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Dr. Muhammad Zubair Khan

Lecture-3
Fuel Cells Classification

 Fuel cells can be classified according to various criteria, based on

electrolyte, operating temperature, fuel or oxidant used, reforming process,
etc.
 The most common criterion, is the type of the electrolyte used for operation.
 Based on the type of the electrolyte:
1. Proton exchange membrane fuel cells (PEMFC).
2. Alkaline fuel cells (AFC).
3. Phosphoric acid fuel cells (PAFC).
4. Molten carbonate fuel cells (MCFC).
5. Solid oxide fuel cells (SOFC),
1. intermediate temperature solid oxide fuel cells (ITSOFC), with operating temperature < 800°C,
2. high temp. solid oxide fuel cells (TSOFC), with operating temperatures > 800°C

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FUEL CELLS CLASSIFICATION
 Based on the type of the electrolyte:

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Fuel Cells Classification

 Based on the type of the temperature fuel cells can be classified as:

1. Low-temperature fuel cells (operating temperature < 200°C); mainly for

transportation and small utilities
 Proton exchange membrane fuel cell (PEMFC)
 Alkaline fuel cell (AFC)

2. Medium-temperature fuel cells (operating temperature ~ 200°C);

 Phosphoric acid fuel cell (PAFC)

3. High-temperature fuel cell (operating temperatures > 600 °C); are intended
for large power utilities
 Molten carbonate fuel cell (MCFC) and solid oxide fuel cell (SOFC)

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Fuel Cells Classification
1. Proton Exchange Membrane Fuel Cells

 The PEMFCs were developed originally by General Electric in the

1960s for NASA’s space explorations.

 These fuel cells have been known under various names, such as ion
exchange membrane, solid polymer electrolyte, proton exchange
membrane, or simply, polymer electrolyte fuel cells.

 They use hydrogen as fuel, oxygen or air as oxidant, and a solid

polymer membrane as electrolyte.

 PEMFCs are intended to be used also in small applications, such as

portable devices (i.e., laptops) and electronics

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1. Proton Exchange Membrane Fuel Cells (PEM-FC)

Design Characteristics

The different components of a PEMFC are:

 Bipolar plates
 Graphite plates or stainless steel; current collectors
and they also contain gas flow fields
 Electrodes
 Porous Carbon, Pt-C composite film; ~5–10 μm thick,
 Catalyst,
 e.g. Pt, situated adjacent to the membrane,
 Proton conducting membrane as electrolyte,
 Nafion® membranes, DowMembrane; Thickness of 50–175 μm,
 Assembly of membrane located between two catalyst-impregnated electrodes is referred to as the
membrane-electrode assembly (MEA).
 Backing layers
 carbon cloth or carbon paper with more PTFE added to expel water; Thickness 100-300 μm, to
provide some rigidity to the MEA and to ensure ease of gas diffusion
 Necessary hardware such as gaskets.
 Teflon masks, confine gas flow to active area, providing an effective seal along the periphery of the
membrane

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1. Proton Exchange Membrane Fuel Cells (PEM-FC)

Electrodes
 In PEMFC a composite layer is
formed by deeply mixing the Pt/C
catalysts with the electrolyte
ionomers, forming a three-phase
reaction zone.
 3M (company) developed MEA
based on Pt-coated nanowhiskers
as nanostructured thin-film
catalyst.

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1. Proton Exchange Membrane Fuel Cells (PEM-FC)

Proton Exchange Membrane Fuel Cell (PEMFC)

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1. Proton Exchange Membrane Fuel Cells (PEMFC)
Operation Characteristics
 Hydrogen gas is supplied to the anode, where it dissociates into hydrogen atoms in
the presence of platinum catalyst.
 The atoms further split into protons and electrons, which travel separate ways from
anode to cathode.
 Protons are conducted through the electrolyte membrane, and electrons are forced to
go via an external circuit to the cathode, producing electricity. Oxygen is supplied to
the cathode, where a reduction process occurs and water and heat are created as
byproducts.

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2. Alkaline Fuel cells (AFC)

 The first notable AFC was developed by Sir Francis Bacon, with an
output of 0.6 V at 1.11 A/cm2 (very high) current density and 240°C
operating temperature.
 20 AFCs have been used by NASA on their space explorations during
the 1960s and 1970s.
 Specialized applications Space explorations, military use,
The different components of a AFC are
 electrolyte,
 potassium hydroxide (KOH), aqueous solution or stabilized in porous asbestos
 catalyst
 nickel (Ni) and, silver (Ag), Noble metals, metal oxides, or spinels
 operating temperature
 65- 200°C

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2. Alkaline fuel cells (AFC)
Operation Characteristics
 Hydrogen and oxygen are supplied to the electrodes similarly to PEMFCs.
 The carrier in this case is the hydroxyl ion (OH), which travels from the
cathode to the anode, where it combines with H2 and creates water and
electrons.
 Electrons formed at the anode are conducted to the external circuit to
create the electrical output and then forced to the cathode, closing the
circuit. The basic electrochemical reactions for the AFC are:

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2. Alkaline fuel cells (AFC)

Problems with AFC:

1. The KOH electrolyte is extremely sensitive to potential poisoning with

CO or reaction with CO2 and, thus, only pure hydrogen and oxygen
can be used as reactants

2. If the electrolyte is in a solution form, it mixes up with the water

created at the anode, therefore water should be continuously removed
from the electrolyte.

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3. Phosphoric acid fuel cells (PAFC)

 These cells have been developed for medium-scale stationary

applications and are the only commercialized type of fuel cells.
 The PAFC have a similar design with the PEMFC
 The different components of a PAFC are
 electrolyte,
 concentrated phosphoric acid (H3PO4) contained in a silicon carbide matrix
 catalyst
 Pt
 operation at temperatures
 higher than the PEMFC (i.e., over 100°C)

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3. Phosphoric acid fuel cells (PAFC)
Operation Characteristics
 Operation of PAFC is similar to PEMFC, as Hydrogen-rich fuel is supplied to the
anode, where protons and electrons split and start traveling to the cathode,
following different pathways through the membrane layer (protons) and via an
external circuit, producing electricity (electrons).
 At cathode, they will combine with oxygen, and water and heat are obtained as
byproducts.
 The basic reactions are same as for PEMFC.

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3. Phosphoric acid fuel cells (PAFC)

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4. Molten Carbonate Fuel Cells (MCFC)
 MCFC are intended to be used for power plant applications.
 The different components of a MCFC are
 electrolyte,
 mixture of lithium carbonate (~68%) and potassium carbonate (~32%), contained
in a lithium-aluminum oxide (LiAlO2) matrix
 Catalyst
 Ni
 Fuel
 Hydrogen and CO2
 operation at temperatures
 temperatures (about 650°C), thus making it possible to process the fuel internally,
thus increasing the overall efficiency of the fuel cell and minimizing emissions

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4. Molten Carbonate Fuel Cells (MCFC)
Operation Characteristics
 CO2 and O2 are supplied at cathode, and they react with the available
electrons. The resulting carbonate ions travel to the anode, where they
combine with the hydrogen to produce water, CO2, and electrons.
 These electrons are then forced to go back to the cathode through the
external pathway to create electricity.

 The basic reactions for MCFC are:

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5. Solid Oxide Fuel Cells (SOFC)

 The mature technology of the fuel cells, SOFCs are characterized by extremely
high operating temperatures.
 SOFCs are intended to be used for large power and cogeneration utilities
 The fuel/oxidant mixture is less restricted, compared to all the other fuel cells,
owing to the high operating temperature of the cell, which allows for more
combinations.
 The different components of a MCFC are
 electrolyte,
 solid coated zirconia oxide ceramic (Y2O3-stabilized ZrO2)
 Catalyst
 Ni cermet, perovskites materials
 Fuel
 can be hydrogen, CO, or CH4, and the oxidant
 Operation at temperatures
 600-1000°C,

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5. Solid Oxide Fuel Cells (SOFC)
Operation Characteristics
 In this case, oxygen ions formed at the cathode from reaction of oxygen
and electrons travel through the electrolyte to the anode. There they
combine with fuel, creating by-products (i.e., water) and electrons.
 These electrons travel to the cathode through an external circuit,
producing electricity.
 The basic reactions are:

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Electrochemical Reactions

 The electrolyte separates the two reactants. Therefore two half-

reactions occur at the electrodes surface:

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Fuel Cells: Electrochemical Reactions

 - The electrolyte separates the two reactants. Therefore two half-

reactions occur at the electrodes surface:

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Thermal Efficiency
 Heat engines use chemical energy to produce intermediate heat,
which is subsequently transformed into mechanical energy, which in
turn leads to electrical energy.
 Fuel cells use a direct conversion process, transforming the chemical
energy directly into electrical energy

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Fuel Cell Efficiency

 The efficiency of fuel cells is very high which one of the primary benefits of the technology.
 The amount of energy released when hydrogen and oxygen combine to form water
according to the reaction H2 + ½O2H2O is quantified as the “enthalpy of reaction” (ΔH).
 This value is measured experimentally and depends on whether the water is formed as a gas
or a liquid as can be seen in the table.
 For fuel cells, the water forms as a gas and the enthalpy of reaction (ΔH)= -242 KJ/mol
 The negative sign denotes that the energy is released during the reaction, and not absorbed

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Fuel Cell Efficiency
 This value of the enthalpy of reaction is only strictly correct at 77 ºF (25 ºC),
298K and 1 atmosphere.
 The amount of released energy decreases as the temperature goes up.
 This change in available energy only varies by a few percent within PEMFC
operating temperatures, but can be as much as 30% lower for high-temperature
fuel cells.
 Unfortunately, not all of the enthalpy of reaction is available to do useful
work. A portion of the enthalpy adds to the disorder of the universe in the
form of entropy and is lost; the remainder is known as the “Gibbs free
energy” (ΔGo).
 So the thermodynamic expression for the maximum useful work obtained
from a fuel cell becomes:
 ΔGo = ΔHo - TΔSo
where
 ΔGo is the free energy
 ΔHo is the enthalpy of the reaction
 ΔS is the entropy
 TΔSo represents the “unavailable” energy (that which cannot be converted to useful work).

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Fuel Cell Efficiency
 Since fuel cells use materials that are typically burnt to release their
energy, the fuel cell efficiency is described as the ratio of the
electrical energy produced to the heat that is produced by burning the
fuel (its enthalpy of formation or ΔHo)
 From the basic definition of efficiency: η = W / Qin
 where W is given by ΔG, and Qin by ΔHo. The Gibbs function change
measures the electrical work and the enthalpy change is a measure of
the heating value of the fuel.

ΔG
 η = Δ𝑯 o or
o

 For hydrogen fuel cell ΔG was 237 kJ/mol and ΔHo was 286 kJ/mol,
the maximum efficiency of the fuel cell would be 83%.

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Fuel Cell Efficiency
 Another measure of the fuel cell efficiency is known as the "Voltage
Efficiency" and is the ratio of the actual voltage under operating
conditions to the theoretical cell voltage.
Voltage Efficiency = (Actual Voltage)/(Theoretical Voltage)
= (VA / 1.23)
 Where 1.23V is the electrochemical potential generated by the
reaction of oxygen and hydrogen
 For a real fuel cell, typical voltages are between 0.5 and 0.6 V at
normal operating loads and can reach 1.1 V at open circuit conditions.
The electrochemical efficiency is therefore typically between
approximately 40 and 50% with open circuit conditions reaching
90%.

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Fuel Cell Voltage
 Under ideal conditions, operation of fuel cells is performed without
any losses.
 In reality fuel cells achieve their highest output voltage at open circuit
(no load) conditions and the voltage drops off with increasing current
draw. This is known as polarization.

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Fuel Cell Voltage
Classification of Losses in an Actual Fuel Cell
1. Activation Losses: These losses are caused by the slowness of the
reaction taking place on the surface of the electrodes. A proportion
of the voltage generated is lost in driving the chemical reaction that
transfers the electrons.
2. Ohmic Losses: The voltage drop due to the resistance to the flow of
electrons through the material of the electrodes. This loss varies
linearly with current density.
3. Concentration Losses: Losses that result from the change in
concentration of the reactants at the surface of the electrodes as the
fuel is used.

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Operational Issues
1) Water and Heat Management
 Conductivity properties of polymers/ membranes / electrolytes are extremely sensitive to
the level of hydration of membranes, and maintaining adequate humidity conditions is a
challenging task. A fine balance of equilibrium has to be maintained to avoid either
flooding or dehydration of the membrane.

 Water management depends on several factors, such as;

 operating parameters (temperature and pressure),
 water content, and
 the presence of the impurity ions in the membranes.

 PEMFC typically operate efficiently at approximately 80°C at atmospheric pressure; if

increased above 100°C, dehydration of the membrane occurs, and conductivity of the
membrane decreases significantly.

 The water content depends on the water transport (through Diffusion and electro-
osmosis), which is a complex phenomenon still not very well understood.

 Impurities in membranes are due to the impurities present in the fuel or oxidant, or to the
corrosion of materials, and water management can be seriously affected by their
presence.

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Operational Issues
2) CO Poisoning
 Hydrogen-rich fuels used for fuel cells are either pure hydrogen or
reformed fuel. During the reforming process CO is produced, and
trace amounts of carbon monoxide remain present in the flow to the
electrodes.

 For low-temperature fuel cells using platinum catalysts, the presence

of carbon monoxide even in trace levels poisons the catalysts as with
CO has an affinity for platinum, blocking H2 from reaching the
catalysts and thus deteriorating the overall performance of fuel cells.

 Removal of CO is critical for fuel cell operation, requiring additional

design modifications which increases the overall costs.

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Operational Issues
3) Hydrogen Safety
 Handling of hydrogen, similar to any other flammable fuel, entails a
number of hazards.

 It has been demonstrated that risks associated with it are manageable

and are similar to those with other gaseous fuels.

 Hydrogen is characterized by high volatility and flammability, but it

also has very low density, which means that it disperses extremely
rapidly, and the ignition and detonation levels are not easily reached.

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Environmental Impact of Fuel Cells

 Minimum impact on
the environment
during operation.

 Drastic reductions in
greenhouse gas
emissions can be
observed when
comparing fuel cells
with internal
combustion engines.

 If direct hydrogen is
used as primary fuel
for fuel cell operation,
greenhouse gas
emissions are
practically zero.

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Environmental Impact of Fuel Cells

 The 200-kW PC25™

system produced by UTC
(USA) Fuel Cells is the
only commercially
available fuel power
system.
 It is estimated that after 1
year of operation this
system will generate less
than half of the total CO2
emissions compared to an
average fossil fuel plant.
 The remaining greenhouse
emissions are estimated to
be negligible compared to
the same average fossil
fuel plant

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Benefits and Disadvantages of Fuel Cells
Advantages:
 Negligible air pollution (if fossil fuels are used, otherwise none) greatly reduces
CO2 and harmful pollutant emissions
 Clean alternative to internal combustion engines, batteries, and thermal
combustion power plants.
 Reduced weight, and more compact especially in mobile applications
 Constant efficiency at low load
 Wide variety of applications from small to large scale power production
 Low maintenance cost and very few moving parts (or none)
 A long term service life and stability to generate energy continuously
 Quiet or completely silent

Disadvantages
 Expensive to manufacture due the high cost of catalysts (platinum)
 Lack of infrastructure to support the distribution of hydrogen
 A lot of the currently available fuel cell technology is in the prototype stage and
not yet validated.
 Hydrogen is expensive to produce and not widely available

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