DIRECT CONVERSION OF

CHEMICAL TO ELECTRICAL
ENERGY
Dr.A.Manivannan
Associate Professor
Department of Mechanical Engineering
Anna University, Chennai – 600 025
 Content
Fuel Cell :
Basics – working, advantages and drawbacks
– types
–comparative analysis
– thermodynamics and kinetics of fuel cell process
– performance of fuel cell
– applications
 History
• The principle of the fuel cell was discovered by German scientist C. F. Schönbein in 1838.

• Based on this work, the first fuel cell was demonstrated by Welsh scientist Sir W.R. Grove in
1839

• In 1939, British engineer F.T. Bacon successfully developed a 5 kW stationary fuel cell.

• In 1955, W.T. Grubb, a chemist working for the General Electric (GE) Company (USA), further
modified the original fuel cell design by using a sulphonated polystyrene ion-exchange
membrane as the electrolyte.

• Three years later another GE chemist, L. Niedrach, devised a way of depositing platinum onto
the membrane, which served as catalyst for the necessary hydrogen oxidation and oxygen
reduction reactions.
• This was the first commercial use of a fuel cell. In 1959, a team led by H. Ihrig built a 15 kW
fuel cell tractor for Allis-Chalmers, which was demonstrated across the U.S. at state fairs.

• This system used potassium hydroxide as the electrolyte and compressed hydrogen and
oxygen as the reactants.

• In the 1960s, Pratt and Whitney licensed Bacon's U.S. patents for use in the U.S. space
program to supply electricity and drinking water (hydrogen and oxygen being readily available
from the spacecraft tanks).

• International Fuel Cells (IFC, later UTC Power) developed a 1.5 kW alkaline fuel cell (AFC) for
use in the Apollo space missions. The fuel cell provided electrical power as well as drinking
water for the astronauts for the duration of their mission.
• IFC subsequently developed a 12 kW AFC, used to provide onboard power on all space
shuttle flights.
 FUEL CELL

• A fuel cell is an electrochemical device, which

converts the chemical energy of fuel into electricity
directly, without intermediate stages of combustion
and production of mechanical work.
H2 Electricity

Fuel Cell
O2 H2O

Heat

5
 Basic Working Principle of Fuel Cell
• In its basic form a fuel cell operates as follows: hydrogen
reacts with oxygen in the presence of an electrolyte and
produces water, while at the same time an electrochemical
potential is developed, which causes the flow of an electric
current in the external circuit (load)

• The fuel (hydrogen gas) supplied to the anode side is split

into ions due to the catalyst action and gives off electrons:

2 H2 → 4 H+ + 4e-
Basic Operation Principle of Fuel Cells

7
• At the anode, ions and free electrons are produced. Ions
move towards the cathode through the electrolyte.

• Electrons move towards the cathode through the

external circuit, which includes the load (external
resistance). The reaction is exothermic. The released
heat can be used in thermal processes.

• Electrolyte is typically 40% KOH because of high

electrical conductivity
• Porous nickel electrode and Porous Carbon electrode are generally
used in fuel cells for commercial application. Platinum and other
precious material are being used in certain fuel cells

• The required hydrogen is usually produced from hydrocarbons, most

frequently natural gas, by a process known as reforming, which can
be either external or internal to the fuel cell unit, depending on the
type of the fuel cell. Also, it can be produced by electrolysis of water.

• In certain types of fuel cells, carbon monoxide can be used as fuel,

instead of hydrogen
 Types of Fuel Cells
• Based on Temperature
– Low Temperature fuel cell (25oC to 100oC)
– Medium Temperature fuel cell (100 C to 500 C)
o o

– High Temperature fuel cell (500oC to 1000oC)

– Very High Temperature fuel cell (above 1000oC)
• Type of electrolyte
– Aqueous
– Non-aqueous
– Molten or Solid
 Types of Fuel Cells
• State of fuel
– Gas (Hydrogen, lower hydrocarbon)
– Liquids ( alcohols, hydrazine, higher hydrocarbon)
– Soild (Metals)
• Type of Fuel
– Hydrogen
– Fossil fuel
– Hydrocarbon fuel
– Alcohols fuels
– Hydrazine fuels
 Types of Fuel Cells
• TYPE OF THE ELECTROLYTE
– Alkaline fuel cells (AFC)

– Polymer electrolyte fuel cells (PEFC)

– Direct Methanol Fuel Cells (DMFC)

– Phosphoric acid fuel cells (PAFC)

– Molten carbonate fuel cells (MCFC)

– Solid oxide fuel cells (SOFC)

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 Low Temperature High Temperature
Other Types
Fuel Cells Fuel Cells
• Phosphoric acid FC • Molten • Regenerative FC
• Alkaline FC Carbonate FC
• PEM FC • Solid Oxide FC
• Direct Methanol FC
 Alkaline fuel cells (AFC)
• The AFC was one of the first modern fuel cells to be developed,
beginning in 1960. The application at that time was to provide on-
board electric power for the Apollo space vehicle.

• Potassium hydroxide (KOH), which is the most conducting of all

alkaline hydroxides, is the electrolyte, at a concentration around
30%. Pure hydrogen is the fuel and pure oxygen or air is the oxidiser.
Alkaline fuel cells operate at a temperature 60-80°C.

• This is why they are characterised as low temperature fuel cells. The
operating pressure in some cases is a few atmospheres, but most
often it has been the atmospheric pressure.
14
• The electrolyte in this fuel cell is concentrated (85 wt percent)
KOH in fuel cells operated at high temperature (~250 °C), or
less concentrated (35 to 50 wt percent) KOH for lower
temperature (<120 °C) operation

• The electrolyte is retained in a matrix (usually asbestos), and a

wide range of electro-catalysts can be used (e.g., Ni, Ag, metal
oxides, spinels, and noble metals).

• They are one of the most attractive systems for transportation

applications. Units with a power up to 100 kW have been
constructed
• Each cell generates a voltage between 0.5 V and
0.9 V depending on the design with an electrical
efficiency that can be up to 65%
• Three different designs of Alkaline Fuel Cells that have to
be accounted:
– Mobile electrolyte AFC’s
– Static electrolyte AFC’s
– Dissolved fuel AFC’s
 Mobile Electrolyte AFC’s
• This design sends pure hydrogen at the anode and air at the cathode while the
electrolyte is pumped inside the cell by an external circuit.

• Since it tends to evaporate the water product, the hydrogen have to be done to
circulate in order to extract the evaporated water solution with a condenser.

• The bigger problem inside this design is the chemical reaction between the
potassium hydroxide (KOH) and the carbon dioxide (CO2) that is present in the air.

• This reaction is unfavorable because the efficiency of the fuel cell depends upon the
purity of the potassium hydroxide solution.

• In order to solve this problem a carbon dioxide scrubber (very expensive) is used to
maintain the solution as pure as possible. This type of design is the one that was
used inside the Apollo space shuttle , where the cost was not a problem .
 Static electrolyte AFC’S
• In this design, the potassium solution is held inside
asbestos with a matrix structure which prevents the
electrolyte to circulate.

• This AFC variant, in order to work, requires the injection

of pure oxygen inside the cathode. As the other design
the hydrogen is done to circulate in order to remove the
gaseous water product while a cooling system works to
keep the fuel cell within the required operational
temperature range
 Dissolved fuel AFC’s
• This is the simplest type of AFC regarding the realization. Inside this
design, like in the others, potassium hydroxide is used but this time
the electrolyte is combined with a fuel like hydrazine or ammonia.

• This type of AFC, which is not suitable for large power generators,
have high problems regarding the fuel crossover but they can be
ignored since the catalyst used is not platinum (thus greatly reducing
the costs for the substitution of the catalyst)

• Another big problem is that the most suitable fuel for this cell is the
hydrazine (due to the capacity to dissociate into hydrogen and
nitrogen) which is a toxic, carcinogen and explosive fuel
 Advantages & Disadvantages
• Advantages
– excellent performance on hydrogen (H2) and oxygen (O2)
compared to other candidate fuel cells due to its active O2
electrode kinetics and its flexibility to use a wide range of
electro-catalysts
– wide operating temperature range;
– high simplicity of the cell structure;
– fast start up;
– Competitive costs for the cell construction (due to the
simplicity of the materials involved);
– Capacity to reach an electrical efficiency of 65% (which is
really high for cold fuel cells);
– a life cycle time between 10,000 and 15,000 hours due to
the good compatibility of the materials in the cell
(however life cycles of 40,000 hours are required in order
to a full commercialization of a fuel cell technology).
– As a result if compared with PEM fuel cells the AFCs are
cheaper and more efficient.
• Disadvantages
– The sensitivity of the electrolyte to CO2 requires the use
of highly pure H2 as a fuel. As a consequence, the use of a
reformer would require a highly effective CO and CO2
removal system.
– In addition, if ambient air is used as the oxidant, the CO2
in the air must be removed. While this is technically not
challenging, it has a significant impact on the size and
cost of the system.
 Applications
• AFCs are still the main technology used inside the space
environment as well as inside many applications regarding
submarines, but they are not considered a suitable
technology for static or mobile applications on earth.

• Consideration the space and defense sector up to today only

a few power units between 1 and 10 kW have been realized.

• Astris Energy and Apollo Energy Systems in USA and AFC

energy, Hydro Cell OY and Vito in Europe
 Polymer electrolyte fuel cells (PEFC)
• They are also known with the initials PEM (Polymer
Electrolyte Membranes). The electrolyte consists of a
solid polymeric membrane, which is sandwiched
between two platinum-catalysed porous electrodes.

• Polymer electrolyte fuel cells (PEMFCs) are

environmental friendly and efficient energy conversion
devices that are expected to play a dominant role in
future energy solutions.
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• The operating temperature is around 80oC and the operating
pressure 1-8 atm. PEFC units with a power output up to 100
kW have been constructed.

• The low operating temperature allows them to be started

quickly (low warm-up time) and results in less wear on system
components thus increasing the cell durability.

• However a noble-metal catalyst (typically platinum) is

required in order to start the electrochemical process at low
temperatures.
• This fuel cell is fed with hydrogen, which is oxidized at the
anode, and oxygen that is reduced at the cathode.

• The protons released during the oxidation of hydrogen are

conducted through the proton exchange membrane to the
cathode.

• Since the membrane is not electronically conductive, the

electrons released from the hydrogen travel along the
electrical external load, provided thus generating an electrical
current.
• The only liquid in this fuel cell is water; thus, corrosion problems are
minimal.

• Typically, carbon electrodes with platinum electro-catalyst are used for both
anode and cathode, and with either carbon or metal interconnects.

• Water management in the membrane is critical for efficient performance;

the fuel cell must operate under conditions where the by-product water
does not evaporate faster than it is produced because the membrane must
be hydrated.

• Because of the limitation on the operating temperature imposed by the

polymer, usually less than 100 °C
 PEMFC Structure
• The PEMFC, like all fuel cells, consists of three basic parts; the
anode, the cathode, and the membrane. These three areas are often
manufactured from separate sheets, and the PEM is no exception

• The electrodes and the electrolyte layer are then joined together, by
hot pressing process, in order to create a “membrane electrode
assembly” (MEA)

• The MEA is composed by a proton exchange membrane, two catalyst

layers, and two gas diffusion layers (GDL). Typically, these
components are individually fabricated and then pressed to together
at moderate temperatures and pressures.
 MEA structure

PEMFC structure
PEMFC Cell Stack
 The Membrane
• Although many different types of membranes are used, by far that
most common is Nafion (DuPont), a sulphonated polymer with a
PFTE (Poly Tetra Fluoro Ethylene)backbone.

• The Nafion is created through the addition of sulfonic acid groups

into the bulk of a polymer matrix of Teflon and its layer has a
thickness between 50 and 175 µm.

• The thinner Nafion membrane allows a higher conductivity of the

cell, but introduces a more problematic water management; a
thicker membrane slows down the conductivity.
• The function of this structure is to act as an electrolyte (ionic
conduction) and a separator between oxygen and hydrogen.

• Other types of membranes that being researched are: polymer-

zeolite nanocomposite proton exchange membrane, sulfonated
polyphosphazene based membranes and phosphoric acid-doped
poly (bisbenzoxazole) high temperature ion-conducting membrane.

• However the Nafion membrane is so commonly used (due to his

high chemical stability) that it is considered an industry standard,
and all new membranes are compared to it.
• The main characteristics of the membrane are:
– High water uptake;

– Good proton (H+ ) conductor if well hydrated, but doesn’t allow the
conduction of electrons which are constricted to follow an external
path thus generating an electrical current;

– does not allow the intermixing of the hydrogen and oxygen thus
maintaining the two gas separated;

– high chemical and mechanical resistance due to the properties of

Teflon backbone.
 The Catalyst Layer
• The catalyst layer is in direct contact with the membrane and the gas
diffusion layer. It is also referred to as the active layer.

• In both the anode and cathode, the catalyst layer is the location of the half-
cell reaction in a PEM fuel cell. The catalyst layer is either applied to the
membrane or to the gas diffusion layer.

• In either case, the objective of the catalyst layer is to place catalyst

nanoparticles (generally 5-15 nm platinum or platinum alloys, such as
PtxRuy) within close proximity of the membrane.

• The aim is to generate a gas/solid/membrane triple contact to allow to take

place the electrochemical reactions.
 The Gas Diffusion Layer
• The porous gas diffusion layer in PEM fuel cells ensures that
reactants effectively diffuse to the catalyst layer. In addition,
the gas diffusion layer is the electrical conductor that
transports electrons to and from the catalyst layer.

• The functions of the backing layer are to:

– (1) act as a gas diffuser
– (2) provide mechanical support
– (3) provide an electrical pathway for electrons
– (4) channel product water away from the electrodes
• Typically, gas diffusion layers are constructed from porous
carbon paper, or carbon cloth, with a thickness in the range of
100–300 µm, coated with a layer of microporous carbon
powder/PTFE.

• The function of polytetrafluoroethylene is to prevent water

from “pooling” within the pore volume of the backing layer so
that gases freely contact the catalyst sites.

• Furthermore, it facilitates product water removal on the

cathode as it creates a non-wetting surface within the
passages of the backing material.
• The gas diffusion layer also assists in water
management by allowing an appropriate amount of
water to reach and be held at the membrane for
hydration.

• In addition, gas diffusion layers are typically wet-

proofed with a PTFE (Teflon) dispersion coating to
ensure that the pores of the layer do not become
congested with liquid water .
• A typical fuel cell provides a voltage between 0.6 and
0.7 V @ 0.5 A/cm2 so, in order to provide greater
voltage and power, a great number of cells is placed
in series creating a structure called cell stack.

• Inside a cell stack each MEA assembled is placed

between two bipolar plates with the exception of the
first and the last cell
 Advantages
• The power density of the cell stack is very high, particularly in
pressurized systems.

• The operative pressure difference between the anode and the

cathode can be very large due to the mechanical properties of the
solid polymer electrolyte. Therefore, operating with a pressurized
system it is quite easy.

• A wide variety of cell component materials can be adopted on

account of its low operating temperature (80 °C). In particular, use of
low cost carbon materials may contribute to the cost reduction of
cell stack
 Advantages
• The PEFC has a solid electrolyte which provides excellent resistance
to gas crossover.

• The PEFC’s low operating temperature allows rapid start-up .

• Absence of corrosive cell constituents, the use of the exotic

materials required in other fuel cell types, both in stack construction
and in the BoP (balance of plants) is not required.

• Test results have demonstrated that PEFCs are capable of high

current densities of over 2 kW/l and 2 W/cm2 .
 Disadvantages
• The low and narrow operating temperature range makes thermal
management difficult, especially at very high current densities, and
makes it difficult to use the rejected heat for cogeneration or in
bottoming cycles.

• Water management is another significant challenge in PEFC design,

as engineers must balance ensuring sufficient hydration of the
electrolyte against flooding the electrolyte.

• In addition, PEFCs are quite sensitive to poisoning by trace levels of

contaminants including CO, sulfur species, and ammonia. To some
extent, some of these disadvantages can be counteracted by
lowering operating current density and increasing electrode catalyst
loading, but both increase cost of the system.
• Therefore, the CO concentration has to be reduced
below 10 ppm with CO removal if the reformate
from hydrocarbons or alcohols is used as a fuel for
the PEMFC.

• The temperature of recovered waste heat is lower

than that of other fuel cells. As a result recovered
heat can be utilized only as hot water.
• If hydrocarbon fuels are used, the extensive fuel
processing required negatively impacts system size,
complexity, efficiency and system cost.

• Finally, for hydrogen PEFC the need for a hydrogen

infrastructure to be developed poses a barrier to
commercialization
 PEMFC Applications
• PEM Fuel cells can generate power from some W to hundreds
of kW. Because of this, they may be used in almost every
application where local electricity generation is needed.

• PEMFC are already being tested inside applications such as

automobiles, buses, utility vehicles, scooters, bicycles,
aerospace/military applications (e.g. Shuttle and submarines).

• PEMFC are also being tested for distributed power generation

inside individual homes, buildings or communities due to their
modularity and excellent flexibility in power supply.
• Transportation (up to 70 kW)
• Stationary power applications (up to 500 kW)
• Portable power applications (up to some kW)
 Transportation
• Actually most of the major car makers and the
governments of some states (like USA and JAPAN) are
actively engaged in the development of FCVs.

• Main requirements that the automotive PEM stack

technology still needs to fulfill in order to became a
major technology on the market are:
– a very short start-up time (fraction of a minute);
– small size and weight of the PEMFC systems;
– an operating life time which spans from 3000 to 5000
operational hours.
 Stationary Applications for Distributed Power Generation

• The high modularity, high efficiency and lower emission

of PEMFC stacks allow their use for the expansion of the
electric network.

• As a result part of the loads of the network can be

directly managed by many power systems which are
distributed inside different types of buildings and
structures, thus lowering the burden placed on the
power plants.
• The requirements that these systems have to fulfill
are:
– a lower noise level since the power unit are usually
installed indoor;
– short start-up time for emergency power systems;
– power units designed for outdoor use must be able to
operate in extreme ambient conditions;
– an operational life cycle which spans from 40,000 to
80,000 hours (five to ten years).
 Portable Power Systems
• PEMFC technology consists in 2 main types of applications
• power cells for battery replacements with power below 100
W;
• portable generators with at least 1 kW power based on power
cells;
• The main factors that must be considered in those systems
are:
– The operative time of the battery
– The size and weight of the system.
Direct Methanol Fuel Cells (DMFC)
• DMFCs are another technology of fuel cells, based upon a polymer electrolytes
membrane (PEM) which operates at temperatures between 70 and 100 °C.

• The differences between DMFC and PEMFC resides in the fuel used, which in this
case is constituted by liquid methanol dissolved in water.

• As the PEMFC, the DMFC are considered an environmental friendly technology

since there is no production of sulfur or nitrogen oxides (only carbon dioxide).

• The main advantage of DMFC resides in the fuel used, since methanol is a cheap
and easy to produce fuel which can be directly injected and used inside the cell
itself thus allowing a simple cell structure and consequently lower weights.
 DMFC Structure
• The core of a Direct Methanol Fuel Cell is the polymer
electrolyte ion exchange membrane. As the PEMFC the
state of the art in membranes is Nafion. This polymer
has sites with strong ionic properties acting as proton
exchange sites

• The membrane faces are in direct contact with the

anode and the cathode which both consists in a three
layer structure made by: a catalytic layer, a diffusion
layer and a backing layer
• The catalytic layer is composed by a mixture of a catalyst, which is
usually a combination of platinum ( at the cathode) and platinum-
ruthenium alloy (at the anode) nanoparticles and a ionomer.

• As the membrane the ionomer is composed by a perfluorosulfonic

acid polymer. The main characteristic of the catalytic layer is its
mixed conductivity for both protons and electrons.

• The diffusion layer is composed by a mixture of carbon and Teflon

with hydrophobic properties which allows both the transportation
of oxygen molecules to the catalyst layer of the cathode and the
escape of CO2 molecules from the anode.
DMFC structure
CH3OH + H2O → CO2 + 6H+ + 6e-
• The combination of the membrane and the electrodes gives life to the MEA
assembly which thickness is usually around 1 millimeter

• When the cell is activated a liquid flux of methanol is injected into the anode
from where it is diffused inside the diffusion layer.

• The methanol reaches the catalytic layer where it is oxidized into carbon
dioxide, protons and electrons.

• At this point the protons diffuse trough the Nafion membrane and electrons
trough the catalytic layer but, while the electrons are collected by the
cathode thus generating an electrical current, the protons that diffuses
through the membrane react at the cathode with oxygen to produce water
 Advantages
• These cells is that they work on methanol which is much
more easy to store and to produce than hydrogen,
without the hazard of explosions as in the case of the
hydrogen

• Thanks to the small dimensions, the low temperature

operative range and the high usability of the fuel, DM
fuel cells are actually a well seen technology for portable
applications and generators.
 Drawback
• The drawback of the technology is that DMFC actually detain
an efficiency around 35% which is the lowest among all the
fuel cells.

• Still, due to the low efficiency, the power density that the
DMFC are able to provide, which is around 200-400 mW/cm , 2

is still too low. As a consequence DMFC can’t at the moment

meet the energy production requirements for many of their
actual portable applications.
 Applications
• Portable power generation

• Low weight substitute of the batteries for both civil

and military environments.
Phosphoric Acid Fuel Cells (PAFC)
• PAFC is at the moment the most advanced fuel cell technology for
terrestrial applications. Packaged units of 200-250 kWe are already
commercially available for electricity generation or cogeneration,
while demonstration systems of 25 kW–11 MW have been
constructed in Europe, USA and Japan.

• Phosphoric acid (H3PO4) is the electrolyte. Hydrogen is produced by

an external reformer from fuels such as natural gas or methanol.
Air is the oxidiser. The operating temperature is around 200oC,
which makes PEFC’s attractive for cogeneration applications, in
particular in the tertiary sector.

60
• The basic cell structure is made of a ceramic matrix
impregnated with a solution of phosphoric acid which is
surrounded by a couple of porous electrodes used to
collect the ions and to diffuse the gasses

• The ceramic matrix which contains the phosphoric acid is

made of approximately 1 µm silicon carbide particles.

• Thick martix to avoid gasses cross-over from the anode

to the cathode.
• The gas diffusion electrodes are made using platinum
nanocatalyst, supported on high surface carbon,
dispersed inside a layer made of carbon bonded with
polytetrafluoroethelyne (PTFE).

• This generates a porous structure with a well dispersed

high conductive catalyst, which have the duty to both
efficiently disperse the reactant gasses up to the matrix
layer interface and to collect the electrons
• Phosphoric acid requires high operative temperature
ranges, and does not react with CO2 to form
carbonate ions, both carbon monoxide poisoning
and the formation of carbonate are not an issue for
PAFCs.

• PAFCs are mostly developed for stationary

applications.
• Due to the high temperature range of the cells pure
hydrogen is not required. This allows the cell to be
fueled with relatively impure hydrogen which can be
easily derived from fuel reforming process.

• The overall cell efficiency is between 37% and 42%

however, if the heated water/steam generated by
the cell is used inside a combined heath system, the
total efficiency can go over 60%.
• Operating life cycle which exceeds 65,000 hours with
an operative temperature between 150 oC and
o
220 C;

• The largest demonstration PAFC plant is also in Japan

with 11 MW capacity that went into operation in
1991 in the Tokyo Electric Power Company system at
the Goi Thermal station.
 Advantages
• PAFCs are much less sensitive to CO than PEFCs and AFCs: PAFCs tolerate
about one percent of CO as a diluent.

• The operating temperature also provides considerable design flexibility for

thermal management.

• PAFCs have demonstrated system efficiencies of 37 to 42 percent (based on

LHV of natural gas fuel), which is higher than most PEFC systems could
achieve (but lower than many of the SOFC and MCFC systems).

• In addition, the waste heat from PAFC can be readily used in most
commercial and industrial cogeneration applications, and would technically
allow the use of a bottoming cycle.
 Disadvantages
• Cathode-side oxygen reduction is slower than in AFC,
and requires the use of a Platinum catalyst.

• Although less complex than for PEFC, PAFCs still require

extensive fuel processing, including typically a water gas
shift reactor to achieve good performance.

• Finally, the highly corrosive nature of phosphoric acid

requires the use of expensive materials in the stack
(especially the graphite separator plates).
Molten Carbonate Fuel Cells (MCFC)
• Molten carbonate fuel cells (MCFC) represent an
high temperature technology of fuel cells which are
currently being developed as a solution for static
electrical power generation or to work with other
static generation applications which are already on
the market like coal based power plants or some
industrial facilities
• Molten alkali carbonate mixture, retained in a porous lithium
aluminate matrix, is used as the electrolyte.

• The eutectic mixture consists of 68% Li2CO3 and 32% K2CO3, which at
the operating temperature of 600-700oC is at liquid phase.

• The fuel consists of a gaseous mixture of H2, CO and CO2, which is

obtained with reforming of hydrocarbons such as natural gas, or
with coal gasification. The high operating temperature makes
internal reforming possible. For this purpose, the heat released by
the fuel cell itself is used.
71
73
• The base structure of a MCFC is made with a ceramic matrix
containing the electrolyte which is surrounded by the anode,
fueled by hydrogen rich fuel, and the cathode, fueled by
oxygen (usually air).

• Two mixtures of molten carbonate salts (the high temperature

is required in order to melt this mixture) that could be used as
the electrolyte. The two mixtures can be a combination of
lithium carbonate and potassium carbonate or lithium
carbonate and sodium carbonate.
• The anode is a porous electrode made with a nickel alloy (Ni-
5Cr, Ni-xAl) as the catalyst. This alloys contains a small percent
of aluminum or chromium in order to suppress the hot creep
inside the electrode structure.

• The cathode is realized with a porous nickel catalyst. During

the cell start-up, the nickel in contact with the electrolyte
(eutectic mixture of Li2CO3 and K2CO3) is converted to high
conductive lithium doped nickel oxide (LixNi1-xO2)
• At the high operating temperatures in MCFCs, Noble metals
are not required for operation, and many common
hydrocarbon fuels can be reformed internally.

• Due to the high temperature, MCFCs can be fueled with gases

like methane, natural gas or coal reformed gases.

• High temperature they suffers from many problems such as

fast degradation of the cell structure, due to
mechanical/corrosion problems, and constant loss of the
electrolyte, due to evaporation, inside the cell
• The cell requires time in order to start since it needs to
reach a temperature of 650 °C. Upon reaching this
temperatures the carbonate salts begin to melt and
becomes conductive by carbonateions (CO3 ). 2-

• Carbonate ions are transferred through the electrolyte.

In order to sustain the flow of ions, carbon dioxide is
supplied continuously with air at a molar fraction of
2 2
O /CO equal to ½.
• MCFC’s have good prospects for utility and industrial applications of
medium to large size (at the order of MW).

• MCFC represent an high temperature fuel cell technology which can

reach an efficiency of 45% that can be potentially raised up to 60% -
70% if the waste heat is correctly utilized.

• The high temperature available heat can be used either for thermal
processes (cogeneration) or in a bottoming cycle for additional
power production. Experimental units have been constructed, but
the MCFC technology is still at the development phase.
78
• The focus of MCFC development has been larger
stationary and marine applications

• Where the relatively large size and weight of MCFC and

slow start-up time are not an issue.

• MCFCs are under development for use with a wide range

of conventional and renewable fuels
 Advantages
• The relatively high operating temperature of the MCFC (650 °C)
results in several benefits:

– no expensive electro-catalysts are needed as the nickel electrodes provide

sufficient activity

– both CO and certain hydrocarbons are fuels for the MCFC, as they are
converted to hydrogen within the stack (on special reformer plates)
simplifying the BoP and improving system efficiency to the high forties to
low fifties

• In addition, the high temperature waste heat allows the use of a

bottoming cycle to further boost the system efficiency to the high
fifties to low sixties.
 Disadvantages
• The main challenge for MCFC developers stems from the very
corrosive and mobile electrolyte, which requires use of nickel and
high-grade stainless steel as the cell hardware (cheaper than
graphite, but more expensive than ferritic steels).

• The higher temperatures promote material problems, impacting

mechanical stability and stack life.

• Also, a source of CO2 is required at the cathode (usually recycled

from anode exhaust) to form the carbonate ion, representing
additional BoP components. High contact resistances and cathode
resistance limit power densities to around 100 – 200 mW/cm2 at
practical operating voltages.
Solid Oxide Fuel Cells (SOFC)
• Solid Oxide Fuel Cells (SOFC) are another technology of
high temperature fuel cell which was developed for
stationary power applications of all sizes.

• SOFC operative temperature ranges between 800 °C and

1000 °C.

• Hydrogen (coal gas, bio gas, propane, natural gas,

hydrogen) can be used since the fuel reforming takes
place directly inside the cell.
• SOFC detain a very good power efficiency, near 60%, a long
term performance stability and an high thermal efficiency.

• It is due to the high quality waste heat that the steam

generated can be used, when pressurized, with a gas/steam
turbine based combined heat system which is theoretically
able to boosts the electrical efficiency up to 80%.

• Two types of Solid Oxide Fuel Cells actually exists: the oxygen
ion conducting type and the hydrogen ion conducting type
• The solid oxide fuel cell is an all-solid-state power
system, which uses yttria-stabilised zirconia (Y2O3-
ZrO2), a ceramic material, as the electrolyte layer.

• It operates at temperatures of 950-10000C. Pure

hydrogen or a mixture of H2 and CO is used as fuel,
which is produced with internal reforming of
hydrocarbons or with coal gasification.
85
• Typically, the anode is Co-ZrO2 or Ni-ZrO2 cermet,
and the cathode is Sr-doped LaMnO3 (strontium(Sr)-
Lanthanium manganite

• Early on, the limited conductivity of solid electrolytes

required cell operation at around 1000 °C, but more
recently thin-electrolyte cells with improved
cathodes have allowed a reduction in operating
temperature to (650 – 850 °C).
88
89
• SOFC’s also have good prospects for utility and industrial
applications of medium to large size (at the order of MW) with
efficiencies higher than 50%.

• The system provides high quality waste heat, which is ideal for
cogeneration or for additional power production by a bottoming
cycle. It is envisaged that units at the order of tens of megawatts
can be combined with a gas turbine – steam turbine combined
cycle: hot gases exiting the cell stack will drive a gas turbine.

• After the exit from the gas turbine they will pass through an
exhaust gas boiler producing steam for thermal processes or for
additional power production by a steam turbine.
90
 Advantages
• The SOFC is the fuel cell with the longest continuous development period,
starting in the late 1950s, several years before the AFC. Because the
electrolyte is solid, the cell can be cast into various shapes, such as tubular,
planar, or monolithic. The solid ceramic construction of the unit cell
alleviates any corrosion problems in the cell.

• The solid electrolyte also allows precise engineering of the three-phase

boundary and avoids electrolyte movement or flooding in the electrodes.

• The kinetics of the cell are relatively fast, and CO is a directly useable fuel as
it is in the MCFC. There is no requirement for CO2 at the cathode as with the
MCFC.
• The materials used in SOFC are modest in cost. Thin-
electrolyte planar SOFC unit cells have been demonstrated to
be cable of power densities close to those achieved with
PEFC.

• As with the MCFC, the high operating temperature allows use

of most of the waste heat for cogeneration or in bottoming
cycles. Efficiencies ranging from around 40 percent (simple
cycle small systems) to over 50 percent (hybrid systems) have
been demonstrated, and the potential for 60 percent+
efficiency exists as it does for MCFC
 Disadvantages
• The high temperature of the SOFC has its drawbacks. There are
thermal expansion mismatches among materials, and sealing
between cells is difficult in the flat plate configurations.

• The high operating temperature places severe constraints on

materials selection and results in difficult fabrication processes.

• Corrosion of metal stack components (such as the interconnects in

some designs) is a challenge. These factors limit stack-level power
density (though significantly higher than in PAFC and MCFC), and
thermal cycling and stack life (though the latter is better than for
MCFC and PEFC).
Cost for Fuel Cell Systems
• Cost reductions are being investigated include:
– Material reduction and exploration of lower-cost material
alternatives
– Reducing the complexity of an integrated system
– Minimizing temperature constraints (which add complexity
and cost to the system)
– Streamlining manufacturing processes
– Increasing power density (footprint reduction)
– Scaling up production to gain the benefit of economies of
scale (volume) through increased market penetration.
 FUEL CELL
APPLICATIONS

Stationary Mobility Portable Space

Power Systems Applications Applications Applications

Distributed
Light Traction Portable Power
Power
Vehicles (Cars) Generators
Generators

Heavy Traction
Combined Heat Consumer
Vehicles (Buses,
and Power Electronics
Trucks)

Marine Portable Applications

Back-Up Power
Propulsion Military of Fuel Cell
Supply
Equipment

Remote Area Aerial Battery

Power supply Propulsion Chargers
 APPLICATION
• Stationary Electric Power
– Initial stationary plant development has been focused on
several hundred kW to low MW capacity plant
– Smaller plants (several hundred kW to 1 to 2 MW) can be
sited at the user’s facility and are suited for cogeneration
operation, that is, the plants produce electricity and
thermal energy.
– Larger, dispersed plants (1 to 10 MW) are likely to be used
for distributed generation.
Stationary fuel-cell applications
are fuel cells that are either
connected to the electric grid
(distributed generation) to provide
supplemental power and
as emergency power system for
critical areas, or installed as a grid-
independent generator for on-site
service

STATIONARY FUEL-
CELL POWER
SYSTEMS
Fuel Cell Power Plant Major Processes
 Fuel cell used in
Mobility Applications
Fuel cell used in Portable Applications
[ELECTRONICS]
 Fuel cell used in
Portable Applications
[MILITARY]
Typical Gadgets used by a
Armed person in Mission
Fuel Cell used in Space Applications

• Both Gemini and Apollo

Spacecraft obtained Electrical
Power from Hydrogen and
Oxygen Fuel Cell.

• For Space applications, Fuel

Cells are better because they
have high power density.

• The other advantage of a fuel

cell is that the product produced
is water which can be used for
other applications.
Type of Fuel Cell used in various applications
FUEL CELL PERFORMANCE
 THERMODYNAMICS OF FUEL CELL PROCESS

H2 Electricity

Fuel Cell
O2 H2O
Fuel Cell

Heat

Anode: 2 H2→ 4 H+ + 4e-

Cathode: O2 + 4 H+ + 4 e-→ 2 H2O
Overall reaction: 2 H2 + O2 → 2H2O
• The overall reaction in fuel cells is,
1 Τ
𝐻2 𝑔 + 2 𝑂2 𝑔 → 𝐻 𝑂 𝑙 + 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛 ℎ𝑒𝑎𝑡
( ) ( ) 2 ( )

• The heat or enthalpy of a chemical reaction is the

difference between the heat of formation of products
and reactants,
∆𝐻𝑓 = ෍ 𝑃𝑟𝑜𝑑𝑢𝑐𝑡𝑠 − ෍ 𝑅𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠

1
= ℎ𝑓 − ℎ𝑓 + ℎ𝑓
𝐻2 𝑂(𝑙) 𝐻2 (𝑔) 2 𝑂2 (𝑔)
H2 1 Τ
+ 2 O2 g → H O 𝐥 +
286 kJ/mole
( g) ( ) 2 ()

1 Τ
H2 + 2 O2 g → H O 𝐠 + 242 kJ/mole
( g) ( ) 2 ( )
The overall reaction in the direct methanol fuel cell is
CH3OH(l) + 3/2 O2 (g) → CO2 (g) + 2H2O(l)

Heat of formation of Liquid methanol = ℎ𝑓 = −239 𝑘𝐽/𝑚𝑜𝑙𝑒

CH3OH l
()

Heat of formation of element oxygen = ℎ𝑓 =0

𝑂2 (𝑔)

Heat of formation of gaseous carbondioxide= ℎ𝑓 = −394 𝑘𝐽/𝑚𝑜𝑙𝑒

𝐶𝑂2 (𝑔)

Heat of formation of Liquid water = ℎ𝑓 = −286 𝑘𝐽/𝑚𝑜𝑙𝑒

𝐻2 𝑂 (𝑙)

∆𝐻𝑓 = ෍ 𝑃𝑟𝑜𝑑𝑢𝑐𝑡𝑠 − ෍ 𝑅𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠

3
= 2 ℎ𝑓 + ℎ𝑓 − ℎ𝑓 + ℎ𝑓
𝐻2 𝑂(𝑙) 𝐶𝑂2 (𝑔) CH3OH l
()
2 𝑂2 (𝑔)

∴ 𝐹𝑜𝑟 𝐷𝑖𝑟𝑒𝑐𝑡 𝑚𝑒𝑡ℎ𝑎𝑛𝑜𝑙 𝐹𝑢𝑒𝑙 𝐶𝑒𝑙𝑙, ∆𝐻𝑓 = −727 𝑘𝐽/𝑚𝑜𝑙𝑒

 The Role of Gibbs Free Energy and Nernst Potential

• The maximum electrical work (Wel) obtainable in a fuel

cell operating at constant temperature and pressure is
given by the change in Gibbs free energy (∆G) of the
electrochemical reaction.

– n is the number of electrons participating in the reaction,

– F is Faraday's constant (96,487 coulombs/g-mole electron)
– E is the ideal potential of the cell
• The Gibbs free energy change is also given by the following
state function:

– ∆H is the enthalpy change

– ∆S is the entropy change.
The amount of heat that is produced by a fuel cell operating
reversibly is T∆S.
Reactions in fuel cells that have negative entropy change generate
heat (such as hydrogen oxidation)
positive entropy change (such as direct solid carbon oxidation) may
extract heat from their surroundings
 Ideal Performance
• The Nernst potential, E, gives the ideal open circuit
cell potential. This potential sets the upper limit or
maximum performance achievable by a fuel cell.

• The Nernst equation provides a relationship

between the ideal standard potential (E°) for the cell
reaction and the ideal equilibrium potential (E) at
other partial pressures of reactants and products.
 Cell Efficiency
• The thermal efficiency of a fuel conversion device is
defined as the amount of useful energy produced
relative to the change in enthalpy, ∆H, between the
product and feed streams.
• Fuel cells convert chemical energy directly into electrical
energy.

• In the ideal case of an electrochemical converter, such as

a fuel cell, the change in Gibbs free energy, ∆G, of the
reaction is available as useful electric energy at the
temperature of the conversion.

• The ideal efficiency of a fuel cell, operating reversibly, is

then
• The thermal efficiency of a hydrogen/oxygen fuel cell
can then be written in terms of the actual cell
voltage:
 Fuel Cell Calculations
1. What hydrogen flow rate is required to generate 1.0
ampere of current in a fuel cell?
Solutions:
• For every molecule of hydrogen (H2) that reacts within a
fuel cell, two electrons are liberated at the fuel cell
anode.
• The solution requires knowledge of the definition of an
ampere (A) and an equivalence of electrons.
H2 → 2H+ + 2e-
The moles of hydrogen liberated to generate one amp can
be calculated directly:
• One equivalence of electrons is 1 g mol of electrons or 6.022 x1023 electrons
(Avagadro’s number).
• This quantity of electrons has the charge of 96,487 coulombs (C) (Faraday’s
constant).
• Thus, the charge of a single electron is 1.602 x10-19 C. One (1) ampere of current
is defined as 1 C/sec.
2. A 1.0 MWDC fuel cell stack is operated with a cell
voltage of 700 mV on pure hydrogen with a fuel
utilization, Uf of 80 percent.
(a) How much hydrogen will be consumed?
(b) What is the required fuel flow rate?
(c) What is the required air flow rate for a 25
percent oxidant utilization, Uox?
• Solution:
• The solution of this problem will be simplified by
assuming that the individual fuel cells are arranged in
parallel. That is, the fuel cell stack voltage is the same as
each individual cell voltage, and the fuel cell stack
current is equal to the current of an individual cell times
the number of cells.

• Recalling that power (P) is the product of voltage (V)

and current (I),
P=IxV
• Therefore, the current through the fuel cell stack can
be calculated as
k gH 2 k gH 2
mH 2 ,Consumed  (1429 k A) X 0.037605  53.73
hr  k A hr

kgH 2 kgH 2
mH 2 ,Consumed  (1429 kA) X 0.037605  53.73
hr  kA hr
• Note that without the simplifying assumption that the fuel cells
were arranged in parallel, the same hydrogen mass flow could have
been calculated with a few extra steps.

• For example, if the fuel cell stack was composed of 500 cells in
series, then the stack voltage would have been 350 volts [(500
cells)(0.7 V/cell)],

• The stack current would have been 2.858 kA/cell [1429 kA / 500
cells]. Because this stack current passes through 500 cells arranged
in series, the hydrogen consumption is calculated as
 kA kgH 2 kgH 2
mH 2 ,Consumed  2.858 X 0.037605 X 500 Cells  53.73
Cell hr  kA hr
(b) The utilization of fuel in a fuel cell is defined as

Therefore the fuel flow rate required to generate 1 MWDC can be

calculated as
H 2,consumed 53.73 k gH2
H 2,in    67.172
Uf 80% hr
(c) To determine the air requirement, first observe that
the stoichiometric ratio of hydrogen to oxygen is 2 to
1 for H2O. Thus, the moles of oxygen required for the
fuel cell reaction are determined by
 kgH 2  1kg mol H 2  1 kg mol O2  kg mol O2
nO2 ,Consumed   53.73    13.33
 hr  2.0158 kg H 2  2 kg mol H 2  hr
• If 25 percent utilization is required, then the air feed
must contain four times the oxygen that is consumed
 kgO2,consumed  1kg mol O2 , sup plied  kg mol O
nO2 ,sup plied  13.33    53.32 2
 0.25 kg mol O 
 hr  2,consumed  hr
• Because dry air contains 21 percent O2 by volume, or
by mole percent, the required mass flow rate of dry
air is

 kg mol O2  1kg mol air  28.85kg dry air  kg dry air

mair sup plied   53.32     7325 .15
 hr  0.21 kg mol O2  1kg mol air  hr
 References
• Fuel Cell Handbook (Seventh Edition), U.S. Department of Energy Office of Fossil
Energy National Energy Technology Laboratory P.O. Box 880 Morgantown, West
Virginia 26507-0880 November 2004

• Leonardo Giorgi, and Fabio Leccese, “Fuel Cells: Technologies and Applications”,
The Open Fuel Cells Journal, 2013, 6, 1-20.