Batteries and Fuel Cells

Introduction
• A battery is a device that converts the chemical energy
contained in its active materials directly into electric energy by
means of an electrochemical oxidation-reduction (redox)
reaction.
• In the case of a rechargeable system, the battery is recharged
by a reversal of the process. This type of reaction involves the
transfer of electrons from one material to another through an
electric circuit.
• In a nonelectrochemical redox reaction, such as rusting or
burning, the transfer of electrons occurs directly and only heat
is involved.
• As the battery electrochemically converts chemical energy into
electric energy, it is not subject, as are combustion or heat
engines, to the limitations of the Carnot cycle dictated by the
second law of thermodynamics.
• Batteries, therefore, are capable of having higher energy
conversion efficiencies.
• While the term ‘‘battery’’ is often used, the basic electrochemical unit
being referred to is the ‘‘cell.’’
• A battery consists of one or more of these cells, connected in series or
parallel, or both, depending on the desired output voltage and capacity.

The cell consists of three major components:

• 1. The anode or negative electrode—the reducing or fuel electrode—

which gives up electrons to the external circuit and is oxidized during the
electrochemical reaction.
• 2. The cathode or positive electrode—the oxidizing electrode—which
accepts electrons from the external circuit and is reduced during the
electrochemical reaction.
• The electrolyte—the ionic conductor—which provides the medium for
transfer of charge, as ions, inside the cell between the anode and
cathode. The electrolyte is typically a liquid, such as water or other
solvents, with dissolved salts, acids, or alkalis to impart ionic conductivity.
Some batteries use solid electrolytes, which are ionic conductors at the
operating temperature of the cell.
Cell vs. Battery:

• A cell is the basic electrochemical unit providing a source of electrical

energy by direct conversion of chemical energy.

• The cell consists of an assembly of electrodes, separators, electrolyte,

container and terminals.

• A battery consists of one or more electrochemical cells, electrically

connected in an appropriate series / parallel arrangement to provide
the required operating voltage and current levels, including, if any,
monitors, controls and other ancillary components (e.g. fuses,
diodes), case, terminals and markings.

• (Although much less popular, in some publications, the term

‘‘battery’’ is considered to contain two or more cells.)
 CLASSIFICATION OF BATTERIES
• Electrochemical cells and batteries are identified as primary
(nonrechargeable) or secondary (rechargeable), depending on their
capability of being electrically recharged.
Primary Cells or Batteries
• These batteries are not capable of being easily or effectively recharged
electrically and, hence, are discharged once and discarded. Many primary
cells in which the electrolyte is contained by an absorbent or separator
material (there is no free or liquid electrolyte) are termed ‘‘dry cells.’’ Ex:
Zinc-carbon cells, Alkaline battery, Lithium battery, Mercury battery, Silver
oxide battery

Secondary or Rechargeable Cells or Batteries

• These batteries can be recharged electrically, after discharge, to their
original condition by passing current through them in the opposite
direction to that of the discharge current.
• They are storage devices for electric energy and are known also as ‘‘storage
batteries’’ or ‘‘accumulators.’’ Ex: Lead acid battery, Nickel-cadmium
battery, Lithium ion battery, Nickel metal hydride battery
 The applications of secondary batteries

• The secondary battery is used as an energy-storage device,

generally being electrically connected to and charged by a prime
energy source and delivering its energy to the load on demand.
Examples are automotive and aircraft systems, emergency no-fail
and standby (UPS) power sources, hybrid electric vehicles and
stationary energy storage (SES) systems for electric utility load
leveling.

• The secondary battery is used or discharged essentially as a

primary battery, but recharged after use rather than being
discarded. Secondary batteries are used in this manner as, for
example, in portable consumer electronics, power tools, electric
vehicles, etc., for cost savings (as they can be recharged rather
than replaced), and in applications requiring power drains
beyond the capability of primary batteries.
 Primary Battery
• In the primary batteries, the reaction occurs only once and after use over a
period of time battery becomes dead and cannot be reused again. The most
familiar example of this type is the dry cell which is used commonly in our
transistors and clocks.
• The cell consists of a zinc container that acts as anode
and the cathode is a carbon (graphite) rod surrounded by
powdered manganese dioxide and carbon. The space
between the electrodes is filled by a moist paste of
ammonium chloride (NH4Cl) and zinc chloride (ZnCl2).
• The electrode reactions as follows :
Anode: Zn(s) ⎯→ Zn2+ + 2e–
Cathode: MnO2+ NH4++ e–⎯→ MnO(OH) + NH3

• In the reaction at cathode, manganese is reduced from

the + 4 oxidation state to the +3 state. Ammonia
produced in the reaction forms a complex with Zn2+ to
give [Zn(NH3)4]2+. The cell has a potential of nearly 1.5 V.
• Mercury cell, suitable for low current devices like hearing aids, watches,
etc. consists of zinc – mercury amalgam as anode and a paste of HgO
and carbon as the cathode.
• The electrolyte is a paste of KOH and ZnO. The electrode reactions for
the cell are given below:

Anode: Zn(Hg) + 2OH– ⎯→ ZnO(s) + H2O + 2e–

Cathode: HgO + H2O + 2e– ⎯→ Hg(l ) + 2OH–

The overall reaction is represented by

Zn(Hg) + HgO(s) ⎯→ ZnO(s) + Hg(l )

The cell potential is approximately 1.35 V

and remains constant during its life as the
overall reaction does not involve any ion
in solution whose concentration can
change during its life time.
 Secondary Batteries
• The most important secondary cell is the lead storage battery (Fig. commonly used
in automobiles and invertors.
• It consists of a lead anode and a grid of lead packed with lead dioxide (PbO2 ) as
cathode. A 38% solution of sulphuric acid is used as an electrolyte.
The cell reactions when the battery is in use are given below:
Anode: Pb(s) + SO42–(aq) → PbSO4(s) + 2e–
Cathode: PbO2(s) + SO42–(aq) + 4H+(aq) + 2e– → PbSO4 (s) + 2H2O (l )
i.e., overall cell reaction consisting of cathode and anode reactions is:
Pb(s)+PbO2(s)+2H2SO4(aq)→ 2PbSO4(s) + 2H2O(l)
On charging the battery the reaction is reversed and PbSO4(s) on
anode and cathode is converted into Pb and PbO2, respectively.
 Redox Batteries
The term ‘‘redox’’ is obtained from a contraction of the words
‘‘reduction’’ and ‘‘oxidation.’’ Although reduction and oxidation occur
in all battery systems, the term ‘‘redox battery’’ is used for those
electrochemical systems where the oxidation and reduction involves
only ionic species in solution and the reactions take place on inert
electrodes. This means that the active materials must be mostly
stored externally from the cells of the battery. Although redox
systems are capable of long life, their energy density is low because
of the limited solubility of the active materials typically involved.

Vanadium Redox Battery or VRB as it is known, has any

significant development continuing as of 2001.
The electrolytes in the positive and negative electrode compartments of
Vanadium Redox Batteries are different valence states of vanadium
sulfate. Both solutions are 2 M in concentration and contain sulfuric
acid as a supporting electrolyte. The electrode reactions occur in
solution, with the reaction:

at the negative electrode in discharge being:

Both reactions are reversible on the carbon felt electrodes that are used.
An ion-selective membrane is used to separate the electrolytes in the
positive and negative compartments of the cells. Cross-mixing of the
reactants would result in a permanent loss in energy storage capacity
for the system because of the resulting dilution of the active materials.
Migration of other ions (mainly H) to maintain electroneutrality, however,
must be permitted. Thus, ion-selective membranes are required.
 LITHIUM-ION BATTERIES
Lithium-ion (Li-ion) batteries are comprised of cells that employ lithium
intercalation compounds as the positive and negative materials. As a
battery is cycled, lithium ions (Li) exchange between the positive
and negative electrodes. They are also referred to as rocking chair
batteries as the lithium ions ‘‘rock’’ back and forth between the positive
and negative electrodes as the cell is charged and discharged. The
positive electrode material is typically a metal oxide with a layered
structure, such as lithium cobalt oxide (LiCoO2), or a material with
a tunneled structure, such as lithium manganese oxide (LiMn2O4),
on a current collector of aluminum foil. The negative electrode
material is typically a graphitic carbon, also a layered material, on
a copper current collector. In the charge/ discharge process, lithium
ions are inserted or extracted from interstitial space between atomic
layers within the active materials.
Schematic of the electrochemical process in a Li-ion cell.
In this scheme, LiMO2 represents the metal oxide positive material, such as
LiCoO2, and C the carbonaceous negative material, such as graphite. The
reverse happens on discharge. As metallic lithium is not present in the cell, Li-
ion batteries are chemically less reactive, safer, and offer longer cycle life than
possible with rechargeable lithium batteries that employ lithium metal as the
negative electrode material. The charge/discharge process in a Li-ion cell is
further illustrated graphically in Fig. In the figure, the layered active materials
are shown on metallic current collectors.

Electrode and cell reactions in a Li-ion cell.

Advantages and Disadvantages of Li-ion Batteries
 Fuel Cells
• Fuel cells, like batteries, are electrochemical galvanic cells that
convert chemical energy directly into electrical energy and are not
subject to the Carnot cycle limitations of heat engines.
• Fuel cells are similar to batteries except that the active materials are
not an integral part of the device (as in a battery), but are fed into
the fuel cell from an external source when power is desired.
•

• The fuel cell differs from a battery in that it has the capability of
producing electrical energy as long as the active materials are fed to
the electrodes.
• The battery will cease to produce electrical energy when the limiting
reactant stored within the cell is consumed.
• The electrode materials of the fuel cell are inert and have catalytic
properties which enhance the electroreduction or electrooxidation
of the reactants (the active materials).
• The anode active materials used in fuel cells are generally gaseous
or liquid (compared with the metal anodes generally used in most
batteries) and are fed into the anode side of the fuel cell.
• Oxygen or air is the predominant oxidant and is fed into the
cathode side of the fuel cell.

Fuel cell technology can be classified into two categories

• Direct systems where fuels, such as hydrogen, methanol and

hydrazine, can react directly in the fuel cell
• Indirect systems in which the fuel, such as natural gas or other fossil
fuel, is first converted by reforming to a hydrogen-rich gas which is
then fed into the fuel cell
• One of the most successful fuel cells uses the reaction of hydrogen with
oxygen to form water. The cell was used for providing electrical power in
the Apollo space programme.
• The water vapours produced during the reaction were condensed and
added to the drinking water supply for the astronauts.
• In the cell, hydrogen and oxygen are bubbled through porous carbon
electrodes into concentrated aqueous sodium hydroxide solution.
• Catalysts like finely divided platinum or palladium metal are incorporated
into the electrodes for increasing the rate of electrode reactions.
The electrode reactions are given below:
Anode: 2H2 (g) + 4OH–(aq) ⎯→ 4H2O(l) + 4e–
Cathode: O2(g) + 2H2O(l ) + 4e–⎯→ 4OH–(aq)

Overall reaction being:

2H2(g) + O2(g) ⎯→ 2 H2O(l )

• The cell runs continuously as long as the reactants are supplied.

• Fuel cells produce electricity with an efficiency of about 70 %
compared to thermal plants whose efficiency is about 40%.
• There has been tremendous progress in the development of new
electrode materials, better catalysts and electrolytes for
increasing the efficiency of fuel cells.
• These have been used in automobiles on an experimental basis.
• Fuel cells are pollution free and in view of their future
importance, a variety of fuel cells have been fabricated and tried.
 Alkaline Fuel Cells
Alkaline fuel cells differ from other types of fuel cells in the chemical reaction
and the operating temperature. Hydrogen and oxygen are reactants and
Potassium hydroxide and electrolyte
The chemical reaction that occurs at the
anode is:
2H2 + 4OH
− 4H2O + 4e
−

The reaction at the cathode occurs

when the electrons pass around an
external circuit and react to form
hydroxide ions, OH−, as shown:

O2 + 4e− + 2H2O 4OH−

Alkaline fuel cells have some major advantages over other types of fuel cells.
The rest is that the activation overvoltage at the cathode is usually less than
with an acid electrolyte fuel cell. The second advantage is that the electrodes
do not have to be made of precious metals.
 Molten Carbonate Fuel Cell
The defining characteristic of a molten carbonate fuel cell (MCFC) is the
material used for the electrolyte. The material is a molten mixture of alkali
metal carbonates. The electrolyte is usually a binary mixture of lithium and
potassium, or lithium and sodium carbonates which is held in a ceramic
matrix of LiAlO2. A highly conductive molten salt is formed by the carbonates
at very high temperatures.
 Direct Methanol Fuel Cells
The use of pure hydrogen in fuel cells is not the only way to convert hydrogen
into useful electric energy. A variety of reactions can produce hydrogen
indirectly, thus enabling the classic hydrogen fuel cell chemical reaction to
take place.
The fuel is a mixture of water and of methanol; it reacts directly at the
anode according to:
CH3OH + H20 6H+ + 6e− +CO2

As mentioned above the boiling point of methanol at atmospheric pressure is

65oC, thus the cells requires an operating temperature around 70oC (to avoid a
too high vapor pressure). The reaction mechanism is much more complex with
the appearance of species adsorbed as well as with HCOH and HCOOH. If
one considers this reaction on a Pt/Ru catalyst, it can be represented with the
following stages.
The compounds PtCOH and PtCO are poisons for Platinum, and after research
it was found that the addition of Ruthenium makes it possible to cure the Pt,
and prevent poisoning.

The above reactions give the production of the hydrogen, which can in turn
be used by the cathode. The cathode undergoes the typical fuel cell reaction
with hydrogen combining with oxygen. The total DMFC equation,
representing only the initial and final products for both the cathode and
anode is as follows:
 Difference between a fuel cell and
a battery
Batteries
• A battery stores the chemical
reactants, usually metal
compounds like lithium, zinc
or manganese.
• Batteries will produce
electricity as long as reactive
materials are present.
• Once used up, you must
recharge or throw away the
battery.
Fuel Cell
• A fuel cell creates electricity
through reactants (hydrogen
and oxygen) stored externally.
• A fuel cell will produce
electricity as long as it has a
fuel supply.
• In short, a fuel cell vehicle is
refueled instead of recharged.