BATTERIES

Batteries
• Batteries are a collection of one or more cells whose chemical
reactions create a flow of electrons in a circuit.
• A battery slowly converts chemicals packed inside it into
electrical energy, typically released over a period of
days, weeks, months, or even years.
• All batteries are made up of three basic components: an
anode (the '-' side), a cathode (the '+' side), and some kind of
electrolyte (a substance that chemically reacts with the
anode and cathode).
 Contents in a battery system

• CATHODE
• ANODE
• ELECTROLYTE
• SEPARATOR
• CONTAINER
Working Principle
 CELL REACTIONS IN A BATTERY SYSTEM
• ANODE REACTION: is an oxidation reaction which releases
electrons (Anode is the –ve electrode in EC cell)
• CATHODE REACTION: is a reduction reaction which
consumes electrons (Cathode is the +ve electrode in EC cell)
• ELECTROLYTE :is an ion-conducting medium which conducts
ions between the electrodes so that the above reactions
can take place
 CLASSIFICATION OF BATTERIES
1. PRIMARY BATTERY - - for single use only
- - Chemical reaction is irreversible

2. SECONDARY BATTERY -for repeated use

-Chemical reaction is reversible
 I. Primary Batteries (or) Primary Cells
Primary batteries are those batteries in which the chemical reaction occurs
only once and the cell becomes dead after sometime and it cannot be used
again. Dry cell (Leclanche Cell) and Mercury cell, Lithium cell.
Requirements of Primary cell:
It should satisfy these requirements
1) It must be convenient to use.
2) Cost of discharge should be low.
3) Stand-by power is desirable.
 A. Dry cell (or) Leclanche Cell

• It consists of a cylindrical Zinc container that acts as an anode.

• A graphite rod placed in the center (but not touching the base) acts as a cathode.
• The space between anode and cathode is packed with the paste of NH4Cl and ZnCl2 .The
graphite rod is surrounded by powdered MnO2 and carbon as shown in Figure.
❖ The cell is called dry cell because of the absence of any liquid phase, even the electrolyte
consists of NH4Cl, ZnCl2 and MnO2 to which starch is added to make a thick paste which
prevents leakage.
❖ The graphite rod is fitted with a metal cap and the cylinder is sealed at the top with a pitch.
Cell Reactions:
At anode : (Oxidation, loss of electrons)
Zn(s) → Zn+2(aq.)+2e-
At Cathode : (Reduction, gain of electrons)

MnO2(s) + NH4+ + e- → MnO(OH) + NH3 (gas) * 2

Therefore, the net cell reaction is:

Zn(s) + 2MnO2(s) + 2NH4+ → Zn2+(aq.) + 2MnO(OH) + 2NH3 (gas)

This NH3 produced is not liberated as gas but immediately combines with the Zn2+ to form complex ion

Zn2+ + 2NH3(g) → [Zn(NH3)4]+2(aq.)

Advantages:
1) These cells have voltage ranging from 1.25V to 1.50V.
2) The electrolyte used in dry cell is relatively not so harmful to the environment.
3) Price is low.
4) Suitable for a wide range of consumer applications, like in Wall clocks, TV
remotes, Toy cars, Torches etc.

Disadvantages:
1) These cells does not have a long life, because the acidic NH 4Cl corrodes the
container even when the cell is not in use.
2) Potential difference keep on decreasing as time passes.
3) Tendency of getting leaked as the zinc casing gets used in the anodic reaction.
4) Poor low temperature performance. Do not function well in sub-zero
temperatures.
 B. Lithium cells
▪ Lithium Cells are Primary cells in which Lithium acts as anode and cathode is MnO2 .
▪ Lithium metal is used as anode because of its light weight, high standard oxidation potential(>3V) and
good conductivity.
▪ As the reactivity of Lithium in aqueous solution is more, Lithium cells use non aqueous solvents as
electrolyte.

The electrolyte in these systems is a solid electrolyte most widely used cell is Lithium-Manganese dioxide
cell. MnO2 should be heated to over 3000C to remove water before keeping it in the cathode, there by the
efficiency of the cell is increased.

➢ Anode: Lithium metal.

➢ Cathode: MnO2 as an active material.
➢ Electrolyte: LiBF4 salt in a solution of Propylene Carbonate and Dimethoxy Ethane.
Cell Reactions:

At Anode:
Li → Li+ +e-
At Cathode:
e-+ MnO2 → MnO-2

Net reaction:
Li + MnO2 → LiMnO2

Applications: 1) The coin type cells are used in watches and calculators
2) Cylindrical cells are used in fully automatic cameras.

Uses: 1) They are used for military and space application.

2) In Medicinal devices like neuro-stimulators drug delivery system
 C.Mercury cell
Mercury batteries uses mercuric oxide (HgO) as the cathode. Mercuric oxide is a non
conductor so a graphite is mixed with it. The anode is made of zinc and separates from
cathode with a layer of paper or porous material soaked with electrolyte (NaOH).

The reactions occur are:

At anode:
Zn +2OH-→ZnO+2H2O + 2e-
At cathode:
HgO + H2O + 2e- → Hg + 2OH-

Net reaction:
Zn+ HgO → ZnO +Hg
 II. Secondary Cells (or) rechargeable batteries
These cells can be recharged by passing an electric current through them and can be used again and again.
Eg: A. Lead storage battery
B. Nickel-Cadmium battery
C.Nickel-metal-hydride
D. Lithium-ion cell battery
These are reversible cells, they behave as galvanic cell while discharging and as electrolytic cell while
charging.
Secondary cells are widely used in cars,trains,motors,electric clocks, power stations, laboratories,
emergency lights, telephone exchange, digital cameras, laptops etc.
To improve the performance of battery for commercial purpose
a) The anodes and cathodes with very small separation to conserve space are used.
b) Current discharge should be high at low temperature.
c) It should have less variation in voltage during discharge.
 Lead –acid battery:
The lead storage battery is one of the most common batteries that is used in
the automobiles. A 12 V lead storage battery is generally used, which consists
of six cells each providing 2V.

▪ Each cell consists of a lead anode, a grid of lead packed with lead oxide
as the cathode.
▪ These electrodes are arranged alternately, separated by a thin wooden piece
and suspended in dil.H2SO4 (38%), which acts as an electrolyte. Hence it is
called Lead-acid battery.
▪ Anode: Pb
▪ Cathode: PbO2
▪ Electrolyte: H2SO4(38%)

EMF=2*6 = 12V
Lead storage battery
To increase the current output of each cell, the cathode and the anode plates are
joined together, keeping them in alternate positions. The cells are connected parallel
to each other (anode to anode and cathode to cathode).
In the process of discharging, i.e. when battery produces current, the reactions at
the electrodes are as follows:
At anode:
Pb(s) → Pb+2 (aq.)+ 2e-
Pb2+(aq.) + SO42-(aq.) → PbSO4 (s)
At cathode:
PbO2(s) + SO42-(aq.) + 4H+ (aq.) + 2e– → PbSO4 (s) + 2H2O
Therefore overall reaction is:
Pb(s) + PbO2 (s) + 2H2SO4 (aq.) → 2PbSO4 (s) + 2H2O

During discharging the battery, H2SO4 is consumed, and as a result, the density of
H2SO4 falls; when it falls below 1.20 g/cm3, the battery needs recharging. In
discharging, the cell acts as a voltaic cell where oxidation of lead occurs.
During recharging: The cell is operated like an electrolytic cell, i.e. electrical
energy is supplied to it from an external source. The electrode reactions are the
reverse of those that occur during discharge.
At anode:
PbSO4(s) + 2e– → Pb(s) + SO42-(aq.)
At cathode:
PbSO4 (s) + 2H2O → PbO2(s) + SO42-(aq.) + 4H+ (aq.) + 2e–
Net reaction : 2PbSO4 (s) + 2H2O → Pb(s) + PbO2 (s) + 2H2SO4(aq.)

Advantages: Lead acid batteries are used for supplying current to railways, mines,
laboratories, hospitals, automobiles, power stations, telephone exchange, gas engine
ignition, UPS(stand-by supplies).
Other advantages are its recharge ability, portability and Its relatively constant
potential & low cost.
Disadvantages: Use of Conc.H2SO4 is dangerous, use of lead battery is fragile.
 Nickel-cadmium (Secondary Battery)
▪ ANODE : Cd
▪ CATHODE : NiOOH
▪ ELECTROLYTE : KOH
▪ CELL VOLTAGE : 1.2 V
▪ Nickel-cadmium (NiCd, pronounced "nicad") are widely used as
replacements for disposable 1.5-volt batteries in things like toys,
flashlights, and power tools.
▪ They are relatively cheap, can be charged and discharged
hundreds of times. And if properly treated, will last about a
decade.
 Nickel–cadmium cell (Ni-cad cell)
The cell reactions during discharging are as follows:
At Anode:
Cd(s) + 2OH- (aq.) → Cd(OH)2(s) + 2e-
At Cathode:
2NiO(OH)(s) + 2H2O + 2e- → 2Ni(OH)2 + 2OH-(aq.)

Overall reaction:
Cd(s) + 2NiO(OH) + 2H2O → Cd(OH)2 (s) + 2Ni(OH)2(s)

EMF=1.2V

During recharging of Ni-Cd battery, the above cell reactions go from

right to left(i.e.Cell reactions are reversible)
Advantages and uses:

▪ The Nickel-Cadmium cell has small size and high rate charge/discharge capacity,
which makes it very useful.

▪ It has also very low internal resistance and wide temperature range (up to 70°C).

▪ Cells are used in electronic calculators, electronic flash units, transistors etc.

▪ Ni-Cd cells are widely used in medical instrumentation and in emergency lighting etc.

▪Used for the production of electric vehicles in the 90s,

▪ Ni-Cd batteries are now prohibited due to the toxicity of cadmium.

 Disadvantages

• Lower power density

• Contains toxic metal

 Applications
• Aircraft Batteries, Communication Equipment, Memory
Backup, Photography Equipment, Etc.
Lithium-ion (Secondary Battery)
• ANODE : CARBON
• CATHODE : LiCoO2
• ELECTROLYTE : LiPF6 in EC:PC
• CELL VOLTAGE : 4 V
• The latest lithium-ion batteries can store about twice
as much energy as traditional Ni-Cd rechargeable,
work at higher voltages, and are more environmental
friendly
 Lithium Battery
• Lithium is the lightest of metals and it can float on water.
• The electrochemical properties of lithium are excellent and it is also a highly
reactive material.
• These properties gives Lithium the potential to achieve very high energy and
high power
density
• Li-ion batteries are secondary batteries.
• The battery consists of a anode of Lithium, dissolved as ions, into a carbon.
 Lithium-Ion Battery
• The cathode material is made up from Lithium liberating
compounds, typically the
three electro-active oxide materials,
• Lithium Cobalt-oxide (LiCoO2 )
• Lithium Manganese-oxide (LiMn2 O4 )
• Lithium Nickel-oxide (LiNiO2)
• Lithium-ion batteries are the most popular types of
rechargeable batteries for portable electronics, with a high
energy density, tiny memory effect and low self-discharge.
 Principle of Working
• During the charge and discharge processes, lithium ions
are inserted or extracted from interstitial space
between atomic layers within the active material of the
battery.
• Simply, the Li-ion is transfers between anode and
cathode through lithium Electrolyte.
• Since neither the anode nor the cathode materials
essentially change, the operation is safer than that of a
Lithium metal battery
 Construction of Li-ion Battery
• Li-ion cell has a four-layer structure.
• A positive electrode made with Lithium Cobalt Oxide has a current collector made
of thin aluminum foil - cathode
• A negative electrode made with specialty carbon has a current collector of thin
copper foil – anode
• A separator is a fine porous polymer film.
• An electrolyte made with lithium salt in an organic solvent.
• The electrolytes are selected in such a way that there should be an effective
transport of Li-ion to the cathode during discharge.
• The type of conductivity of electrolyte is ionic in nature rather than electronic
 Working of Li-ion Batteries
• The traditional batteries are based on galvanic action but Lithium ion secondary battery
depends on an "intercalation" mechanism.
• This involves the insertion of lithium ions into the crystalline lattice of the host electrode
without changing its crystal structure.
• These electrodes have two key properties. One is the open crystal structure, which allow
the insertion or extraction of lithium ions and the second is the ability to accept compensating
electrons at the same time. Such electrodes are called intercalation hosts.
• The chemical reaction that takes place inside the battery is as follows, during charge and
discharge operation:
 Working of Li-ion Batteries
• The lithium ion is inserted and exerted into the lattice
structure of anode and cathode during charging and discharging.

• During discharge current flows through external circuit

and light glows

• During charging, the electrons flows in the opposite direction

Working of Li-Ion Batteries

▪During charging, lithium in positive

electrode material is ionized and
moves from layer to layer and
inserted into the negative electrode.
• During discharge Li ions are
dissociated from the anode and
migrate across the electrolyte and
are inserted into the crystal
structure of the host compound
of cathode.
 Working of Li-ion batteries
• At the same time the compensating electrons travel in the external circuit and are
accepted by the host to balance the reaction.
• The process is completely reversible. Thus the lithium ions pass back and forth
between the electrodes during charging and discharging.
• Because of this reason, the lithium ion batteries are called ‘Rocking chair, ‘Swing’cells.
• A typical Li-ion battery can store 150 watt-hours of electricity in 1 kilogram of battery
as compared to lead acid batteries can store only 25 watt-hours f electricity in one
kilogram
• All rechargeable batteries suffer from self-discharge when stored or not in use.
• Normally, there will be a three to five percent of self-discharge in lithium ion batteries
for 30 days of storage.
 Advantages of Li-ion Batteries
• They have high energy density than other rechargeable
batteries. They have less weight
• They produce high voltage about 4 V as compared with other
batteries.
▪ They have improved safety, i.e. more resistance to overcharge
▪ No liquid electrolyte means they are immune from leaking.
• Fast charge and discharge rate
 Disadvantages
• They are expensive
• They are not available in standard cell types.
 Applications of Li-ion Batteries
• The Li-ion batteries are used in cameras, calculators, smart phones
and most of the consumer electronics device.
• They are used in cardiac pacemakers and other implantable device.
• Electric vehicles: Because of their light weight Li-ion batteries are
used for propelling a wide range of electric vehicles such as aircraft,
electric cars, hybrid vehicles, advanced electric wheelchairs, radio-
controlled models, and model aircraft .
• Power tools: Li-ion batteries are used in tools such as cordless
drills, sanders, saws and a variety of garden equipment like hedge
trimmers
Lithium ion secondary Batteries

▪ The lithium ion battery (LIB) system has been most successful in recent
development of battery.
▪ Li is lightest metal and has one of the highest standard reduction
potentials (-3.0 V)
▪ The first commercial lithium-ion battery was released by Sony in 1991
▪ Battery performance is related not only capacity but also to how fast current
can be drawn from it:
▪ specific energy (Wh/Kg),
▪ energy density (Wh/cm3)
▪ power density (W/Kg)
Schematic representation of a Lithium-ion cell
 Advantages of Lithium-ion batteries
POWER – High energy density means greater power in a smaller package.
▪ 160% greater than NiMH
▪ 220% greater than NiCd

HIGHER VOLTAGE – a strong current

allows it to power complex mechanical devices.

LONG SHELF-LIFE – only 5% discharge loss per month.

✓10% for NiMH, 20% for NiCd
 Disadvantages of Lithium-ion batteries
❑EXPENSIVE -- 40% more than NiCd

❑DELICATE -- battery temperature must be monitored from

within (which raises the price), and sealed particularly well

❑REGULATIONS -- when shipping Lithium-ion batteries in

bulk (which also raises the price)
 Applications
• Electric Vehicles, Cell Phones, Camcorders, Lap-top And
Palmtop Computers, Portable Electronic Devices, Etc.
 Electrolytes
Role
1) ion conductor between cathode and anode
2) generally, Lithium salt dissolved in organic solvent
3) solid electrolyte is also possible if the ion conductivity is high at operating
temperature.
Requirement
1) Inert
2) High ionic conductivity, low viscosity
3) low melting point
4) Appropriate concentration of Lithium salt
5) Chemical/thermal stability
6) Low cost
7) Environmental -friendly, non-toxic
Commercial electrolytes:
LiPF6 in Carbonate solvent
Anode materials

Requirements
• Large capability of Lithium adsorption
• High efficiency of charge/discharge
• Excellent cyclability
• Low reactivity against electrolyte
• Fast reaction rate
• Low cost
• 8) Environmental -friendly, non-toxic
Commercial anode materials:
Hard Carbon, Graphite
 Cathode Material
❑One facet of battery research in which there have been many
interesting discoveries is the area of cathodes
❑A cathode is the electrode of an electrochemical cell at which
reduction occurs
❑Common cathode materials of Lithium-ion batteries are the
transition metal oxide based compounds such as
LiCoO2, LiMn2O4, LiNiO2, LiFePO4
 Desired Characteristics of cathode materials
• A high discharge voltage
• A high energy capacity Li
Co
c
• A long cycle life O

• A high power density

• Light weight
a
• Low self-discharge LiCoO 2

• Absence of environmentally hazardous

elements
Parameters effecting Cathode behavior
➢Method of preparation
➢Particle size
➢Morphology
➢Oxygen Deficiency
➢Temperature
 CATHODE MATERIALS

➢ Layered oxide cathodes

➢ Spinel oxide cathodes
➢Zigzag layered LiMnO2 compound
➢Olivine structure of LiMPO4
➢ Other compounds
 Structures of cathode materials

Structures of different cathode materials for lithium ion batteries:

a) LiCoO 2 layered structure
b) LiMn2O4 spinel structure and
c)LiFePO4 olivine structure.
The green circles are lithium ions, Li+
 Li FePO4 Advantages

1.Good Structural Stability--Safety, long life

2 . Fe and Phosphates are abundant-Low cost

3 . Environmentally friendly-non toxic elements

Disadvantages
a. LiFePO4 Structure

Symmetry : 1.Slow Lithium-ion diffusion

Orthorhombic
2.Low electronic conductivity

3.Lower power capability

 Next generation cathodes
➢Most abundant isiron, with stable trivalent state
➢Second most abundant is titanium, with stable tetravalent
state
➢Vanadium, with wide valence change (V 2+ –V 5+ )
➢ Molybdenum, with wide valence change (Mo 4+ – Mo 6+ )
Conclusions and what does the future hold
▪ In present day common Lithium transition compounds such as
LiCoO2, LiNiO2, LiMn2O4 and LiFePO4 are used as cathode
material in battery cell production, and they have shown a
good performance during charge and discharge cycling
▪ For the future there are still a number of actions of interest to
further develop the performance of derived LiFePO4/C cathode
material
▪ We expect upcoming researches on this new framework will lead
to better cathode materials for lithium-ion batteries
 LITHIUM BATTERY – SALIENT FEATURES
• High working voltage (>3.8V)
• High inherent capacity (>150mAh/g)
• High energy density (>100Wh/Kg)
• Wide electrochemical window (2.5V - ~5V)
• Wide operating temperature (-40 - +80o)
• Light weight (variable with configuration)
• Long shelf-life (~8 years)