05-10-2018

An Electrochemical cell

• An electrochemical cell is a device in which a

Electrochemical energy redox reaction is utilized to get electrical
systems energy.
• Commonly referred to as voltaic or galvanic
cell.
Batteries
• The electrode where oxidation occurs is
called anode while the electrode where
reduction occurs is called cathode.

Electrochemical cell or galvanic cell Electrolytic cell

• A device used to convert the chemical energy produced in a redox
reaction to electrical energy is called an electrochemical cell or chemical • A device in which the electrical energy is converted to
cell. Depending upon the changes occuring in the electrochemical cell , chemical energy and resulting in a chemical reaction
these can be of two types electrolytic cell and galvanic or voltaic
Voltages generated by such cells have been referred to as electromotive
force.

Batteries
Nernst equation
• 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.

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Types of
batteries
• Primary battery (Primary cells) in 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) in 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 in which materials (reactants,
products, electrolytes) pass through the battery, which is
simply an electrochemical cell that converts chemical to
electrical energy.
Lithium
batteries
• One of the main attractions of lithium as an anode material is its position
as the most electronegative metal in the electrochemical series
combined with its low density, thus offering the largest amount of
electrical energy per unit weight among all solid elements.
• 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.
• 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 Whilst the primary lithium battery has been well established for
nearly two decades,

• SystemNominal Cell Voltage (V) Advantages

Disadvantages Applications
Chemistry
• The cell is represented as
Li/Li+(nonaqueous)/MnO2,Mn(OH)2,C.
• Li/SOCl2 3.60 High Energy density; long shelf life.
Only low to moderate rate applications. Memory • The anode is lithium. The cathode is carbon in contact with
devices; standby electrical power devices manganese (III), Manganese(IV) electrode. The electrolyte is
an aprotic solvent

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

temperature performance; long shelf life. High-cost Li --- Li+ + e-
pressurized system, Military and special industrial
needs
• At cathode
MnO2+2H2O+ e- --- Mn(OH)3 + OH-
• Li/MnO2 3.00 High energy density; good low-
temperature performance; cost effective. Small in size, • The overall reaction is
only low-drain applications, Electrical medical devices; • Li + MnO2+ 2H2O -- Li + + Mn(OH)3 + OH-
memory circuits;

Advantages and uses Lithium batteries

• 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

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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.
• 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.
Discharging
• The following reactions take place upon discharge:
• At the anode: LixC6→ xLi+ + 6C + xe-
• At the cathode: xLi+ + Mn2O4 +xe-→ LixMn2O4
05-10-2018
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
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.
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.
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Lithium ion Cells

Lithium Polymer batteries are better than Lithium ion batteries
Charging Discharging

Exploded laptop
Anode: lithium ions in the carbon material
Cathode: lithium ions in the layered material (lithium compound) • Li-ion batteries use organic solvents to suspend the lithium ions.
• In situations where the structure of the battery is compromised, that
Anode Cathode solvent can ignite and vent from the pressurized battery.
Li1-XCoO2+ CnLix  LiCoO2 + Cn LiCoO2+ Cn  Li1-XCoO2 + CnLix • The result is a dangerous explosion
• The main advantage of Li-poly batteries that has been discussed in
The lithium ion moves from the anode to the cathode during the press recently is their reluctance to explode under duress
discharge and from the cathode to the anode when charging.

Applications: Laptops, cellular phones, electric vehicles

Lithium Polymer Battery Lithium polymer (Poly-Carbon

Monofluoride) batteries
• Electrolyte is a polymer ← Charging

Lithium battery-battery of the

• Now !! stop imagining because its going to happen
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 !!!
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.

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Fuel Cells Fuel Cell Energy Exchange

• 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

http://hyperphysics.phy-astr.gsu.edu/hbase/thermo/electrol.html

Fuel Cells • Hydrogen (through anode) and oxygen (through

cathode) gases are bubbled through the respective
• Fuel cell – Electric energy is obtained without compartments.
combustion from oxygen and a gas that can be
oxidized. Thus, a fuel cell converts chemical energy • Electrode – porous , good conducting, excellent
of the fuels directly to electricity. catalyst for the reactions that take place on their
surfaces, not deteriorating by the electrolyte heat or
electrode reactions.
• Fuel + Oxygen oxidation products + Electricity
• Graphite impregnated with finely divided platinum,
H2 – O2 fuel
or alloy of Pd, Ag and Ni serves the purpose if
• 2H2 + 4 OH- H2O + 4e- (Anode)
hydrogen is the fuel.
• O2 + 2 H2O + 4 e- 4 OH- (Cathode) • Electrolyte - aqueous KOH or H2SO4
• 2H2 + O2 2H2O

Proton Exchange Membrane (PEM)

• Applications:
• Auxiliary energy source in space vehicles,
submarines or other military-vehicles. thin permeable polymer sheet
electrolyte
• Source of fresh water
40 – 50% efficiency
50 – 250 kW
80˚C operating temperature

Figure 7

electrolyte will not leak or crack

temperature good for home or vehicle use
pla num catalyst on both sides of membrane → $$

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Chemical structures of some membrane materials

Nafion Membrane
PSSA PESA Chemical Structure
poly(styrene-co- (Polyepoxy-
styrenesulfonic succinic Acid)
acid) (PSSA)

Nafion,TM
Membrane C ,,-Trifluorostyrene grafted
onto poly(tetrafluoro-
ethylene) with post-
sulfonation)

Dow
Poly – AMPS
Poly(2-acrylamido-
2-methylpropane sulfonate)

PEM Fuel Cell

In a proton−exchange−membrane fuel cell, hydrogen
and oxygen react electrochemically. At the anode,
hydrogen molecules dissociate, the atoms are ionized,
and electrons are directed to an external circuit;
protons are handed off to the ion−exchange
membrane and pass through to the cathode. There,
oxygen combines with protons from the ion−exchange
membrane and electrons from the external circuit to
form water or steam. The energy conversion efficiency
of the process can be 60% or higher.

Solid Oxide Fuel Cell (SOFC)

Solid oxide fuel cells (SOFC)
• Anode, cathode and electrolyte all made up of ceramic hard ceramic oxide electrolyte
substances
~60% efficient
• Anode : porous, to allow the fuel to flow to the electrolyte –
Nickel mixed with ceramic material of the electrolyte ~1000˚C operating temperature
cells output up to 100 kW
• 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
Figure 8
high temp / catalyst can extract the hydrogen from the fuel at the electrode
high temp allows for power generation using the heat, but limits use
SOFC units are very large
solid electrolyte won’t leak, but can crack

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• Operate at temperatures as high as1000oC Advantages / Disadvantages

• Can be configured as rolled tubes or flat plates
• High efficiency
• Oxygen ions diffuse through the electrolyte from
cathode and oxidize hydrogen fuel at the anode. This • Long term stability
reaction produces oxygen and electricity • 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