Energy Technology

chemical energy storage

 Introduction
 This source includes augmentation of efforts on the development of fuel cells and
batteries. The development of particular type of fuel cells and batteries holds promise
for:
1. running small and light commercial vehicles in the beginning followed by for heavy
vehicles ;
2. rural electrification of remote small villages having a population of 100—500 through
rechargable power batteries, (the batteries can be charged with the help of wind mills).
This would also help achieving the social objectives of the Government to provide
electricity for lighting rural areas where laying of transmission faces hazards. The work on
batteries and fuel cells, viz. sodium sulphur batteries, metal air rechargable cells, hydrogen
oxygen and lithium fuel cells etc. is already in progress in a number of places in our
country.
 The Department of Non-conventional Sources (DNES), India, has been promoting
R&D efforts relating to chemical and electrochemical sources of enerW keeping in
view their potential role in the long term.
 The Department extended support for studies relating to Beta, Alumina for Sodium
Sulphur batteries, Lithiumion conductors for solid state batteries, fuel cell materials
and development of high energy density storage batteries suitable for photo voltaic
and other applications.
 Fuel cells
Introduction
 A cell (or combination of cells) capable of generating an electric current by
converting the chemical energy of a fuel directly into electrical energy.
 The fuel cell is similar to other electric cells in the respect that it consists of positive
and negative electrodes with an electrolvte between them.
 Fuel in a suitable form is supplied to the negative electrode and oxygen, often from
air, to the positive electrode. When the cell operates, the fuel is oxidised and the
chemical reaction provides the that is converted into electricity.
 Fuel cells differ from conventional electric cells in the respect that the active material
(i.e. fuel and oxygen) are not contained within the cell but are supplied from outside.
 But for its costs, pure (or fairly pure) hydrogen gas would be preferred fuel for fuel
cells.
 Alternatively impure hydrogen obtained from hydrocarbon fuels, such as natural gas
or substitute natural gas (methane), liquefied petroleum gas (propane and butane) or
liquid petroleum products, can be used in fuel cells. Efforts are being made to
develop cells that can use carbon monoxide as the fuel ; if they are successful, it
should be possible to utilize coal as the primary energy source. Main uses of fuel
cells are in power production, automobile vehicle and in special military use.
 Design and principles of operation of a fuel cell

 As stated these are electro-chemical devices in which the chemical energy of fuel is
converted directly into electric energy. The chemical is the free of the reactants used.
This conversion takes place at constant temperature and pressure. The basic feature
of the fuel cell is and its and its oxidant are combined in the form of ions rather than
neutral molecules.
 The first practical fuel cells was demonstrated by Francis T. Bacin and J.C. Frost of
Cambridge University in 1959. As per the fuel used the main types of fuel cells are:
1. Hydrogen (H2) fuel cell,
2. Hydrazine (N2H4) fuel cell,
3. Hydrocarbon fuel cell, and
4. Alcohol (Methanol) fuel cell.
 The operation of the fuel cell can best be described with reference to a specific
device. Fuel cell can be adopted to a variety of fuels by changing the catalyst.
 The main components of a fuel cell are :
1. fuel electrode (anode),
2. an oxidant or air electrode (cathode), and
3. an electrolyte.
 Cont...
 In most fuel cells, hydrogen (pure or impure) is the active material at the negative
electrode and oxygen (from the oxygen or air) is active at the positive electrode.
Since hydrogen and a fuel cell requires a solid electrical conductor to serve as a
current collector and to provide a terminal at each electrode. The solid electrode
material is generally porous.
 Porous nickel electrodes and porous carbon electrodes are applications. Platinum and
other precious metals are being used in certain fuel have potential utility in military
and space applications.
 The porous electrode has a larger number of sites, where the gas, electrolyte and
electrode are in contact; the electro chemical reactions occur at these sites. The
reactions are normally very slow, and catalyst is included in the electrode to expedite
them. The best electrochemical catalysts are finely divided platinum or platinum like
metal deposited on or incorporated with the porous electrode material.
 Since the platinum metals are expensive, other catalysts, such as nickel (for
hydrogen) and silver (for oxygen), are used where possible. The very small catalyst
particles provide a large number of active sites at which the electro-chemical
reactions can take place at a fairly rapid rate.
 Cont...
 Hydrogen gas is supplied to one electrode and oxygen gas (or air) to the other.
Between the electrodes is a layer of electrolyte. Most existing fuel cells operate at
temperature below about 200 ˚C ; the electrolyte is then usually and aqueous solution
of an alkali or acid. The liquid electrolyte is generally retained in a porous membrane
but it may be free flowing in some cells. Different electric current is drawn from the
cell in the usual manner by connecting a load between the electrode terminals.
 Electro-Chemical Reactions
 At
  the negative electrode, hydrogen gas (H 2) is converted into hydrogen ions (H +) , i.e. hydrogen
with a positive electric change, plus an equivalent number of electrons i.e. (e –); thus,
H2 → 2H+ + 2e–
 At this electrode, hydrogen is diffused through the permeable nickel. which is embedded a
catalyst. The catalyst enables the hydrogen molecules, H 2 to be absorbed, on the electrode
surface as hydrogen atoms, which react with the hydroxyl ions (OH –) in the electrolyte to form
water.
 When the cell is operating and producing current, the electrons flow through the external load to
the positive electrode; here they interact with oxygen (O 2) and water (H2O) negatively charged
hydroxyl (OH –) ions ; thus

 The hydroxyl ions and hydrogen then combine in the electrolyte to produce water
H+ + OH – → H2O
 The electrolyte is typically 40 % KOH solution because of its high electrical conductivity and it
is less corrosive than acids.
 The above equations show that hydroxyl ions produced at one electrode are involved in the
reaction at the other. Also electrons are absorbed from the oxygen electrode and released to the
hydrogen electrode. Addition of the three forgoing reactions show that when the cell is
operating, the overall process is the chemical combination of hydrogen and oxygen (gases) to
form water that is
 Classification of fuel cells
 Classification according to the temperature range in which they operate,
 Low temperature : 25 – 100 C
 Medium temperature: 100 – 500 C
 High temperature: 500 – 1000 C and
 Very high temperatureabove – 1000 C
 Classification according to the type of electrolyte, e.g., aqueous, non-aqueous, molten or
solid. One could also classify the fuel cells according to the physical state of the fuel :
 Gas – hydrogen, lower hydrocarbons
 Liquid – alcohols, hydrazine, higher hydrocarbons
 Solid – Metals etc.
 A broad division has been made according to primary or secondary fuel cell.
 A primary fuel cell may be defined as one in which the reactants are passed through the cell only
once, the products of the reaction being discarded e.g., H 2 – O2 fuel cell.
 A secondary fuel cell is one in which the reactants are passed through the cell many times
because they are regenerated from the products by thermal, electrical, photochemical methods,
e.g. Nitric oxide – chlorine fuel cells.
 Types of Fuel Cells and Ion exchange fuel cell
 Types of fuel cells are:
 Hydrogen
 Fossil fuel
 Hydrocarbon
 Alcohol
 Hydrazine

Ion exchange fuel cell

 The basic design of the cell, which consist of a solid electrolyte ion exchange membrane, electro
catalysts and gas feed tubes. The distinctive feature of this cell is that it uses a solid electrolyte in
the form of an ion-exchange membrane. The membrane is non-permeable to the reactant gases,
hydrogen and oxygen, which thus prevent them from coming into contact. The membrane is
however permeable to hydrogen ions which are the current carriers in the electrolyte.
 The desired properties of an idea ion – exchange membrane electrolyte are:
 High ionic conductivity
 Zero electronic conductivity
 Low permeability of fuel and oxidant
 Low degree of electro – osmosis
 High resistance to dehydration
 High resistance to its oxidation or hydrolysis
 Mechanical stability
 Ion-exchange membrane working
 The two electrodes, which consist of the electrocatalyst and a plastic material for water -
proofing the electrode are in the form of fine metallic wire screens. They are bonded on
either side of the electrolyte layer.
 The wire screen material is titanium or platinum. Metallic current collectors are ribbed onto
each electrode. The hydrogen compartment of the cell is enclosed; the hydrogen gas enters
this compartment through a small inlet and circulates throughout the ribbed current
collectors and distributes itself evenly over the electrode.
 On the opposite side oxygen or air enters the compartment, coolant tubes run through the
ribs of the current collectors.
 On the oxygen side, the current
collectors, also hold wicks which
absorb water, the product of fuel-cell
reaction and carry it over by capillary
action. The water leaves the cell
through an exit from the oxygen
compartment. Oxygen is prevented
from leaving its compartment by
inclusion of a differential pressure
water-separation system.
 Reaction
  
The ion-exchange membrane electrolyte is acidic and the current carriers in the
solution are hydrogen ions. The hydrogen ions are produced by the reaction at anode
according to,
2H2 → 4H+ + 4e–
 These ions are then transported to the cathode through the electrolyte and electrons
reach the cathode via the external circuit. At the cathode, oxygen is reduced
producing water as represented by:
O2 + 4H+ + 4e – → 2H2O
 Thus the overall reaction is

 This cell operates at about 40 – 60 ˚C. The thermodynamic reversible potential for
the reaction s 1.23 volts at 25 ˚C.
 Molten carbonate cell
 These are high cells with a molten carbonate mixture as the electrolyte, offer
the prospect, for use with a variety of fossil fuel including coal.
 A special feature of these cells is that during operation they can oxidize
carbon monoxide to carbon dioxide as well as hydrogen to water.
 The electrolyte in the high temperature fuel cells under development is a
molten mixture of alkali metal (lithium, sodium and potassium) carbonates at
a temperature of 600 – 7000 C. This is retained in an inert porous matrix
sandwiched between two porous nickel electrodes.
 Because of the high temperature, electrochemical catalysts are apparently
not necessary on the electrodes. The mixture of hydrogen and carbon
monoxide is supplied to the negative electrode and oxygen (from the air) to
the positive electrode.
 The discharge emf of the cell is about 0.8 volt.
 The electrolyte is usually held in a sponge like ceramic matrix. Metallic
electrodes are place in direct contact with this solid electrolyte. The
hydrocarbon fuel such as methane or kerosene is used.
 The fuel is reacted inside the cell to produce H2 and CO.
 At the fuel electrode, H2 and CO react with CO32– ions in the electrolyte, releasing
electron to the electrode and forming H2O and CO2. at the oxygen electrode O2 reacts
with the returning electron and CO2 diverted from the fuel electrode to form CO32– ions.
These CO32– ions then migrate through the electrolyte to the fuel electrode.
 Cont...
 Thus reaction are as follow:
At the fuel electrode:
H2 + CO32– → H2O + CO2 + 2e
CO + CO32– → 2CO2 + 2e
At oxygen electrode:
O2 + 2CO2 + 4e → 2CO32–
Overall cell reactions:
H2 + CO + O2 → H2O + CO2

 An important aspect of the molten carbonate fuel cells is that the discharged gases,
consisting mainly of the steam and carbon dioxide products and nitrogen from the air,
are at a temperature exceeding 540 C.
 The hot gases could be used to provide industrial process heat, to operate a gas
turbine to produce steam in a waste-heat (heat exchanger) boiler to drive a steam
turbine.
 The turbine would be attached to a generator to produce additional electric power.
 The overall efficiency for fuel use would thus be substantially increased.
 Advantage an disadvantages
Advantages
1. It has very high conversion efficiencies as high as 70 % have been observed since it is a
direct conversion process and does not involve a thermal process.
2. Fuel cells can be installed near the use point, thus reducing electrical transmission
requirements and accompanying losses. Consequently considerably higher efficiencies
are possible.
3. They have few mechanical components; hence, they operate fairly quietly and require
little attention and less maintenance.
4. Atmospheric pollution is small if the primary source is hydrogen, the only waste product
is water; if the source is a hydrocarbon; carbon dioxide is also produced.
5. Their is no requirement for large volumes of cooling water such as are necessary to
condense exhaust me conventional power plant.
6. The fuel cell do not make noise, they can be easily accepted in residential area.
7. As fuel cell takes little time to go into operation.
8. The space requirement for fuel cell power plant is considerably less as compared to
conventional power plants.
Disadvantages
9. The main disadvantages of fuel cells are their high initial cost and low service life.
 Conversion Efficiency of Fuel Cells
 The electrical energy generated by a fuel cell depends on what is called free
energy rather than heat energy of overall cell reaction.
 The free energy of formation of 1 mole (18 grams) of liquid water from
hydrogen and oxygen gases at atmospheric pressure is 56.67 kcal or 237 kJ
at 250 C.
 The heat energy (or enthalpy) of the reaction under the same conditions is
68.26 kcal (286 kJ). The theoretical efficiency of the conversion of heat
energy into electrical energy in a fuel cell is thus (56.67/68.26) x 100 = 83
%.
 Efficiencies as high as 70 % have been observed but the practical cells using
pure hydrogen and oxygen generally have conversion efficiency in the range
of 50 – 60%. The efficiency is some what lower when air is the source of
oxygen. The overall thermal to electrical conversion efficiencies are also
lower when the hydrogen is derived from hydrocarbon sources.
 Cont...
 The discharge voltages observed in actual cells are always below the theoretical
value, the difference increasing with increasing strength of the current drawn from
the cell.
 For the moderate currents at which fuel cells normally operate the emf is 0.7 to 0.8
volts. This deviation from the theoretical emf efficiency of a fuel cell being below
the ideal maximum value.
 Polarization of fuel cells
 The difference between the theoretical voltage and actual voltage is known as
polarization.
 The effect of polarization is to reduce the efficiency of the cell from the theoretical
maximum. The significant drop in the voltage and hence energy loss takes place as
the current density is increased.
 The three main types are:
1. Activation polarization
2. Resistance or ohmic polarization
3. Concentration polarization
 Activation polarization (Chemical polarization)
 This is related to the activation energy barrier for the electron transfer process at the
electrode.
 In fuel cells electrons are liberated and reaction is chemisorption reaction.
 At low current densities significant number of electrons are not emitted, which
results in such a potential loss.
 This process requires that certain minimum activation energy supplied so that
sufficient number of electrons are emitted, this energy supplied by output of the cell.
This loss is known as activation or chemical polarisation.
 This polarisation may be reduced by using better electrode catalysts increasing
surface area, and by raising the operating temperature.
 Resistance Polarisation.
 The voltage drop is linearly related to the current flow according to ohm's law. The
internal resistance is composed of the electrode resistance, bulk electrolyte resistance,
and interface contact resistance between electrode and electrolyte.
 The loss due to resistance polarisation is significant when current density is quite large.
 The reduction in internal resistance is the main design criterion for low resistance
polarisation losses. With large electrodes the resistance may be quite significant
particularly when these are made thin or consists of extremely thin coating on a non
conducting sport or when the electrode catalyst is a poor electric conductor.
 The electrolyte resistance can be decreased usually by :
 using a more concentrated electrolyte,
 closer spacing of electrodes and
 increased temperature.
 Hence loss due to resistance polarisation can be reduced by :
 Selecting proper shape of the electrode to have minimum contact between electrode and
electrolyte,
 Reducing the gap between electrodes,
 By using concentrated electrolyte.
 Concentration Polarisation
 This type of polarisation tends to limit the current drawn.
 This broad heading covers a slow step in any of the mass transport processes in the
cell, and is generally divided into two categories i.e.,
 Electrolyte-side polarisation
 Gas side polarisation.
 Electrolyte side polarization is due to slow diffusion in electrolyte causing a change
in concentration at the electrode.
 This effect can be minimized by increasing the electrolyte concentration or by
stirring or circulating the electrolyte.
 Types of electrodes
 There are of two types:
 Porous electrodes
 Non-porous electrodes.

Porous electrodes
 The design of these electrodes has been based on the
assumption that it is necessary to maintain a three-phase
boundary between gas, electrode and electrolyte.
 Two main methods have been used to maintain such a stable
interface.
 In the first method, dual-porosity electrodes are used, the inter face being
maintained at the junction of the fine pore and coarse pore layers by
means of a differential pressure across the electrode.
 In a dual pore electrode the fine pore need not be a conductor and porous
plastics have been used for this purpose.
 Cont...
 The second method uses a trapped electrolyte held in a porous non. conducting
diaphragm whose pores are smaller than those of the contacting electrodes. This
form has been widely used for high temperature cells.
 The ion exchange membrane cell is a special example of this type.
 Porous nickel electrodes and porous carbon electrodes impregnated with
catalysts are generally used in fuel cells for commercial applications.
 Platinum and other precious metals are being used in certain fuel cells which
have potential utility in military and space applications.
Non-porous electrodes
 The concept of non porous diffusion membrane electrodes, an example of
which is the hydrogen diffusing palladium alloy membrane allows the
complete separation of the reactant gases from the electrolyte. This obviates,
the problems of interface control and of direct chemical reactions with the
electrolyte.
 Application of fuel cell
 applications of fuel cell may be discussed with references to the following :
1. Domestic use
2. Central power stations
3. Automotive vehicles
4. Special applications.
 The e.m.f. or voltage of a fuel cell depends to some extent on the discharge current
strength. The average voltage per cell is 0.75 volt.
 By joining a number of cells in series and parallel can provide any reasonable voltage
and current.
 Fuel cells generate direct current which can be used for electric lamps and some
small applications such as heat pumps, motors etc., conversion into alternating
current by means of an inverter might be necessary.
 Fuel cells can be made in modules of different size are readily transportable.
 They can then be assembled at any location to provide a specified voltage and power
output.
 Cont...
 If fuel cells of reasonably low cost and long life can be produced plant in the major use might be
electric utilities for load leveling
 A long term possibility is a central-station power coal is gasified and the gas is used to generate
electricity directly by means of fuel cells.
 Low temperature fuel cells have a favorable position for operating times of 3,000 to 4,000 hours
per year using methanol as a fuel.
 When the demand or load is less than the rated output, the excess would be used to generate
hydrogen by electrolysis of water. At times when the load is greater than the power supply, the
hydrogen would he used in fuel cells to satisfy the additional demand.
 By siting fuel cells near load centers where the demand exists, electrical transmission and
distribution costs would be reduced, although there would be some cost for transporting the
hydrogen.
 Fuel sources have been proposed for remote or rural areas or unattended locations, for mobile
and emergency power sources, and for vehicle propulsion. The high temperature batteries may be
the best candidates for vehicle propulsion in the long term, but certain fuel cells are potential
alternatives to storage batteries for electric vehicles. Such vehicles may have longer travel ranges
than those with the most advanced storage batteries.
 The fuel cells of special interest are the aluminum-air, methanol-air, and the hydrogen-oxygen
cell. The aluminum-air cell is of special interest for electric vehicle propulSi0D because of the
high specific that is possible. An aluminum-air battery, and associated equipment may weigh
roughly the same as the gasoline engine and fuel in a medium size automobile.