Batteries and Fuel Cells

Module 4
 Batteries
• A Battery is a device that consists of one or more galvanic cells
connected in series and/or parallel, which converts the
chemical energy (redox reaction) to electrical energy in a
stored form and can be used whenever required.
 Terminology
1. EMF of a battery G= - nFE

2. Capacity: Total quantity of electricity that can be

withdrawn from a full charged cell.

3. Energy Density: Voltage of the cell and amount of charge

that can be stored.

4. Long Shelf life

5. Safety

6. Compact and light weight

7. Low price

8. Cycling
 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.
Ex: Dry cell, Leclanché Cell

• 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.
Ex: Lead-Acid Batteries, Ni-Cd, Li-ion

• Flow battery and fuel cell

In which materials (reactants, products, electrolytes) pass through the
battery continuously,
 Primary Cell
In our everyday experience, we know that some batteries are
rechargeable, whereas others are used once and disposed of.

Single-use batteries that cannot be recharged are called primary

cells or primary batteries.

Flashlights almost always rely on alkaline batteries, and many MP3

players or handheld video games can also use them.
 Leclanché Cell

The venerable carbon-zinc

cell or Leclanché cell was
invented in 1866 by
Georges Leclanché and
was the most common
small battery throughout
most of the 20th century

Representation: Zn| Zn2+ || NH4+ | MnO2| C

https://youtu.be/lSq_WVC6Hiw
Anodic reaction : Zn(s)  Zn2+(aq) + 2e-

Cathodic reaction: 2 MnO2(s) + 2 H2O(l) + 2e-  2 MnO(OH)(s) + 2 OH -

Net Cell Reaction : Zn(s) + 2MnO 2 (s) + 2H2O(l)  2MnO(OH)(s) + Zn2+

+2OH-

Drawbacks:
• 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.

MnO2 in the cell removes the H2 according to the following reaction:

2MnO2(s) + H2(g) → Mn2O3(s) + H2O(l)

 Zn-Carbon Dry Cell
• A dry cell has the electrolyte
immobilized as a paste, with only
enough moisture in it to allow
current to flow.

• Unlike a wet cell, a dry cell can

operate in any orientation without
spilling, as it contains no free
liquid.

• The potential is 1.50 V.

• The carbon powder will increase

the electrical conductivity of the
MnO2 and retain the moisture of
the electrolyte.

Cathode: 2 NH4(aq) + 2 MnO2(s) + 2 e-→ Mn2O3(s) + 2 NH3(g) +

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
 Alkaline Battery

The most prevalent type of primary battery in use today is the

alkaline battery.
 Alkaline Battery

• The anode in an alkaline battery is a zinc electrode, and

the oxidation half- reaction can be written:

Zn(s) + 2 OH-(aq)  ZnO + H2O(l) + 2 e-

• The cathode is derived from manganese(IV) oxide, and the

half-reaction is

2 MnO2(s) + H2O(l) + 2 e-  Mn2O3(s) + 2 OH-(aq)

• We can combine these two half-reactions to yield a net

equation that represents the chemistry of an alkaline dry
cell battery.

Zn(s) + 2 MnO2(s) + H2O(l)  Zn(OH)2(s) + Mn2O3(s)

 Alkaline Battery
The essential design features of an alkaline battery:

• The electrolyte used is KOH, but rather than dissolving the

electrolyte in liquid water, it is in the form of a paste or a gel—
hence the term dry cell.

• The MnO2 for the cathode is mixed with graphite to increase

conductivity.

• The anode is a paste containing powdered zinc. (Powdering the

zinc increases the surface area and improves performance.)

• The battery case is also important in the design. Electrons

generated by oxidation are collected by a piece of tin-coated brass
connected to the bottom of the battery case. The remainder of the
battery case is in contact with the cathode, but a protrusion on
top makes it easier for a consumer to identify the positive
terminal.
 Alkaline Battery
Alkaline batteries are prone to leaking potassium hydroxide, a caustic
agent that
can cause respiratory, eye and skin irritation.

This can be avoided by

• Not attempting to recharge disposable alkaline cells,

• Not mixing different battery types in the same device,
• Replacing all of the batteries at the same time,
• storing in a dry place.

Caution

• Once a leak has formed due to corrosion of the outer steel shell,
potassium hydroxide forms a feathery crystalline structure that grows
and spreads out from the battery over time, following up metal
electrodes to circuit boards where it commences oxidation of copper
tracks and other components, leading to permanent circuitry damage.

• The leaking crystalline growths can also emerge from seams around
battery covers to form a furry coating outside the device, that corrodes
any objects in contact with the leaking device.
 Mercury Battery
• For a medical device, such as a heart pacemaker, a battery should
not only be small but long lasting. Mercury batteries have come to fill
this role.

• The mercury battery (also called a zinc-mercuric oxide cell) shown

here has a voltage output that is extremely stable over long times.
Anode: Zn(s) + 2 OH-(aq)  Zn(OH)2(s) + 2 e-

Cathode: HgO(s) + H2O(l) + 2 e-  Hg (l) + 2 OH-(aq)

The potential is 1.35 V
 Mercury Battery
• These batteries are commonly used in devices where frequent
battery changes would be a nuisance or hazard.

• In a mercury battery, sodium hydroxide or potassium hydroxide is

used as an electrolyte.

• Sodium hydroxide cells have nearly constant voltage at low

discharge currents, making them ideal for hearing aids, calculators,
and electronic watches.

• Potassium hydroxide cells, in turn, provide constant voltage at higher

currents, making them suitable for applications requiring current
surges, such as photographic cameras with flash and watches with a
backlight.
 Zinc-air Battery
• These batteries are sold as single-use, long lasting products for
emergency use in cellular phones.

• In a zinc-air battery, one of the reactants is oxygen from the

surrounding air. They can also be kept on hand in sealed bags and
charged when needed by opening the bag to expose the battery
to air.
Anode: Zn(s) + 2 OH-(aq)  Zn(OH)2(s) + 2
e
Cathode: ½ O2 (g) + H2O(l) + 2 e-  2 OH-

• There are obstacles to

the widespread use of
this technology because
environmental factors,
such as humidity, affect
its performance.
 Primary Lithium batteries
• One of the main attractions of lithium as an anode material in
its position as the most electropositive 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 inflammable 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 Primary batteries
Li Cells with solid cathode Li Cells with Soluble Li Cells with Solid
cathode electrolyte

Li Cells with solid cathode

3 to 3.2 V
High energy density, good low-temperature
performance; cost effective. Small in size, long self
life,
Electrical medical devices; memory circuits

Anode: Li,

Cathode: MnO2 or V2O5 mixed with 10% graphite

Electrolyte: Lithium salt in organic solvent

Cathode: Mn4+  Mn3+

V5+  V4+
Li Cells with Soluble cathode:

Anode: Li,
Cathode: SO2; SOCl2or SO2Cl2 dissolved in electrolyte
Electrolyte: Lithium salt in organic solvent
Cathode: 2SO2 + 2e-  S2O42-
2SOCl2 + 4e-  4Cl- + S +SO2
SO2Cl2 + 2e-  2Cl- + SO2

Li Cells with Solid Electrolyte:

Anode: Li,
Cathode: TiS2, V2O5
Electrolyte: Solid electrolyte Such as LiX in PEO (Polyethylene
oxide)

Long Life due to no evaporation of electrolyte

 Secondary Cell
• Rechargeable batteries are examples of secondary cells or
secondary batteries.
 Ni – Cd Battery

Electrolyte: KOH

Discharging

At anode: Cd(s) + 2 OH-  Cd(OH)2(s) +2e-

At cathode : 2NiO(OH) + 2H2O(l) + 2e-  2 Ni(OH)2 (s) + 2 OH- (aq)

Net reaction: 2 NiO(OH)(s) + Cd(s) +2 H2O(l) Cd(OH)2(s) + 2 Ni(OH)2(s)

 Discharge and Charge
Chemistry
• Ni-Cd batteries can be expended and recharged many times, but they
are sometimes susceptible to a performance-decreasing memory
effect, inability to use all of the possible chemical energy of the
battery unless it is completely discharged. So successive recharging
ultimately results in shorter times before the battery appears to die.

• Memory effect is caused due to the formation of a thin layer of

material on the electrodes inside the battery, limiting the redox
reactions in the cell.

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.
 Applications

• Motorized equipment
• Power tools
• Transistors
• Electronic calculators
• Commercial and industrial portable products
• Medical instrumentation
• Emergency lighting
• Toys
• Cordless and wireless telephones

• Medical equipment
• Personal care
• Professional lighting
• Radio communication
• Professional tooling
• Military equipment
• Professional electronic devices
 Ni – Metal-hydride
Battery
Cathode: NiO(OH) + H O + e  Ni(OH) -
+ OH-
(s) 2 (l) 2(s)

Electrolyte: KOH

Cell voltage is 1.2-

1.5 V
Anode: MH(s) + 2 OH-(aq)  M(s) + H2O(l)+ 2 e-
• Nickel-metal-hydride batteries find use in many of the same devices as
Ni-cad cells, and larger versions serve as the main batteries in hybrid
cars.

• Anode is made 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. Some of the alloys used in commercially
available Ni-metal-hydride batteries contain as many as seven different
 Lead-acid Storage
•
Battery
The most widely selling rechargeable batteries are the lead storage
batteries in automobiles, which have been using the same
technology for roughly 100 years.
 Lead-acid Storage
• Battery
The electrolyte for this battery is sulfuric acid.

• Sulfate ion is converted to HSO4- under the highly acidic conditions

of the battery. Because of the importance of sulfuric acid in these
batteries, they are sometimes referred to as lead-acid storage
batteries.

Anode:
Pb(s) + SO42-(aq)  PbSO4(s) + 2 e-

Ecell = 2.0 V

Cathode: PbO2(s) + 4 H+(aq) + SO42-(aq) + 2 e-  PbSO4(s) + 2

Representation of Lead Storage H 2O : Pb, PbSO
Cell | H SO
4(s) 2 |4 (aq)
 Lead-acid Storage
• Ecell = 2 V. Battery
• For a standard 12-V automobile battery, connect six cells wired in
series.

• These batteries are rechargeable because the PbSO4 produced adhere

to the electrode surfaces. Passing electric current (obtained from the
alternator of the automobile) to drive the redox reactions in the
nonspontaneous direction recharges the battery.

• Driving the reactions in a battery in the reverse direction to recharge

it sometimes requires a larger voltage than the discharge voltage to
ensure that all chemical species are returned to their original states.

• Eventually, as the battery experiences mechanical shocks from

bumping and jarring during the normal use of a car, PbSO4 falls away
from the electrodes. Eventually the battery can no longer be
recharged and must be replaced.
Secondary Lithium Ion
Batteries
 Composition
Anode
• Carbon based.
• This lithium content is lower then 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.
• Polymer electrolyte
Cathode materials
• The most common compounds 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
• 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.
 Working

Charging Discharging
The following reactions take place upon working

Cathode: LiCoO2 Charging Li1-xCoO2 + xLi+ + xe-

Discharging

Charging
Anode: xLi+ + C + Xe- Discharging
CLix
Charging
Overall: LiCoO2 + C Discharging Li1-xCoO2 + LixC
 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 (Intercalation), for example

CoO2, is then used as the cathode material, and lithium ions
are exchanged back (deintercalation) 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 Polymer Battery

Electrolyte is a polymer
Fuel Cells
 Fuel Cells

An electrochemical cell in which the energy of a reaction between

a fuel (such as liquid hydrogen) and an oxidant (such as liquid
oxygen) is converted directly and continuously into electrical
energy.

Fuel cell: Operates with continuous replenishment of fuels at

electrodes which doesn’t require charging.

Representation: Fuel| electrode| electrolyte| electrode| Oxidant

At Anode: Fuel → Oxidized product + ne-

At Cathode: Oxidant + ne- → reduced product
 Fuel Cells
Classification :
1. Low Temperature fuel cells (< 100oC)
2. Moderate Temperature fuel cells (100 to 250oC)
3. High Temperature fuel cell (> 500oC)

Types :
• Alkaline Fuel Cells (AFC): US spacecraft

• Phosphoric Acid Fuel Cells (PAFC): Stationary power generation, city

buses

• Molten Carbonate Fuel Cells (MCFC): Military application, power plants

• Polymer Electrolyte Membrane Fuel Cells (PEMFC): Car, Bus

• Solid Oxide Fuel Cells (SOFC): Industry

•
 Alkaline Fuel Cells (or) H2- O2 Fuel Cells

Unreacted Oxygen
or Air free from CO2
Unreacted H2

- +
e- e-

2 H2 + 4 OH-  H2O + 4 e- (Anode)

O2 + 2 H2O + 4 e-  4 OH- (Cathode)

2 H 2 + O 2  2 H 2O (Net reaction)
K+OH-

Voltage: 1.15 V
Power: 10-100 KW
Porous carbon Anode with Pt/Ni catalyst
 Task

Q1. What is a fuel cell? What are its basic characteristics? How are fuel cells
different from galvanic cell?
 Solid Oxide Fuel Cells (SOFC)

Electrolyte all made up of ceramic substances

• Anode : porous carbon
• Cathode: Thin porous carbon layer where oxygen reduction occurs.
• Fuel: Hydrogen
• Electrolyte : Solid oxide or ceramic electrolyte - Dense layer of
oxygen conducting ceramic. - mixture of Ni, ZrO 2 and CaO coated on
either side by porous electrode materials. Others include yettrium
stabilized zirconia (YSZ) and gadolinium doped ceria (GDC)
• Operating Temp: >1000 0C
• Efficiency: 50-60% due to low conductivity solid oxide electrolyte
 Construction

• High efficiency
• Long term stability
• Fuel flexibility
• Low emissions
• High operating temp – longer start up
times
• Mechanical / Chemical compatibility issues.
 Micro Fuel Cell Powered Small Gadgets

music player cell phone

fuel cartridge