Electrochemical energy

systems

Batteries
 Electrolytic cell
• A device in which the electrical energy is converted to
chemical energy and resulting in a chemical reaction
 Batteries
• Batteries use a chemical reaction to do work on charge and
produce a voltage between their output terminals.

• The basic element in a battery is called an electrochemical cell

and makes use of an oxidation/reduction reaction.

• An electrochemical cell which produces an external current is

called a voltaic cell. Voltages generated by such cells have
historically been referred to as emf (electromotive force).

• Batteries are devices where several electrochemical systems

are connected together in series.

• And can store chemical energy for later release as electricity

• It is a source of direct electric current at a constant voltage.

 Types of
batteries
• Primary battery (Primary cells)
• which the cell reaction is not reversible. When all the
reactants have been converted to product, no more electricity
is produced and the battery is dead.

• Secondary battery (secondary cells)

• which cell reactions can be reversed by passing electric
current in the opposite direction. Thus it can be used for a
large number of cycles.

• Flow battery and fuel cell

• which materials (reactants, products, electrolytes) pass
through the battery, which is simply an electrochemical cell
that converts chemical to electrical energy.
 Primary/Secondary/Advanced
secondary batteries
Primary batteries
Dry or lachlanche cell
Alkaline battery
Lithium batteries
Secondary batteries
Lead acid
Nickel-Cadmium
Advanced secondary batteries
Nickel Metal hydride
Lithium ion
DRY(or LACLANCHE) CELL

• The venerable
carbon-zinc cell
or Lechlanche' cell
was invented in
1866 by Georges
lachlanche and
was the most
common small
battery throughout
most of the 20th
century
• Dry cell contains Zn, NH4Cl, ZnCl2 and MnO2

• Anodic reaction
• Zn(s) -> Zn2+(aq) + 2e-

• Cathodic reaction
• 2NH4+(aq) + 2MnO2(s) + 2e- -> Mn2O3(s) + H2O(l) + 2NH3(aq)

• Some of the complexity of this reaction comes from the fact that the
reduction of the ammonium ion produces two gaseous products

• 2NH4+(aq) + 2e- -> 2NH3(g) + H2 (g)

• which must be absorbed to prevent the buildup of gas pressure.

• ZnCl2 (aq) + 2NH3 (g) -> Zn(NH3)2Cl2 (s)
• 2MnO2 (s) + H2(g) -> Mn2O3(s) + H2O(l)
 Applications and
disadvantages
• Used in flash lights, transistor radios, calculators etc

• Disadvantages of dry cell

• The voltage of this cell is initially about 1.5 volts, but decreases as energy
is taken from the cell. Due to the accumulation of the products on
electrodes. It also has a short shelf life and deteriorates rapidly

• Oxidation of the zinc wall eventually causes the contents to leak out, so
such batteries should not be left in electric equipment for long periods.

• While these batteries have a long history of usefulness, they are declining
in application since some of their problems are overcome in ALKALINE
BATTERIES.
 ALKALINE DRY
CELLS
• Alkaline cells overcome some of the problems
with carbon-zinc batteries by using potassium
hydroxide in place of ammonium chloride in
the electrolyte.

• Potassium hydroxide is a base or alkaline

material, hence "alkaline" batteries. The
active materials used are the same as in the
Leclanché cell – zinc and manganese dioxide.
 Chemistry
• The zinc anode does not form the container; it is in the form of
a powder instead, giving a large surface area. The following
half-cell reactions take place inside the cell:

• At the anode: Zn + 2OH – → Zn(OH)2 + 2e–

Zn(OH)2 + 2OH – → [Zn(OH)4] 2 –

• At the cathode:
• 2MnO2 + H2 O + 2e – → Mn2 O3 + 2OH –
For full discharge: MnO2 + 2H2O + 2e– → Mn(OH)2 + 2OH –

• Overall: Zn + 2MnO2 → ZnO + Mn2 O3

For full discharge:
Zn + MnO2 + 2H2 O → Mn(OH)2 + Zn(OH)2
 Construction
This cell is “inside out” compared to the Leclanché
cell

•These cells have much

longer shelf life and
perform better under
drain and in cold weather.

•They avoid the use of

the zinc-corroding
ammonium ions and do
not produce any gaseous
products.
 Advantages and Uses

• Zinc doesnot dissolve as readily in alkaline

medium
• Long life
• Used in calculators and watches
 Lithium Battery
• The cell is represented as
Li/Li+(nonaqueous)/KOH(paste)/MnO2,Mn(OH)2,C.

• The anode is lithium. The cathode is carbon in contact with

manganese (III), Manganese(IV) electrode. The electrolyte is a
paste of aqueous KOH

• At anode
Li --- Li+ + e-

• At cathode
MnO2+2H2O+ e- --- Mn(OH)3 + OH-

• The overall reaction is

• Li + MnO2+ 2H2O -- Li + + Mn(OH)3 + OH-
• System Nominal Cell Voltage (V) Advantages
Disadvantages Applications

• Li/SOCl2 3.60 High Energy density; long shelf life.

Only low to moderate rate applications. Memory
devices; standby electrical power devices

• Li/SO2 3.00 High energy density; best low-

temperature performance; long shelf life. High-cost
pressurized system, Military and special industrial
needs

• Li/MnO2 3.00 High energy density; good low-

temperature performance; cost effective. Small in size,
only low-drain applications, Electrical medical devices;
memory circuits;
 Advantages and uses

• Advantages of lithium ion batteries are

High electron density
Long shelf life
Low self discharge
Need less maintenance
Can provide very high current
• Uses
Used in auto focus cameras
 Uses
For constant power supply for electrical
vehicles,
gas engine ignition,
in telephone exchangers,
trains,
mines,
laboratories,
hospitals,
automobiles and in power
stations
 Nickel Cadmium battery

• The nickel-cadmium battery (commonly

abbreviated NiCd or nicad) is a type of
rechargeable battery using nickel oxide
hydroxide (NiOOH) and metallic cadmium
(Cd) as electrodes and an alkaline
potassium hydroxide KOH electrolyte.

• The first NiCd battery was created by of

Sweden in 1899. But introduced in the early
1960's
 Characteristics

• 1.4 Volt
• Energy density about double that of lead
acid batteries.
• Their small size and high rate discharge
capacity made portable tools and other
consumer applications practical for the first
time.
 Chemistry
• At anode
Cd + 2OH- --Cd(OH)2 +2e-

• At cathode
2NiO(OH) +2H2O +2e- --2Ni(OH)2+2OH-

• Net reaction
2NiO(OH) + Cd +2H2O-Cd(OH)2 + 2Ni(OH)2
 Advantages
• Constant voltage(1.4V)
• No gaseous products
• Wide temperature range (Up to 70°C)

• Charging process is strongly endothermic-the battery

cools during charging. This makes it possible to
charge very quickly

• Rapid charge typically 2 hours, but can be as low as

10 to 15 minutes.

• The sealed nickel-cadmium cell can be stored in the

charged or discharged state without damage.

• Available in a large variety of sizes and capacities

 Applications
• Motorised equipment
• Power tools
• Transistors
• Electronic calculators
• Commercial and industrial portable products
• Medical instrumentation
• Emergency lighting
• Toys
• Cordless and wireless telephones
 Disadvantages
• NiCad batteries will damage by overcharging.

• Low cell voltage of 1.4 Volts compared with primary

alkaline cells 1.5 Volts and only quarter of the
capacity of the alkaline cells.

• Self re-sealing safety vents must be incorporated to

prevent damage due to overheating and pressure
build up.

• The use of Cadmium in consumer products is now

deprecated on environmental grounds.
 Problem with NiCad
• Overcharging must be considered in the design of
most rechargeable batteries. In the case of NiCds,
there are two possible results of overcharging:

• If the negative electrode is overcharged, hydrogen gas

is produced.

• If the positive electrode is overcharged, oxygen gas is

produced.

• NiCd cells are vented, with seals that fail at high

internal gas pressures. The sealing mechanism must
allow gas to escape from inside the cell, and seal
again properly when the gas is expelled. This complex
mechanism, unnecessary in alkaline batteries,
contributes to their higher cost.
 Nickel Metal Hydride
Batteries
• Their basic structure is identical to that of Ni-Cd

• The NiMH battery was patented in 1986 by Stanford

Ovshinsky.

• Now NiMH batteries have begun to find use in high

voltage automotive applications. The energy density
is more than double that of Lead acid and 40%
higher than that of NiCads
 Anode
• Instead of cadmium, hydrogen is used as
the active element at a hydrogen-absorbing
negative electrode (anode).
• This electrode is made from a metal hydride
usually alloys of Lanthanum and rare earths
that serve as a solid source of reduced
hydrogen that can be oxidized to form
protons.
 Components
• The components of NiMH batteries include a
cathode of Nickel-hydroxide, an anode of
Hydrogen absorbing alloys
• Potassium-hydroxide (KOH) electrolyte.
• They are more expensive than Lead-acid and
NiCd batteries, but they are considered better for
the environment.
• The electrolyte is alkaline potassium hydroxide.
Cell voltage is 1.2 Volts
 Advantages
• High energy density
• Rapid charge possible in 1 hour
• overcharging can cause deterioration of the battery.
Chargers should therefore incorporate a timer to prevent
overcharging.
• Because of potential pressure build up due to gassing
they usually incorporate a re-sealable vent valve
• Reconditioning is possible.
• Environmentally friendly (No cadmium mercury or lead)
 Applications
• Low cost consumer applications
• Electric razors
• Cameras
• Mobile phones
• Pagers
• Medical instruments and equipment
• Automotive batteries
Lithium batteries
 Lithium batteries
• The main attractions of lithium as an anode
material is
– It is the most electronegative metal in the
electrochemical series
– It has very low density,
– Means, the largest amount of electrical energy
per unit weight

• But 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 product.
 Li batteries
• In the 1980s progress was made in the use of Li
as an anode material with MnO2, liquid SO2 or
thionyl chlorides as the cathode, and
hexaflurophosphate dissolved in propylene
carbonate as a typical organic electrolyte.

• Li cells are generally properly sealed against

contact with air and moisture
• Cathode materials

• The most common compounds used for

cathode materials are LiCoO2, LiNiO2 and
LiMn2O4.
• Of these, LiCoO2 has the best
performance but is very high in cost, is
toxic and has a limited lithium content
range over which it is stable.
• LiNiO2 is more stable, however the nickel
ions can disorder.
• LiMn2O4 is generally the best value for
money, and is also better for the
environment.
 Anode material and
electrolyte
• The anode material is carbon based.
• This lithium content is lower than would be ideal,
however higher capacity carbons pose safety issues.

• Electrolyte
• Since lithium reacts violently with water, and the cell
voltage is so high that water would decompose, a
non-aqueous electrolyte must be used.
• A typical electrolyte is LiPF6 dissolved in an ethylene
carbonate and dimethyl carbonate mixture.
 Discharging

• The following reactions take place upon discharge:

• At the anode: LixC6→ xLi+ + 6C + xe-
• At the cathode: xLi+ + Mn2O4 +xe-→ LixMn2O4
• Overall: LixMn2O4 + 6C → LixC6 + LixC6
 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 CoO2,
is then used as the cathode material, and lithium ions
are exchanged back and forth between the two during
discharging and charging. These 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.
 Lithium ion Cells
Charging Discharging

Anode: lithium ions in the carbon material

Cathode: lithium ions in the layered material (lithium compound)

Anode Cathode
Li1-XCoO2+ CnLix  LiCoO2 + Cn LiCoO2+ Cn  Li1-XCoO2 + CnLix

The lithium ion moves from the anode to the cathode during
discharge and from the cathode to the anode when charging.

Applications: Laptops, cellular phones, electric vehicles

Lithium Polymer batteries are better than Lithium ion batteries

Exploded laptop
• Li-ion batteries use organic solvents to suspend the lithium ions.
• In situations where the structure of the battery is compromised, that
solvent can ignite and vent from the pressurized battery.
• The result is a dangerous explosion
• The main advantage of Li-poly batteries that has been discussed in
the press recently is their reluctance to explode under duress
 Lithium Polymer Battery
• Electrolyte is a polymer
Lithium polymer (Poly-Carbon
Monofluoride) batteries
← Charging
 Lithium battery-battery of the
future
• Imagine your electrical equipment powered by
Lithium ion battery refuse to die out of charge.

• Imagine your 2 hour battery backup of your

laptop increases to 20 hours.

• 6 days of standby time of cell phones increases to

60 days i.e 2 months ( charging a mobile just 6
times a year !!!
• Now !! stop imagining because its going to happen
very soon. scientists from Stanford University have
found a way to use silicon nanowires to produces 10
times the amount of electricity of existing lithium-
ion, known as Li-ion, batteries that power laptops,
iPods, video cameras, cell phones, and countless
other devices. A laptop that now runs on battery
for two hours could operate for 20 hours.
 Fuel Cells
• Do not store chemical energy
• Constant supply of reactants and removal of products
• Efficiency is higher than conventional power plant
• Free of noise, vibration, heat transfer, thermal pollution
etc.,
• Limitation:
• Choice and availability of suitable autocatalysts (for
electrodes) able to function efficiently for long periods
without deterioration and contamination
 Fuel Cells
• Fuel cell – Electric energy is obtained without
combustion from oxygen and a gas that can be
oxidized. Thus, a fuel cell converts chemical energy
of the fuels directly to electricity.

• Fuel + Oxygen oxidation products + Electricity

H2 – O2 fuel

• 2H2 + 4 OH- H2O + 4e- (Anode)

• O2 + 2 H2O + 4 e- 4 OH- (Cathode)

• 2H2 + O2 2H2O
• Hydrogen (through anode) and oxygen (through
cathode) gases are bubbled through the respective
compartments.
• Electrode – porous , good conducting, excellent
catalyst for the reactions that take place on their
surfaces, not deteriorating by the electrolyte heat or
electrode reactions.
• Graphite impregnated with finely divided platinum,
or alloy of Pd, Ag and Ni serves the purpose if
hydrogen is the fuel.
• Electrolyte - aqueous KOH or H2SO4
• Applications:
• Auxiliary energy source in space vehicles,
submarines or other military-vehicles.
• Source of fresh water
 Solid oxide fuel cells (SOFC)
• Anode, cathode and electrolyte all made up of ceramic
substances
• Anode : porous, to allow the fuel to flow to the electrolyte –
Nickel mixed with ceramic material of the electrolyte

• Cathode: Thin porous layer where oxygen reduction occurs

• Electrolyte : Solid oxide or ceramic electrolyte - Dense layer

of oxygen conducting ceramic. - mixture of ZrO and CaO
coated on either side by porous electrode materials. Others
include yttrium stabilized zirconia (YSZ) and gadolinium
doped ceria (GDC
• Operate at temperatures as high as1000oC
• Can be configured as rolled tubes or flat plates
• Oxygen ions diffuse through the electrolyte from
cathode and oxidize hydrogen fuel at the anode. This
reaction produces oxygen and electricity
 Advantages / Disadvantages
• High efficiency
• Long term stability
• Fuel flexibility
• Low emissions

• High operating temp – longer start up times

• Mechanical / Chemical compatibility issues.
 Applications
• Auxiliary power units in vehicles
• Stationary power generation
• By product gases – channeled to turbines
to generate more electricity – cogeneration
of heat and power and improves overall
efficiency