Battery

A battery is an electrical device consisting of one or more galvanic cells, with

external connections provided to allow the battery to power electrical
devices.
It produces electricity from a spontaneous
redox reaction.

For such reactions, ΔG is negative (ΔG < 0)

The maximum work done by the system is,

W'max = ΔG

At equilibrium ΔG = 0, then, W’max = 0

That is the condition where the battery is fully

discharged, chemical reactants are nearly
consumed.
 Components of Battery
A battery consists of an anode, a cathode, an electrolyte, a half-cell
separator.
 Choice of Anode and
Cathode
Generally the electron releasing component of an anode is a metal
or metal hydrides, Zn, Cd, Li, Pb etc.
The redox couple that form the anode reaction has lower standard
reduction potential, reducing agents, they readily donate electrons

The electron accepting component of a cathode is a metal oxide,

MnO2, Ag2O, HgO, PbO2, Mn2O4, CoO2 etc.
The redox couple that form the cathode reaction has higher
standard reduction potential , oxidizing agents, they readily accepts
electrons.

Electrolytes are ionic compounds: KOH, H2SO4, Li+PF6-, NH4+Cl-

 Classification of Battery
Based on nature of electrolytes Based on rechargeability

Wet Cell Dry Cell Primary Secondary

(electrolyte is a (electrolyte is battery battery
liquid) a past or solid) (Non (Rechargeable)
rechargeable)

Both primary battery and secondary batteries are portable voltaic cells.

4
Primary Battery

Primary batteries cannot be returned to their original state

by recharging (non-rechargeable).

Examples
1. Zinc-carbon battery
2. Zinc alkaline battery (alkaline battery)
3. Silver and mercury battery (button cell)
4. Primary lithium ion battery
A Primary Battery: The Leclanche
Cell
The first primary battery was developed by Leclanche in
the year 1866.

Wet Cell Dry Cell

Modern version
(Zinc – Carbon
Battery)

A flashlight battery, or dry cell, is

constructed with a zinc shell that serves
The original design as the anode; a graphite rod which
of Leclanche cell serves as the cathode; and a moist
Contains aqueous mixture of ammonium chloride, zinc
electrolyte solution. chloride, and manganese dioxide is
6
used as an electrolyte past.
Do not afraid of explosion!
We are safe! Because the gaseous product formed in this voltaic
cell is taken care by the chemical reaction. The gaseous NH3 forms
coordination complex with Zn2+. The H2 gas is oxidized by MnO2.
These reactions also prevents the electrode polarization that stops
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the cell functioning.
 Zinc-Alkaline Battery (or Alkaline Battery)

The battery is still composed of a zinc anode and a carbon/MnO2

cathode, but the electrolyte is potassium hydroxide.

Anode reaction:
Oxidation Zn to Zn2+

Cathode reaction:
Reduction of Mn4+ to Mn3+

Overall two electron process

Alkaline Battery

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 Comparison of alkaline battery
with zinc carbon battery
The capacity of a alkaline battery is
3 to 5 times greater than the zinc-carbon battery
because of the construction.

The MnO2 in alkaline battery is purer and denser. A

high amount active material is present in smaller
volume as compared to zinc-carbon battery resulting in
a smaller battery design.

Alkaline battery powers portable radios, toys, flashlights, and so

on, is safe.

It has no voltage drop, longer shelf life, and better performance

 Size and life time of alkaline battery
Alkaline battery comes in many sizes, AAA, AA, C, and D size cells.

Life time of a battery depends on it’s capacity.

Capacity of a battery, Cd = I x td ,
(Where, I is current, td is the discharge duration in hours)

Larger the cell size, the larger material content, higher the capacity
and longer life.

For a given current output, a relatively large D-cell would last longer
than a small AAA-cell.

AAA D
Mercury and Silver (Button)
Batteries
• Mercury and silver batteries are quite similar. Both use a zinc
container as the anode (reducing agent) in a basic medium.
• The mercury battery employs HgO as the oxidizing agent, the silver
uses Ag2O, and both use a steel can around the cathode.
• The solid reactants are compacted with KOH and separated with
moist paper.
The half-reactions for silver battery:

The half-reactions for mercury battery:

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Primary Lithium Battery
The primary lithium battery is widely
used in watches and implanted medical
devices. It offers an extremely high
energy/mass ratio, producing 1 mol of e-
(1 F) from less than 7 g of metal.
The anode is lithium metal foil, which
requires a nonaqueous electrolyte.
The cathode is one of several metal
oxides in which lithium ions lie between
oxide
layers. Some implantable medical devices
have a silver vanadium oxide (SVO;
AgV2O5.5) cathode and can provide
power for several years, but at a low rate
because energy storage is limited
Li 7 gm/mol (atomic weight), can provide 1 F of
electricity
Zn 65 gm/ mol (atomic weight), can provide 1 F of
electricity,.

For lithium, large amount of electricity is stored in

smaller mass (weight). That means energy density of
is high for lithium as compared with Zn.

Suppose we take H2. Compare its energy density

with Li.
Which one has high energy density?
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The cell reactions of primary lithium battery:
Secondary Batteries

Secondary batteries, or rechargeable batteries, can be

returned to their original state by the application of an
external electric current, which reverses the oxidation-
reduction half cell reactions

Examples:

1)Lead acid battery

2)Nickel-cadmium battery
3)Nickel-metal hydride battery
4)Lithium ion battery
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 Secondary Batteries
One of the first commercially available secondary batteries is the lead-
acid battery, which is still in use today. This battery, invented by Gaston
Plante in 1859, is the oldest type of wet cell battery.

Output voltage
of a single cell is
2.1 V

An automobile
battery, 6 single
cells combined in
series, produces
12.6 V
 Discharging of Lead Acid Battery

During the discharge

a) Lead is being oxidized at lead anode and forming lead sulphate
b) Lead oxide is being reduced at the lead oxide cathode to form
lead sulphate
c) It is two electron redox process

What is the overall reaction?

Lead-Acid Battery
For Discharge: Voltaic

When the cell is recharged, it uses electrical

energy as an electrolytic cell, and the half-cell
and overall reactions are reversed

For Recharge: Electrolysis

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 Advantages of lead acid batteries
 Comparative advantages in performance:
 The battery with the longest industrial production time (long
history) and the most mature technology has stable, reliable
performance and good applicability;
 Dilute sulfuric acid (4.5 M) is used as electrolyte without
flammability. The battery is designed at normal pressure or low
pressure with good safety;
 High working voltage, wide operating temperature range,
suitable for hybrid electric vehicle (HEV) and other high rate
discharge applications;
 The large-capacity battery technology is mature and can be made
into batteries with thousands of ampere-hours, providing
convenience for large-scale energy storage.
 Comparative advantage in cost: Lead-acid batteries are
the cheapest secondary batteries, with unit energy costs about
a third of those of lithium-ion or nickel-hydrogen batteries.
 Comparative advantages of recycling: Lead-acid battery has
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 Disadvantages of lead acid batteries
 Low energy density: Traditional lead-acid batteries are low in
quality and volume energy density. The energy density is only
about 1/3 of that of lithium ion batteries and 1/2 of that of
nickel-hydrogen batteries.
 Short cycle life: The cycle life of traditional lead-acid batteries
is short, and the theoretical cycle times are about 1/3 of that of
lithium-ion batteries.
 Lead pollution risks exist in the industrial chain: Lead is
the main raw material of lead-acid batteries. Lead accounts for
more than 60% of the battery quality. Lead used in lead-acid
batteries accounts for more than 80% of the total lead used
globally. Lead is a heavy metal, and the lead-acid battery
manufacturing industry chain (including primary lead smelting,
battery manufacturing, battery recycling, and secondary lead
smelting) has a high risk of lead pollution.
 Other safety concerns: Older batteries had a cap on each cell
for monitoring electrolyte density and replacing water lost on22
 Nickel-cadmium (NiCad) battery
Another secondary rechargeable battery, invented by Waldemer
Jungner in 1899, is the nickel-cadmium (NiCad) battery. This battery
is composed of a nickel oxide hydroxide cathode, a cadmium metal
anode, and a potassium hydroxide electrolyte. During discharge, the
cadmium is oxidized to Cd2+ at the anode and Ni3+ is reduced to Ni2+at
the cathode.

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 Nickel-cadmium (NiCad) battery

Nickel-cadmium rechargeable batteries produce a nearly constant

voltage at 1.2V and were once used widely in portable devices, but
the high cost and disposal restrictions because of the high toxicity
of cadmium have reduced their use.

Other batteries, such as the rechargeable nickel-metal hydride or

lithium-ion batteries, have replaced them because of the toxicity
and environmental problems related to cadmium.

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 Nickel-Metal Hydride Battery (Ni-MH)
In the nickel-metal hydride battery (NiMH), the nickel oxide hydroxide
is the cathode material. A hydrogen-absorbing metal alloy composed
of a mixture of metals with the stoichiometric formulas AB2 or AB5 acts
as an anode. The most common composition is the AB5, where A is
actually a mixture of rare earth metals and B is nickel, cobalt,
manganese, or aluminum. In AB2 form, A is titanium or vanadium and
B is zirconium or nickel. Whatever the stoichiometric form they all
serve the same purpose, the reversible formation of a metal hydride
(MH) H- H+ + 2 e -
+ -
1

The cell reaction is reversed during recharging.

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Lithium ion battery

26
"for the development of lithium-ion
batteries."
[Link] 27
Lithium Ion Battery
The secondary lithium-ion
battery has an anode of Li
atoms that lie between sheets
of graphite (designated LixC6).
The cathode is a lithium
metal oxide, such as LiMn2O4
or LiCoO2
A typical electrolyte is 1 M
LiPF6 in an organic solvent,
such as dimethyl carbonate
(often mixed with methylethyl
carbonate).
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Cell reactions:

29
Lithium Intercalation in Graphite Anode

30
Advantages of Li-ion battery
 High energy density: The high energy density is one of
the chief advantages of lithium ion battery technology. With
electronic equipment such as mobile phones needing to
operate longer between charges while still consuming more
power, there is always a need to batteries with a much
higher energy density.
 Self-discharge: One issue with many rechargeable
batteries is the self-discharge rate. Lithium ion cells is that
their rate of self-discharge is much lower than that of other
rechargeable cells such as Ni-Cad forms.
 Low maintenance: One major lithium ion battery
advantage is that they do not require and maintenance to
ensure their performance.
 No requirement for priming: Some rechargeable cells
need to be primed when they receive their first charge.
There is no requirement for this with lithium ion cells and
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 Disadvantages of Li-ion battery
 Protection required: Lithium ion cells and batteries are not as
robust as some other rechargeable technologies. They require
protection from being over charged and discharged too far.
 Ageing :One of the major lithium ion battery disadvantages for
consumer electronics is that lithium ion batteries suffer from
ageing.
 Transportation: This li-ion battery disadvantage has come to the
fore in recent years. Many airlines limit the number of lithium ion
batteries they take, and this means their transportation is limited
to ships.
 Cost: A major lithium ion battery disadvantage is their cost.
Typically they are around 40% more costly to manufacture than
Nickel cadmium cells.
 Immature technology: Although lithium ion batteries have been
available for many years, it can still be considered an immature
technology by some as it is very much a developing area. 32
Fuel Cells

33
34
CHP – Combined Heat and Power system
FCEVs – Fuel Cell Electric Vehicles
ICEVs - Internal Combustion Engine Vehicles
PHEVs -Plug-in Hybrid Electric Vehicles 35

Fuel Cells
In contrast to primary and
secondary batteries, a fuel cell,
sometimes called a flow battery,
is not self-contained.
Electricity is produced through
the controlled oxidation of a fuel
in anode.
The oxidizing agent in the
 The combustion product is water which is
cathode is O2
environmentally benign. H2 2H+ + 2e- Anodic process
The most common fuel cell being developed for use in
cars is the proton exchange membrane fuel cell
(PEMFC), which uses H2 as the fuel and has an
operating temperature of2H
around
+ 80 o
C. 36
Cell reaction in proton exchange membrane
fuel cell (PEMFC),
 Type of fuel cells
S. Fuel Cell Electrolyte Operation
NO Temperatu
re (oC)
1 Proton Exchange Membrane Proton exchange 25-80
Fuel Cell (PEMFC) polymer
membrane
2 Solid oxide fuel cell (SOFC) Solid oxide 800-1000
electrolyte
(ZrO2)
3 Alkaline fuel cell An anion 80-90
exchange
membrane
4 Phosphoric acid fuel cell (PAFC) A polymer 190-200
membrane doped
with phosphoric
acid
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roton Exchange Membrane Fuel Cell (PEMFC)

The H+ produced in
anode chamber
moves to cathode
chamber through
PEM.

The protons
combine with O2- to
form H2O in cathode
chamber.
PEM refers
polymeric
proton exchange
membrane.
PEM 39
Solid Oxide Fuel Cell (SOFC)

In this cell:
A solid oxide acts as
an electrolyte as well
as separator.

Ceramic oxides are

used as electrolytes.

O2-

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Advantages and disadvantages of SOFC
Advantages of SOFC:
As the operation temperature is high level of fuel
flexibility
(H2, methane, other hydrocarbon fuels can be used
in the system)

Energy conversion efficiency is high as compared to

the conventional fuel combustion systems.
Disadvantage of SOFC:
The ceramic solid oxide becomes ionically conductive
only at high temperature (1100–1400K).
It causes high manufacturing cost, performance
degradation.
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Power density and
energy density of energy storage systems

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Energy density vs Power density
Energy density
Energy density is the amount
of energy available in a given mass (or volume)
If a system has a high energy density then it is
able to store a lot of energy in a small amount
of mass.
Energy density vs Power density
Power density
Power density is the amount of power in a given
mass.

A tiny capacitor may have the same power output as

a large battery.
 Formulas to calculate power and energy
density
• Power density = =

• Energy density =

• ==
Ecell = iR

• where i and ECell are current and EMF generated in a cell,

respectively. R is the resistance in the circuit.

• Power (Watt) = iEcell 45

Ragone Plot Ragone plot compares the
energy density of various
electrochemical systems.

It is a plot of energy density

Vs power density

The following generalization can

be made from Rogone Plot:

1. An energy storage system with high energy density may have poor
power density.

2. Fuels cells have high energy density (as molecular weight of H2 is

very vey small) but low power density.

3. Among the battery, lithium ion battery has high energy density due
to small atomic weight of lithium is small as compared to Ni-MH and
lead acid battery.
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Why we have to care about power density
and energy density?

The practical application of an electrochemica

systems is decided by it’s power and energy d

Operation of certain application requires high

power density electrochemical energy storag
system.

Whereas some other application requires the

high energy density systems with low power47
Examples
A battery with a high energy density, but low
power density can perform work for a relatively
long period of time.
Example, lithium ion battery in a mobile phone

High power density systems operate in burst mode,

they undergo charging and discharging quickly.
Example, a small capacitor powering the flash light of a
camera.
The capacitor has to be small enough to fit
inside the camera (or cell phone) but have a
high enough power output to light up the
subject of your photo. This makes a system
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Examples
The starting battery needs to
deliver a high power to crank
the engine, but not for very
long. Therefore it needs to be
built with a high power
density, but not necessarily
a very high energy density
as the starter motor is only
engaged for a few seconds.

The 'house' battery, on the

other hand, has the opposite
conditions. It will be expected
to deliver its energy over a
much longer period of time-
perhaps a few days use. But
the current draw is much less.
This means energy density
How are the units of cell potential (V)
related to those of energy available to do
work?
For two electrodes that differ by 1 volt of
electrical potential, 1 joule of energy is
released (that is, 1 joule of work can be done)
for each coulomb of charge that moves
between the electrodes.
1 V = J/C

50
a) Which electrode is anode during
discharging?

b) Which electrode is cathode during

charging?

c) Write down the reactions that is occurring

during the charging and discharging of the
lead acid battery.

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52
Both a D-sized and an AAA-sized
alkaline battery have an output of 1.5 V.
What property of the cell potential
allows this to occur?
What is different about these two
batteries?

53
 AAA D

A D-sized alkaline battery is much larger than

an AAA-sized one, so the D-sized battery
contains greater amounts of the cell
components. The cell potential is an intensive
property and does not depend on the amounts
of the cell components.

The total charge, however, depends on the

amount of cell components, so the D-sized
battery produces more charge than the AAA- 54
What kind of material is suitable for being
as anode?
Anode must be able to give out electrons:

Metals have tendency to give out electrons

readily, they are very good reducing agents.

So metals are used as anodes.

55
What kind of material is suitable for being
as cathode?
Cathode reactant must be able to readily accept
the electrons.

Metal oxides have tendency to accept electrons

readily, they are very good oxidizing agents.

So metal oxides are generally used as cathode

material.

These metal oxides are good electron acceptors.

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What is the final electron acceptor used in
fuel cells?

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 Corrosion

Corrosion is the natural redox (spontaneous) process

that oxidizes metals to their oxides and sulfides.

It is the reverse of isolating a metal from its oxide or

sulfide ore.

In electrochemical term, corrosion shares many

similarities with the operation of a voltaic (galvanic
cell).

Damage from corrosion to cars, ships, buildings, and

bridges runs into hundred of crores of rupees run
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 O2 as electron sink
H2 is the source of electron in a typical fuel cell
O2 is the sink (receiver) of electron
What is the sink of electron for aerobic respiration of animals/including humans?
2,
hat is the source of electron aerobic respiration?
lucose

What is the sink of electron for internal combustion engine that burns gasoline?
2 is the electron sink, gasoline is the source of electron.

What is the sink of electron for corrosion of iron? O2

Reduction occurs in cathode side of iron) 59
What is the source of electron for corrosion of iron?
ns. Iron (anodic oxidation of iron occurs in anodic side of iron)
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Rusting of Iron
The most common and economically destructive
form of corrosion is the rusting of iron.
Some important points about rusting of iron

1. Iron does not rust in dry air: moisture

must be present.
2. Iron does not rust in air-free water:
oxygen must be present.
3. The loss of iron and the depositing of
rust often occur at different places on
the same object.
4. Iron rusts more quickly at low pH
(high [H+).
5. Iron rusts more quickly in contact with
ionic solutions.
6. Iron rusts more quickly in contact with
a less active metal (such as Cu) and
more slowly in contact with a more 60
Rusting of Iron Resembles a Galvanic Cell
Process
Corrosion usually occurs at place of surface
irregularity.
The process resembles a galvanic cell process.
Same metal bar contains both anodic and cathodic
regions.

61
Summary of Iron Corrosion
1. Anodic and cathodic regions are separated in
space. •
2. In the anodic region, iron behaves like an active
electrode,
whereas in the cathodic region, it is inactive.
3. The moisture surrounding the pit functions
somewhat
like a salt bridge, a means for ions to ferry back
and forth
and keep the solution neutral.
4. The metallic part lies in between the anodic and
cathodic 62
 Oxidations of Fe0 to Fe2+

+
is soluble in water, 2 moles of Fe2+ undergoes further oxidation with 1/2 moles
to form the rust. This also accompanies proton release from 2 moles of H2O

63
2H2O 4H+ + 2 O2-
 Net reaction for rust formation
It is the sum of last two equations (Oxidation
to Fe2+ and Rust formation)

appears in both right and left side of the equation implies that H + is a catalyst
r the rusting process

64
 Effect of other metals on rusting of iron

0.34V -0.76 V

. -0.44 V

The standard reduction potential of Cu2+/Cu > Fe2+/Fe;

So, attachment of Cu to Fe will cause enhanced corrosion.

The standard reduction potential of Zn2+/Zn < Fe2+/Fe;

So, attachment of Zn to Fe prevent the rust formation,
causing cathodic protection. Instead of Fe, oxidation of Zn
occurs.

The coating of Zn on Fe is known as galvanization of iron.

65
Sacrificial Anode

66
Which one of the following can be
used as a sacrificial anode to protect
the iron from corrosion? Explain why?
Standard Reduction Potentials
Fe /Fe , -0.44 V
2+

1. Sn Sn2+/Sn , -0.14V
2. Pb
3. Al Pb2+/Pb , -0.13V
4. Ni Al3+/Al , -1.66 V

Ni2+/Ni -0.23 V

67
n the following example, Mg is used as a
acrificial anode to protect iron from corrosion.
Write the anodic, cathodic, and overall reaction?
Mg2+/Mg
-2.4 V

Anode-Oxidation
Mg + H2O MgO + 2e- + 2H

Fe2+/Fe
Cathode-Reduction
-0.44 1/2O2 + 2e- + 2H+ H2O

Mg + 1/2O2 MgO

68