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 ΔG= - 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 Capacity: Total quantity of electricity that can be withdrawn from a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 Self 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) + 2MnO2 (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)

Anode: Zn(s) 🡪 Zn2+(aq) + 2e-
 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 cathode Li Cells with Solid 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)(s) + H2O(l) + e- 🡪 Ni(OH)2(s) + OH-

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 metals.
 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 H2O

Representation of Lead Storage Cell : Pb, PbSO4(s) | H2SO4 (aq) | PbO2(s), Pb
 Lead-acid Storage Battery
• Ecell = 2 V.

• 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
Anode
Composition
• 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 Li1-xCoO2
Discharging + 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

• Biochemical Fuel cells (BCFC)

 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 H2 + O2 → 2 H2O (Net reaction)

K+OH-

Voltage: 1.15 V
Power: 10-100 KW
Porous carbon Anode with Pt/Ni catalyst
 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, ZrO2 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