 to 200 oC suitable for automobile applications.
For low-temperature (-54 to 72 oC) operation, 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.
Fuel cell poisoning: AFCs can become poisoned if the oxygen is
contaminated with CO2 resulting in the conversion of aq. KOH into K2CO3
leading to subsequent decrease in ionic conductivity of the electrolyte. Hence,
AFCs require the supply of pure O2 thereby increasing the cost.

Applications:
Compared to conventional energy generators, fuels cells occupy less space
and weight and hence used as auxiliary (backup) energy source in space
vehicles, submarines, etc.
Water obtained as product is a valuable source of fresh water for astronauts.
 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)
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 porous ceramic layer 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 cathode (reduction): O2 (g) + 4e- → 2O2-

At anode (oxidation): H2 (g) + CO + 2O2- → H2O + CO2 + 4e- + energy
Principle of operation:
SOFC is made up of all-solid ceramic layers
At high operating temperature (500 to 1,000°C), 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.
Water is given as the byproduct as well as electrons. These electrons then
flow through an external circuit creating electricity.
SOFC design: 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.

Advantages:
•Power output = 100 W to 2 MW.
•High efficiency, long-term stability, fuel flexibility, low emissions and cost.
•Efficiency can exceed 60 %. If SOFC is designed to capture and utilize the
system’s waste heat, the efficiency could reach 80 to 85%.

Disadvantages:
•SOFCs are vulnerable to sulfur poisoning (present as impurity in fuels).
•High operating temperature (500 to 1,000°C) which results in longer start up
times and mechanical/chemical compatibility issues.