• FUEL CELLS •

• Introduction to Fuel Cells

• Advantages of Fuel Cells Over Conventional Power Plants
• Principle of Operation of Fuel Cells
• Classification of Fuel Cells
>Phosphoric Acid Fuel Cells (PAFC)
>Molten Carbonate Fuel Cells (MCFC)
>Polymer Electrolyte Membrane Fuel Cell (PEMFC) or Solid Polymer Fuel Cells (SPFC)
>Solid Oxide Fuel Cells (SOFC)
>Regenerative Fuel Cells (RFC)
• Selection of Fuel Cells
Fuel cell technology is the new emerging technology. The development of this technology has started only few
decades back and it is still under development for its commercial and economical use.

Fuel cell :

• A fuel cell is defined as an electrochemical device that continuously converts the chemical energy of
fuel into electricity and heat without combustion.
• A fuel cell is similar to other electrical cells (battery) in respect that both have the positive and
negative electrodes with an electrolyte between them and both produce dc power. However, the
essential difference between the two is that a fuel cell provides continuous energy input and output
while the battery stores the electric charge. The difference is explained below :
• A fuel cell supply system requires continuous supply of fuel and oxidant and generates dc power and
heat. For example, in hydrogen – oxygen fuel cell, H2 is supplied as fuel and O2 as oxidant
continuously. It generates dc power with water and heat as by-product. Generated heat can be
transferred to the atmosphere. While a battery stores the electrical charge and after supply of power
it discharges and needs recharging.
• In case of conventional power plants, the chemical energy of the fuel is first converted into heat
energy and then it is converted into electrical power. During power generation, lot of cooling
water is needed for rejection of heat which is not utilized. While in case of fuel cells no cooling
water is needed since the heat can be either rejected directly to atmosphere or it can be used as
process heat.
• The efficiency of conventional plant depends on the temperature range of the cycle. Whereas, the
conversion of chemical energy into electrical power in case of fuel cells is an isothermal process.
Therefore, the efficiency of chemical conversion into electric power of fuel cells is higher than the
conventional power plants.

Applications

This advantage of fuel cells makes it an attractive proposition to use in applications like
space and ocean ships, automobiles, portable power plants, military use and for power
production.
 Advantages of Fuel Cells Over Conventional Power Plants

Use of fuel cells for energy storage requirements

1. It is quite in operation and less polluting.
2. Energy conversion efficiency into electrical power is higher.
3. No cooling water needed.
4. Heat generated can be rejected directly to atmosphere, the process being isothermal.
5. Fuel cells can be installed at the point of use thus reducing the power losses due to transmission
and distribution.
6. By use of series-parallel combination of fuel cells, the output power rating at any voltage and
current can be obtained.
7. The capacity can be increased as the demand grows.
8. Space requirement is much less.
9. It has long life.
 Principle of Operation of Fuel Cells
Fuel cell based generation
• As stated above, a fuel cell is an electro-chemical device in which the chemical energy
of fuel is continuously converted into electric energy. This conversion of energy takes
place at constant pressure and temperature.

• For explaining the principle of operation of fuel cells, here we shall consider a
hydrogen (H2) - oxygen (02) called Hydrox fuel cell.

The main components of a fuel cell are:

1. A fuel electrode (anode)
2. An oxidant electrode (cathode)
3. An electrolyte (a solution of H,SO, for acidic fuel cell and KOH for alkali fuel cells)
4. Additional components are container, separators, sealings, fuel and oxidant supply
etc.

• The basic feature of a fuel cell is that the fuel and the oxidant are combined in the form
of ions than in form of neutral molecules. Fig. 7.28.1 represents the
schematic diagram of a fuel cell using hydrogen as fuel and oxygen as oxidant and
alkaline solution of KOH as electrolyte.
• It is called Alkaline Fuel Cell (AFC). It consists of two permeable Nickel electrodes
immersed in an electrolyte of good conductivity. An electrolyte may be an alkaline
solution of KOH as shown or acidic solution of H,SO4 called respectively as alkali fuel
cells and acidic fuel cells.

• The porous fuel electrode is anode (negative pole) and the other porous oxidant electrode is cathode
(positive pole). These electrodes are separated by a porous gas barrier called separator (not shown in
Fig 7.28.1)
•The anode is supplied H_{2} gas as fuel at a certain pressure | and the cathode is supplied O_{2} as oxidant at a
pressure. These gases pass through the respective electrodes and bubble around through the electrolyte solution. The
pores provide an opportunity to gases, electrodes and Overall reaction: electrolyte to come in contact for their
electrochemical reactions. The electrodes are connected through an external circuit as shown.
•The electro-chemical reactions are generally slow and a catalyst is required in the electrodes to accelerate the reaction.
Platinum is the best catalyst but costly. In general, less expensive catalysts like nickel and silver are used according to
application and design.
Chemical reactions with alkaline H2-O2 fuel cell
•The hydrogen gas is ionized at anode and it produces a free electron and H+ ions. Every hydrogen molecules brought to
electrode surface is dissociated into two H atoms by catalytic property of electrode. These enter into electrolyte solution
as hydrogen ions leaving behind two electrons which pass through the external circuit to the cathode (positive
electrode). The reaction at anode is as follows:
Anode H2 2H^ + + 2e
•The oxygen supplied to cathode (positive electrode)e) Molten Carbonate Fuel Cells (MCFC)reacts with water of
electrolyte and the electrons transmitted to it to produce hydroxyl (OH) ions. Thus,
Cathode 1/2 O2 + H2O + 2e -> 2OH^-
•These hydroxyl ions migrate from cathode to anode electrolyte. The hydrogen and hydroxyl ions then combine in the
electrolyte to produce water i.e. 2H^+ +2 OH^- -> 2H2O
•Above equation shows that OH ions produced at one electrode (cathode) are involved in a reaction at the other electrode
(anode). By adding the above three equations, the overall process is chemical reaction of H2 and O2 gases to form water
i.e. H2+1/2 O2 -> H2O
•Thus the net reaction of a fuel cell in which hydrogen and oxygen supplied is the produce water, electrical energy and
heat.

Chemical reaction with acidic electrolyte (H2SO4)

Anode: H2->2H^+ 2e …(v)
Cathode: 1/2 O2 + 2H^+ 2e -> H2O …(VI)
Overall reaction: H2 + 1/2 O2 -> H2O …(VII)

•Thus the chemical reaction is similar to alkaline electrolyte.

•H2-02 fuel cells are efficient in operation. The operating temperatures are generally in the range of 100°C to 200°C. The
ideal e.m.f. produced by a single fuel cell is 1.23 V at one atmosphere and 25 deg * C Which reduces to 1.15 V at 200°C. The
actual value of e.m.f. decreases with current and at rated value of current the e.m.f. lies between 0.7V to 0.8V .
•The rated voltage and current of fuel cells can be increased by using number of cells in series-parallel combination. The
expected life of a fuel cell is ten thousand hours.

Classification of Fuel Cells

The fuel cells can be classified as follows:
1. Based on type of electrolyte
a) Alkaline Fuel Cell (AFC)
b) Phosphoric Acid Fuel Cell (PAFC)
c) Molten Carbonate Fuel Cells (MCFC)
d) Solid Oxide Fuel Cells (SOFC)
e) Proton/polymer exchange membrane fuel cells (PEMFC)
2. Based on type of fuel and oxidants
a) H2(pure) – O2(pure) fuel cell
b) H2(rich gas) – air fuel cell
c) NH3 – air fuel cells
d) Hydrocarbon gas – air fuel cell
e) Synthesis gas – air fuel cell
3. Based on operating tempratures
f) Low temperature fuel cells(below 150 deg C)
g) Medium temperature fuel cells(150 deg C - 250 deg C)
h) High temperature fuel cells(more than 250 deg C)
4. Based on electrolyte
i) Acidic electrolyte type
j) Alkaline electrolyte type
k) Neutral electrolyte type
5. Based on its applications
l) For space application
m) For automobile application
n) For military application
o) For submarine application
p) For other comercial applications
Phosphoric Acid Fuel Cells (PAFC)
•A schematic diagram of phosphoric acid fuel cell is shown in Fig 7.30.1. It was developed in 1980s. It uses either pure
hydrogen or rich hydrogen gas as fuel and oxygen or air as oxidant.
•The concentrated phosphoric acid (H3PO4) is used as electrolyte. It is a medium temperature type of fuel cell.
• It has two electrodes of porous conducting material, usually of nickel material to collect charge.
•The electrochemical reaction is normally very slow, therefore a catalyst is needed in the electrodes to accelerate the
reaction. Finely powdered nickel platinum/silver coating is provided on the outer surface of electrodes which act as
catalyst. Nickel is used since it is comparatively cheaper.
•The working of the fuel cell is similar to H2-O2 fuel cell described above. The chemical reactions in this fuel cell to produce
electrical power with heat and H2O as by products are as follows:
Overall reaction: H2 + 1/2 O2 -> H2O + heat + power
•The operating temperatures for this type of fuel are in the range of 150 deg * C - 220 deg * C .
•At present these are most economical since they have lowest cost per kW. These are used commercially having the plant
capacity in the range of 50 KW to 200 kW
•In case air is used as oxidant instead of O2 ,the inert gas n2 is discharged along with spent O2 and water vapour formed.
Molten Carbonate Fuel Cell (MCFC)
•A schematic diagram of a molten carbon fuel cell isshown in Fig. 7.31.1. It is a high temperature fuel cell.
• The fuel, oxidant, electrodes and the electrolyte used are as follows:
Fuel: Mixture of H₂ and CO
Oxidant: O2 or air
Electrodes: porous nickel electrodes
• Electrolyte : Mixture of carbonate salts either lithium carbonate and potassium carbonate or lithium carbonate and
sodium carbonate.
•Since it uses the carbonates of alkali metals as electrolytes in molten (liquid) phase, its operating temperatures must
be in the range of (650 deg * C - 700 deg * C) The electrolytes are held in a sponge like ceramic matrix. When the
mixture of carbonate salts are heated they become conductive to CO3^-- ions.
•The carbonate ions so produced flow from cathode to anode where they combine with hydrogen to produce CO2
water (H2O) and electrons and while combining with CO it produces CO2 and electrons. The electrons flow from
anode to cathode to generate electrical power and heat.
At anode: H2+CO3^-- = H2O + CO2 + 2e ...(i)
CO + CO3^-- = 2CO2 + 2e …(ii)

At cathode: O2 + 2CO2 +4e = 2CO3^--

Overall cell reaction: H2 + CO + O2 = H2O + CO2 + heat

The e.m.f. produced by each cell is theoretically IV and actual e.m.f. of 0.8 V at 700°C. The expected efficiency is
about 60%.

Advantages of MCFC system

1. It uses comparatively cheaper fuels like H2 and CO.

2. It can utilize even fossil fuel like coal for producing the H2 and CO by its gasification.
3. Discharges are mainly water vapour, CO2 and N2 (if airis used as oxidant) at a temperature exceeding 550°C. These
hot gases can be used for generation of steam for power generation or as process heat for industries.
4. Efficiency of cell is high in the range of 60%. It's overall efficiency can be further increased by utilizing the heat of the
products in co-generation plant.
Polymer Electrolyte Membrane Fuel Cell (PEMFC) or Solid Polymer Fuel Cell (SPFC)

• The schematic diagram of a low temperature polymer electrolyte membrane fuel cell is shown in Fig. 7.32.1.
•In this type of cell, the electrolyte is a solid polymer membrane of an organic material such as polystrene sulphonic acid.
•This polymer is permeable to H^+ ions to pass through it when it is saturated with water but it does not conduct
electrons. Other properties include that this polymer has high resistance to dehydration and oxidation coupled with high
ionic conductivity. The membrane is coated on its both sides with finely powdered platinum which acts as catalyst.
The fuel used is H2 and oxidant as O2. The electrochemical reactions are:
At anode : H2 =2H^+ + 2e

At cathode: 1/2 O2 _ 2H^+ + 2e = H2O

Overall reaction is: H2 + 1/2 O2 = H2O + heat

Advantages of PEMFC are

1. It can be started quickly

2. Polymer membrane retains only limited quantity of water and rejects excess H2O vapour produced in the cell.
3. It is comparatively cheap
4. It has no corrosion problems due to use of polymer.
5. It has an ideal e.m.f. of 1.23V and actual e.m.f. of about 1V at 25°C.
6. It operates at low temperature of 40 deg * C - 60 deg * C..
Desirable properties of an ideal ion-exchange membrane

1. Zero electronic conductivity.

2. Low permeability of fuel and oxidant
3. High ionic conductivity.
4. High resistance to dehydration and hydrolysis.
5. Mechanical stability.

Solid Oxide Fuel Cells (SOFC)

• Certain solid ceramic oxides (e.g zirconium dioxide) are able to conduct electricity at high temperatures, therefore
such ceramic oxides can be used as electrolytes in such fuel cells. This material is able to conduct 0 ^ - ions at high
temperatures. Therefore these cells operate at high temperatures in the range of 650°C to 1000°C. Due to high
temperature operation no catalyst is required.
•The negative electrode (anode) is made of porous nickel and positive electrode (cathode) uses metal oxide.
•The schematic diagram of solid oxide fuel cell is shown in Fig. 7.33.1 using hydrogen as fuel and oxygen as oxidant.
•At the cathode the ½ O2 molecules are split into oxygen ions with addition of two electrons. These O ions migrate to
anode through electrolyte and combine with one hydrogen molecules with formations of H_{2}*O and two electrons.
Thus the chemical reactions are:
 At anode : H2 + O^-- = H2O + 2e

At cathode: ½ O2 + 2e = O^--

Overall reaction: H2 + ½ O2 = H2O + heat

•The electrons move through the external circuit to produce power. The output voltage is about 0.65V at about
800°C. A tubular type of SOFC system has been developed which operates at high temperature of about 900°C-
1000°C.
•Like molten carbonate fuel cell, the heat of discharge can be utilized for process heat or additional power
generation.

Other fuels for SOFC system

•Apart from H2, other sources of fuel for SOFC system could be methanol, ammonia and hydrazine. Methanol can be
catalytically reformed with steam at 200°C to yield the mixture of H2 and CO2 gas. Liquid NH3 - air fuel cell can be
catalytically converted into H2 and N2.The electrolyte used is KOH solution.
•Another source of fuel as hydrazine (N_{2}*H_{2}) and air as oxidant can be used. Disadvantage of N_{3}*H_{4} is
that it is toxic and highly reactive. This uses porous nickel as anode and silver deposit on porous material as cathode.
•The chemical reactions are:

At anode: N2H4 + 4OH^- = N2 + 4H2O + 4e

At cathode: O2 + 2H2O + 4e = 4OH^-

Overall reaction: N2H4 +O2 = N2 + 4H2o

•Thus in this cell nitrogen, water vapour and heat is produced as by-product with generation of power.
Regenerative Fuel Cells (RFC)

•The Regenerative Fuel Cell (RFC) is a system that can operate in a closed loop and could serve as the basis of a hydrogen
economy operating on renewable energy.
•Fuel cells generating electricity, heat, and water from hydrogen and oxygen would be used throughout the economy,
powering factories, vehicles, and houses. The hydrogen would be generated from the electrolysis of water, splitting it into
its constituent components of hydrogen and oxygen, using renewable energy sources such as wind, solar, or geothermal.
•Such a system would not require any specific type of fuel cell, but would need on infrastructure to deliver hydrogen to
the many fuel cells in use. Little to no new technology is required to implement a renewable-based system. However,
there currently does not exist the infrastructure for hydrogen delivery. Also, the cost of electricity would be high, but will
decrease as costs decrease for each of the components: Fuel cells, hydrogen storage and delivery, renewable energy
collection, etc.
•Currently, there is a project led by NASA to develop an efficient and lightweight regenerative fuel cell system for use on
board an airplane called the Helios that can fly at altitudes nearly 30000 m. The predecessor aircraft during the day and
generate a supply of hydrogen that would be stored for use by the fuel cell overnight. Such a system would then be
capable of flights lasting many days.
•If the fuel cell is designed to operate also in reverse as an electrolyzer, then electricity can be used to convert the water
back into hydrogen and oxygen. (Refer Fig. 7.33.2). This dual function system is known as a reversible or unitised
regenerative fuel cell (URFC). Lighter than a separate electrolyzer and generator, a URFC is an excellent energy source in
situations where weight is a concern.
•The regenerative fuel cell, coupled with lightweight hydrogen storage, had by far the highest energy density about 450
watt-hours per kilogram N ten times than of lead acid batteries and more than twice that forecast for any chemical for
any chemical batteries. The Prototype Fuel cells have been used since the 1960s when they supplied on-board power
for the Gemini and Apollo spacecraft.

Selection of fuel cells

Selection criteria of fuel cell

The selection of a fuel cell is mainly based on the following factors:

1. Cost
2. Availability of fuel and its heat
3. Size/volume of cell
4. Transportability
•Hydrocarbons like methane, ethane, and propane gases are not used since they are less reactive and their oxidation
in fuel cell is difficult. Therefore, these fuels are not suitable for use in fuel cells.
•Thus, most of the fuels which can be used in fuel cells are H_{2} N*H_{j} C*H_{3}*OH (Methanol), N_{2}*H_{4}
(Hydrazine), CO etc. Out of these fuels, hydrogen is the best fuel since its heat of reaction per kg of fuel is highest
amongst all the fuels. Thus, fuel cells based on hydrogen - O_{2} air are best suited for applications like spacecraft,
submarines etc.
•Fuels like ammonia, methanol and hydrazine are reasonably reactive and can be conveniently used in fuel cells.
Ammonia is toxic. Hydrazine is toxic, poisonous and does not require any catalyst.
•Though the ammonia is cheaper than hydrazine but it is comparatively less reactive.
•Therefore, hydrazine is quite suitable for use in fuel cells particularly for military applications. On the other hand,
N*H_{2} being cheap and easily available, it is suitable for remote area and low power applications.