Module- Basic concepts of cells and batteries-nominal voltage, 4

6 operating voltage, capacity, self discharge, depth of

discharge, energy density, service life, shelf life.
Electrochemistry of Primary cells – Comparative
features and applications of Lechlanche, alkaline and Li-
primary cells.

Module- Secondary cells - Lead – acid, Ni-Cd, Ni-MH cells; 4

7 Rechargeable lithium cells – chemistry and applications.
Fuel cells – Electrochemistry of a H2–O2 fuel cell, Basics
of solid oxide fuel cells-applications
 UNIT-5
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.

3
5
6
Ecell = EM/M+ – Ecalomel
EM/M+ = Ecell + Ecalomel
Ecell is the total emf of the cell. The electrode potential of the
metal electrode is given by Nernst equation as;
EM/M+ = E° + RT In aMn+
nF
E°M/M+= EM/M+ - RT In aMn+
nF
E°M/M+= EM/M+ – 0.0595 Iog aMn+
n
The potential of saturated calomel electrode (SCE) = 0.244
+ 0.0007 (25°C)

E°M/M+ = EM/M+ – 0.0595 Iog [γc x C]

n
where E° is the standard electrode potential of the metal electrode; aMn+ is the activity
of metal ions in the solution (aMn+ = γc[C]); γc is the activity coefficient (Table 2) and
7
C is the concentration of the electrolyte solution.
Electromotive force = E.M.F
e.m.f units = Volts or Joules/coulomb
e.m.f convert chemical, mechanical, and other forms of energy
into electrical energy.

8
Electrolytic Cell:

A device in which electrical energy is converted into

chemical energy through redox chemical reactions.

This method will be used to decompose the chemicals and

The process is called electrolysis

9
10
11
12
13
14
15
16
17
18
 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
22
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)
25
 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.
27
 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 at cathode : 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 does not dissolve as readily in alkaline

medium
• Long life
• Used in calculators and watches
Alkaline batteries can leak KOH, can cause respiratory, eye and skin
irritation
Reasons:
The reason for leaks is that as batteries discharge — either through
usage or gradual self-discharge — the chemistry of the cells changes and
some hydrogen gas is generated. This out-gassing increases pressure
in the battery. Eventually, the excess pressure either ruptures the
insulating seals at the end of the battery, or the outer metal canister, or
both.
In addition, as the battery ages, its steel outer canister may gradually
corrode or rust, which can further contribute to containment failure
the leak out KOH, that reacts with CO2 in the air to form K2CO3.
Precautions:
Store at lower temperatures
Don’t mix with other kind of batteries
32
Remove the batteries from the device after usage
 Lithium Batteries

Lithium batteries are different from Lithium ion Batteries (also

Known as Li-ion batteries).
Lithium batteries can not be recharged

Most of the common lithium batteries contain:

Anode: Metallic Li
Cathode: MnO2
Electrolyte: Li salts dissolved in organic solvents such as
Acetonitrile (CH3CN), propylene carbonate, ethylene
carbonate
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

• 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 LiAlCl4 dissolved in propylene carbonate as a typical organic
electrolyte.

• Li cells are generally hermitically sealed against contact with air

and moisture Whilst the primary lithium battery has been well
established for nearly two decades, 34
Different types of Lithium Batteries:

• 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; Can operate down to −55 °C and up to +70 °C
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;

35
 Advantages and uses

• Advantages of lithium 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
37
38
 RECHARGEABLE BATTERIES

Energy Density of lead acid battery = 60-120 Wh/kg 39

40
At anode:

At cathode:
42
 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 in

Sweden in 1899. But introduced in the early
1960's
 Characteristics
• 1.4 Volt
• Energy density about double than 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.
51
 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 (Energy Density 60-110 Wh/kg)
and 40% higher than that of NiCads (Energy Density 50-
150 Wh/kg).
• Since small amount of the negative electrode is used in
Ni-MH batteries, it allows a larger volume for the +ve
electrode, which results higher capacity or longer
service life.
 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-oxyhydroxide (NiOOH),
Anode: Hydrogen absorbing alloys
• Eg:La0.8Nd0.2Ni2.5Co2.4Si0.1
• Ti2Ni+TiNi+x 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
 Ni MH Battery

At anode:
Discharging
MH (Alloy Hydride) + OH- M (Alloy) + H2O + e-
Recharging
At cathode:
Discharging
NiOOH + H2O + e- Ni(OH) 2 + OH-
Recharging

55
 Advantages
• High energy density
• Rapid charge possible in 1 hour
• Because of potential pressure build up due to gassing
they usually incorporate a re-sealable vent valve
• Environmentally friendly (No cadmium mercury or lead)

overcharging can cause deterioration of the battery.

Chargers should therefore incorporate a timer to prevent
overcharging.
 Applications
• Low cost consumer applications
• Electric razors
• Cameras
• Mobile phones
• Pagers
• Medical instruments and equipment
• Automotive batteries
Lithium ion batteries

58
 Lithium ion batteries
Li-ion battery is a rechargeable battery best suited to mobile
devices that require small-size, light weight and high
performance. Its characteristics of high energy and high
voltage (3.6V) powerfully fulfill these three key
requirements. Its standard battery-pack, coupled with a
charger, facilitates simple equipment design.
• In 2009: around 38 % of all batteries by revenue were Li-ion.
• Li-ion is a low-maintenance battery and an advantages are many.
• The battery has no memory and does not need exercising to keep
in shape.
• Self-discharge is less than half compared to nickel-based systems.
This makes Li-ion well suited for fuel gauge applications.
• The nominal cell voltage of 3.6V can power cell phones and digital
cameras directly, offering simplifications and cost reductions over
multi-cell designs.
• The drawback has been the high price
 Lithium ion batteries
• Cathode: Lithium metal oxide
• Anode: porous carbon
• Electrolyte: LiPF6 dissolved in
an ethylene carbonate and
dimethyl carbonate mixture

During discharge, the ions flow from the anode to the

cathode through the electrolyte and separator;
During charge the direction of ion flow will be reversed,
where the ions flow from the cathode to the anode.
 Lithium ion batteries
In Li-ion batteries, in order to have high capacity and
superior power delivery, Cathode play very key role.

For the last 10 years or so, the cathode has

characterized the Li-ion battery.

Common cathode material are:

Lithium Cobalt Oxide (or Lithium Cobaltate),
Lithium Manganese Oxide (also known as spinel or
Lithium Manganate),
Lithium Iron Phosphate,
Lithium Nickel Manganese Cobalt (or NMC)
and Lithium Nickel Cobalt Aluminum Oxide (or NCA).

61
 Lithium ion batteries
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.
 Lithium ion batteries
Anodic materials

Sony’s original lithium-ion battery used coke as the anode

(coal product), and since 1997 most Li-ion batteries use
graphite to attain a flatter discharge curve.
Developments also occur on the anode and several additives
are being tried, including silicon-based alloys. Silicon achieves
a 20 to 30 % increase in specific energy at the cost of lower
load currents and reduced cycle life.
Nano-structured lithium-titanate as anode additive shows
promising cycle life, good load capabilities, excellent low-
temperature performance and superior safety, but the specific
energy is low.

63
 Lithium ion batteries
• 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.

LiPF6
Discharging
 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

Discharging Charging

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

􀋙 Li-ion Battery Structure
A lithium-ion rechargeable battery consists of a spiral structure with 4
layers. A positive electrode activated by cobalt acid lithium, a negative
electrode activated by special carbon, and separator are put together in a
whirl pattern and stored in the case. It also incorporates a variety of safety
protection systems such as a gas discharge valve which helps prevent the
battery from exploding by releasing internal gas pressure if it exceeds
the design limit.

68
The chemical reactions for charge and discharge are
as shown below:

The principle behind the chemical reaction in the lithium ion

battery is one where the lithium in the positive electrode lithium
cobalt oxide material is ionized during charge, and moves from
layer to layer in the negative electrode. During discharge, the
ions move to the positive electrode and return to the original
69
compound
70
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 is their reluctance to
explode under pressure
 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 !!!
• 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/electrode//electrolyte//electrode/oxidant
76
 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
77
• 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

78
proton exchange membrane fuel cells
(PEM fuel cells,or PEMFC)
• Applications:
• Auxiliary energy source in space vehicles,
submarines or other military-vehicles.
• Source of fresh water

84
 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.
• 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

85
• 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 water and electricity

• Cathode Reaction: O2 + 4e− → 2O2−

• Anode Reaction: 2H2 + 2O2− → 2H2O + 4e−
• Overall Cell Reaction: 2H2 + O2 → 2H2O

86
 Advantages / Disadvantages
• High efficiency
• Long term stability
• Fuel flexibility
• Low emissions

• High operating temp – longer start up times

• Mechanical / Chemical compatibility issues.

87
 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

88
89