Electrochemical energy systems

Batteries
 An Electrochemical cell

An electrochemical cell is a device in which a

redox reaction is utilized to get electrical
energy.
Commonly referred to as voltaic or galvanic
cell.
The electrode where oxidation occurs is
called anode while the electrode where
reduction occurs is called cathode.
 Electrochemical cell or galvanic cell
• A device used to convert the chemical energy produced in a redox
reaction to electrical energy is called an electrochemical cell or chemical
cell. Depending upon the changes occuring in the electrochemical cell ,
these can be of two types electrolytic cell and galvanic or voltaic
Voltages generated by such cells have been referred to as electromotive
force.
 Electrolytic cell
• A device in which the electrical energy is converted to
chemical energy and resulting in a chemical reaction
Nernst equation
 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) 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.
 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 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

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;
Chemistry
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-
 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
 RECHARGEABLE BATTERIES

Lead-acid batteries, invented in

1859 by French physicist Gaston
Plante, are the oldest type of
rechargeable battery.
 Lead-Acid Battery
• Batteries use a chemical reaction to do work on charge and produce a
voltage between their output terminals.
Discharging
• When the storage cell is operating as a voltaic cell it is
said to be discharging

• In the discharged state both electrodes turn into

lead(II) sulfate (PbSO4) and the electrolyte loses its
dissolved sulfuric acid and becomes primarily water.

• Due to the freezing-point depression of water, as the

battery discharges and the concentration of sulfuric
acid decreases, the electrolyte is more likely to freeze
during winter weather.

• In the charged state, each cell contains electrodes of

elemental lead (Pb) and lead (IV) dioxide (PbO2) in an
electrolyte of approximately 33.5% v/v (6 Molar)
sulfuric acid (H2SO4).
 Charging the Lead-Acid Battery

The discharge reaction can be reversed by

applying a voltage from a charging source.
During discharge process the concentration of
sulfuric acid decreases and while charging the
concentration may attain their initial values.

• In the charged state, each cell contains

electrodes of elemental lead (Pb) and lead (IV)
dioxide (PbO2) in an electrolyte of approximately
33.5% v/v (6 Molar) sulfuric acid (H2SO4).
 Overcharging

• Because of the open cells with liquid

electrolyte in most lead-acid batteries,
overcharging with high charging voltages
will generate oxygen and hydrogen gas by
electrolysis of water, forming an
explosive mix. The acid electrolyte is also
corrosive.
 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 only 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 are also prone to 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.