Fuel Cell Fundamentals

Dr. Sammia Shahid

COURSE OUTLINE
Course Description
Fuel cells are considered the most efficient devices for converting
chemical energy of the fuel to electricity. Stationary and
automotive fuel cells have received a lot of attention and now
micro fuel cells for portable electronics have also entered a period
of intensive research and development. Fuel cell technology also,
continues to attract a great deal of interest as an alternative
power source to the Internal Combustion engine drive train. Even
though significant technical progress has been made, broad
application and the eventual success of Fuel Cell technology in
automotive and other applications remain elusive. Therefore, this
course will cover overview of fuel cell technology,
thermodynamics of direct energy conversion and fuel cell
efficiency, electrochemistry, equilibrium and reaction kinetics, fuel
cell types, fuel cell systems for transportation, buildings, utility
and portable power energy conversion applications.
Learning Outcomes
After successful completion of the course the
students will be able to explain:
general electrochemical and fuel cell principles,
fuel cell efficiency and causes of voltage losses,
fuel cell components and their impact on
performance,
basic fuel processing and safety aspects of
fuels,
role of fuel cells in reducing environmental
pollution,
current trends in fuel cell applications.
Reading Material
REQUIRED:
Fuel Cell Fundamentals, Ryan O'Hayre, Suk-Won Cha,
Whitney Colella, Fritz B. Prinz, 2nd Ed, Wiley, 2009.
OPTIONAL:
Fuel Cells: Principles and Applications, B Viswanathan,
M Aulice Scibioh, 2006, University Press, India
Principles of Fuel Cells, Xianguo Li, University of Waterloo,
Ontario, Canada, 2005, Taylor & Francis
Fuel Cells, Modeling, Control and Applications, Bei Gou,
Woon Ki Na, Bill Biong, 2010, Taylor & Francis
Course Schedule
Week Topics Readings
1*
Fuel Cell Principles
Introduction to simple fuel cell
Fuel cell advantages & disadvantages
Fuel cell types
Fuel Cell operation, performance and technology
Chapter 1
2*
Fuel Cell Thermodynamics
Thermodynamics overview
Heat potential of fuel
Chapter 2
3*
Fuel Cell Thermodynamics
Working potential of fuel
Fuel cell efficiency
Chapter 2
4*
Fuel Cell Reaction Kinetics
Electrode Kinetics
Activation Energy
Exchange current and electro catalysis
Chapter 3
5*
Fuel Cell Reaction Kinetics
Electrode Kinetics
Activation Energy
Exchange current and electro catalysis
Chapter 3
6*, 7*
Fuel Cell Characterization
Overview of characterization techniques
Electrochemical characterization
Ex Situ Characterization techniques
Chapter 7
8 MIDTERM
Course Schedule
Week Topics Readings
9*
Overview of Fuel Cell Types
Phosphoric acid Fuel Cell
Membrane fuel cell
Alkaline fuel cell
Chapter 8
10*
Overview of Fuel Cell Types
Molten carbonate fuel cells
Solid oxide fuel cells
Direct methanol fuel cells
Chapter 8
11*,12*
Overview of Fuel Cell Systems
Fuel cell Stack
Thermal management subsystem
Fuel delivery subsystem
Chapter 10
13*
Fuel Processing Subsystem Design
Fuel reforming overview
Water gas shift reactors
Carbon monoxide clean up
Chapter 11
14*
Environmental Impact of Fuel Cells
Life cycle assessment
Emissions related to global warming
Emissions related to air pollution
Chapter 14
15 Revision
16 Final Exam
Grading Policy
Assignments: 10%
Quizzes: 15%
Midterms: 25%
Final: 50%
Chapter 01
Introduction of Fuel Cell
Outline
Energy Resources
What are Batteries?
What is a Fuel Cell?
History of the fuel cell
Why are we interested in fuel cells?
Fuel Cell Advantages and Disadvantages
What are the different types of fuel cells?
What are the problems that different types of fuel
cells encounter?
How are different types of fuel cells employed?
Humanitys Top Ten Problems
for next 50 years
1. ENERGY
2. WATER
3. FOOD
4. ENVIRONMENT
5. POVERTY
6. TERRORISM & WAR
7. DISEASE
8. EDUCATION
9. DEMOCRACY
10. POPULATION
2003 6.3 Billion People
2050 10 Billion People
Why to Conserve?
Why to Conserve?
Forms of Energy
Mechanical energy
Flowing rivers, wind
Electrical energy
Electromagnetic Field, Batteries
Chemical Energy
Released in Chemical Reactions (Heat,
electrochemical/batteries)
Thermal Energy
Heat (released by chemical reactions, nuclear
reactions, geothermal sources, etc.)
What are the uses of different
forms of energy?
Mechanical Energy
Operate equipment (pump water, grind grains,
weaving machines, etc.)
Moving vehicles
Conversion into electrical energy
Chemical Energy
Produce new chemicals
Make heat
Conversion into electrical energy (batteries, fuel cells)
Thermal Energy
Space heating
Materials processing
Hot water
Conversion to Electrical Energy
Electrical Energy
Most flexible form of energy.
Easily transmitted and converted to other forms of
energy
What are the uses of different
forms of energy?
Availability vs. Utility
Electrical Energy is most useful. Can be
converted into all the other types of
energy.
Thermal Energy is most available. Can
be produced in almost any location by
burning fuels.
Chemical Energy is most easily stored.
Can be converted into thermal or
electrical energy easily.
Energy Conversion
Mechanical to mechanical conversion
Watermills, windmills
Mechanical to electrical
Generators (motors)
Chemical to electrical
Batteries, Fuel Cells
Thermal to Mechanical
Heat Engines, Refrigerators
Energy Conversions
Energy Resources
Renewable (16%)
Solar
Wind
Falling, flowing water
Biomass
Non-renewable (84%)
Oil
Natural gas
Coal
Nuclear power
Important Nonrenewable Energy
Sources
Coal Formation and Types
Stack
Waste heat
Cooling tower
transfers waste
heat to
atmosphere
Pulverizing
mill
Turbine Coal bunker
Generator
Cooling
loop
Condenser
Boiler
Filter
Toxic ash disposal
Asphalt
Gases
Lowest Boiling Point
Highest Boiling Point
Gasoline
Aviation fuel
Heating oil
Diesel
oil
Heated
crude oil
Furnace
Naphtha
Grease
and wax
Carbon Dioxide Emissions Per Unit
of Energy of Different Fuels
A Sustainable Energy Strategy
Decentralized Power System
What are Batteries?
Electrical Energy Storage Devices
Battery Types
Primary
Non-Chargeable
(Disposable) Batteries
Secondary
Chargeable Batteries
Leclanch Cells (zinc carbon or dry cell)
Alkaline Cells
Mercury Oxide Cells
Zinc/MnO
2
Cells
Aluminum / Air Cells
Lithium Cells
Liquid cathode lithium cells
Solid cathode lithium cells
Solid electrolyte lithium cells
Lithium-Iron Cells
Magnesium-Copper Chloride Reserve Cells
Primary Disposable Batteries
Leadacid Cells
Zinc/MnO
2
Cells (Mechanical Recharging)
Nickel/Cadmium Cells
Nickel/Metal Hydride (NiMH) Cells
Lithium Ion Cells
Rechargeable Alkaline Manganese Cells
Secondary Rechargeable Batteries
Applications: Radios, toys, photo-flash applications, watches
Half cell reactions
Zn + 2 OH
-
> ZnO + H
2
O + 2 e
-
2 MnO
2
+ H
2
O + 2 e
-
>Mn
2
O
3
+ 2 OH
-
The overall reaction
Zn + 2MnO
2
> ZnO + Mn
2
O
3
E = 1.5 V
Storage density about twice that of the carbon-zinc cell, but more
expensive
Alkaline Cells
Anode: Amalgamated zinc powder
Cathode: Oxygen (O
2
)
Electrolyte: Potassium hydroxide (KOH)
Half-reactions:
Zn + 2OH
-
> Zn(OH)
2
1/2 O
2
+ H
2
O + 2e > 2 OH
-
Overall reaction:
2Zn +O
2
+ 2H
2
O > 2Zn(OH)
2
E = 1.65 V
Applications: Hearing aids, pagers, electric vehicles
Zinc/ Air Cells
Applications: Motive power in cars, trucks, standby/backup systems
Can be recharged hundreds of times and very cheap, but bulky and
environmentally noxious
Lead Acid Cells
Why are we interested in fuel cells?
Where do fuel cells fit in the overall scheme
of energy production and utilization?
What are the Problems associated with
existing technologies?
We are limited in Efficiency
The fuel cell will compete with many other types of energy
conversion devices, including
the gas turbine in city's power plant,
the gasoline engine in your car and
the battery in your laptop.
Combustion engines like the turbine and the gasoline
engine burn fuels and use the pressure created by the
expansion of the gases to do mechanical work.
Batteries converted chemical energy back into electrical
energy when needed.
Fuel cells should do both tasks more efficiently.
A fuel cell provides a DC (direct current) voltage that can be
used to power motors, lights or any number of electrical
appliances.
Fuel Cell
an electrochemical energy conversion device
To convert the chemicals hydrogen and oxygen into water,
and in the process it produces electricity.
Battery: the other electrochemical device that we are all
familiar.
A battery has all of its chemicals stored inside, and it converts
those chemicals into electricity too.
This means that a battery eventually "goes dead" and you
either throw it away or recharge it.
Discovery Sir William Grove a British
J udge (1839)
Rediscovery Francis Thomas Bacon
an Engineer working in a turbine Company
(1932) behind NASAs use of fuel cells in
space flights
Francis Thomas Bacon
Sir William Grove
History of the Fuel Cells
Brief History
1839 William Grove demonstrates principle of fuel cell operation
1894 Ostwald initiates efforts to replace heat engine with a carbon fuel cell operating
at 1100C
1897 J acques modified the fused salt cell and delivered 150mA
1912 Bantz and Ehrenbeg advocated a direct fuel cell with fused boride electrolyte,
the potential developed was 0.95 V but current was negligible
1938 Baur demonstrates coal fuel cell with oxygen ion conducting electrode
Post WWII Attention directed towards indirect cells using H
2
, CO and alcohols
1960s Gemini and Apollo spacecraft
1980s Space Shuttle
1993 George-town Bus demonstrated, with phosphoric acid fuel cell
1995 Mazda demonstrates H
2
fuelled PEM fuel cell golf cart
1997 Toyota demonstrates PEM Fuel cell car
2001 Fuel cell bike by Aprilia
2002 Honda (FCX4) Toyota (FCHV-BUS2) Nissan (X-Trail FCV) launched
Currently, fuel cell cars and buses provide mileage ranges commensurate with those
of conventional gas-powered vehicles. The principal challenges lie in making these
vehicles cost-competitive and in developing a safe and efficient fuel-distribution
infrastructure.
Fuel Cell Descriptions
Fuel Cells generate electricity through
an electrochemical process
In which the energy stored in a fuel is
converted directly into DC electricity.
Because electrical energy is generated
without combusting fuel,
Fuel cells are extremely attractive from an
environmental stand point.
For a fuel cell
Chemicals constantly flow into the cell
so it never goes dead.
As long as there is a flow of chemicals into
the cell,
the electricity flows out of the cell.
Most fuel cells in use today use
hydrogen and oxygen as the chemicals.
Animation of PEMFC
Chemistry of a Fuel Cell
Anode side:
2H
2
4H
+
+ 4e
-
Cathode side:
O
2
+ 4H
+
+ 4e
-
2H
2
O
Net reaction:
2H
2
+ O
2
2H
2
O
Fuel cell working
The pressurized hydrogen gas (H
2
) entering the fuel
cell on the anode side.
This gas is forced through the catalyst by the
pressure. When an H
2
molecule comes in contact with
the platinum on the catalyst, it splits into two H
+
ions
and two electrons (e
-
).
The electrons are conducted through the anode,
where they make their way through the external circuit
(doing useful work such as turning a motor) and return
to the cathode side of the fuel cell.
Meanwhile, on the cathode side of the fuel cell, oxygen gas
(O
2
) is being forced through the catalyst, where it forms two
oxygen atoms.
Each of these atoms has a strong negative charge.
This negative charge attracts the two H
+
ions through the
membrane, where they combine with an oxygen atom and two
of the electrons from the external circuit to form a water
molecule (H
2
O).
This reaction in a single fuel cell produces only about 0.7 volts.
To get this voltage up to a reasonable level, many separate fuel
cells must be combined to form a fuel-cell stack.
Fuel cell working
A functioning cell
in a Solid Oxide Fuel Cell stack
Classification of Fuel Cells
There are several different types of fuel cells, each using a
different chemistry.
Fuel cells are usually classified by the type of electrolyte
they use.
Some types of fuel cells work well for use in stationary power
generation plants.
Others may be useful for small portable applications or for
powering cars.
The proton exchange membrane fuel cell (PEMFC) is one
of the most promising technologies.
This is the type of fuel cell that will end up powering cars,
buses and maybe even your house. Let's take a look at how
they work...
Phosphoric
Acid
(PAFC)
Alkaline
(AFC)
Polymer
Electrolyte
Membrane
(PEMFC)
Direct Methanol
(DMFC)
Molten Carbonate
(MCFC)
Types of
Fuel
Cells
Polymer Electrolyte
Membrane
(PEMFC)
Direct Methanol
(DMFC)
Solid Oxide
(SOFC)
Fuel Cell Types
- Transportation applications
- Space application
- avoids the need of pure H
2
- envisaged for
stationary power
plants
- high volumetric energy
density
Types of Fuel Cells
Attractive characteristics of Fuel Cell
High energy conversion efficiency
Modular design
Very low chemical and acoustical pollution
Fuel flexibility
Cogeneration capability
Rapid load response
Advantages of Fuel Cells
Operate at low to moderate temperatures
where formation of NOx is eliminated
The heat engine efficiency is not in play
Advantages of Fuel Cells vs.
Internal Combustion Engines
Unlimited supply of fuel
No reliance on foreign oil
Little or no pollutants
Much higher energy conversion %
No moving parts
No noise
Disadvantages of Fuel Cells
Disadvantages
CO
2
discharged with methanol reform
Little more efficient than alternatives
Technology currently expensive
Many design issues still in progress
Hydrogen often created using dirty energy (e.g., coal)
Pure hydrogen is difficult to handle
Refilling stations, storage tanks,
Applications of Fuel cells
Hybrid Gas-electric Car
Hydrogen Fuel-cell Car
Why dont fuel cells rule?
Fuels that work in fuel cells are not
widely available
Efficiency promise has not been
achieved
Tremendous problems with materials
has limited successful engineering
Problems with Fuel Cells
The fuel cell uses oxygen and hydrogen to produce electricity.
The oxygen required for a fuel cell comes from the air.
In fact, in the PEM fuel cell, ordinary air is pumped into the cathode.
The hydrogen is not so readily available, however.
Hydrogen has some limitations that make it impractical for use in
most applications.
For instance, you don't have a hydrogen pipeline coming to your
house, and you can't pull up to a hydrogen pump at your local gas
station.
Hydrogen is difficult to store and distribute, so it would be much more
convenient if fuel cells could use fuels that are more readily available.
This problem is addressed by a device called a reformer.
A reformer turns hydrocarbon or alcohol fuels into hydrogen, which is
then fed to the fuel cell.
PART II
Introduction of the Fuel Cell
What is a Fuel Cell?
A fuel cell is an electrochemical device that combines hydrogen and
oxygen to produce electricity, with water and heat as its by-
product. As long as fuel is supplied, the fuel cell will continue to
generate power. Since the conversion of the fuel to energy takes place
through an electrochemical process, not combustion, the process is
clean, quiet and highly efficient two to three times more efficient
than fuel burning.
Introduction of the Fuel Cell (Cont.)
How does the Fuel Cell work?
A fuel cell generates electrical power by continuously
converting the chemical energy of a fuel into electrical energy
by way of an electrochemical reaction. The fuel cell itself has no
moving parts, making it a quiet and reliable source of power.
Fuel cells typically utilize hydrogen as the fuel, and oxygen
(usually from air) as the oxidant in the electrochemical reaction.
The reaction results in electricity, by-product water, and by-
product heat.
When hydrogen gas is introduced into the system, the catalyst
surface of the membrane splits hydrogen gas molecules into
protons and electrons. The protons pass through the membrane
to react with oxygen in the air (forming water). The electrons,
which cannot pass through the membrane, must travel around it,
thus creating the source of DC electricity.
Parts of a Fuel Cell
Anode
Negative post of the fuel cell.
Conducts the electrons that are freed from the hydrogen molecules so that
they can be used in an external circuit.
Etched channels disperse hydrogen gas over the surface of catalyst.
Cathode
Positive post of the fuel cell
Etched channels distribute oxygen to the surface of the catalyst.
Conducts electrons back from the external circuit to the catalyst
Recombine with the hydrogen ions and oxygen to form water.
Electrolyte
Proton exchange membrane.
Specially treated material, only conducts positively charged ions.
Membrane blocks electrons.
Catalyst
Special material that facilitates reaction of oxygen and hydrogen
Usually platinum powder very thinly coated onto carbon paper or cloth.
Rough & porous maximizes surface area exposed to hydrogen or oxygen
The platinum-coated side of the catalyst faces the PEM.
Other Types of Fuel Cells
Alkaline fuel cell (AFC)
This is one of the oldest designs. It has been used in the U.S. space program since the
1960s. The AFC is very susceptible to contamination, so it requires pure hydrogen and
oxygen. It is also very expensive, so this type of fuel cell is unlikely to be
commercialized.
Phosphoric-acid fuel cell (PAFC)
The phosphoric-acid fuel cell has potential for use in small stationary power-generation
systems. It operates at a higher temperature than PEM fuel cells, so it has a longer
warm-up time. This makes it unsuitable for use in cars.
Solid oxide fuel cell (SOFC)
These fuel cells are best suited for large-scale stationary power generators that could
provide electricity for factories or towns. This type of fuel cell operates at very high
temperatures (around 1,832 F, 1,000 C). This high temperature makes reliability a
problem, but it also has an advantage: The steam produced by the fuel cell can be
channeled into turbines to generate more electricity. This improves the overall efficiency
of the system.
Molten carbonate fuel cell (MCFC)
These fuel cells are also best suited for large stationary power generators. They operate
at 1,112 F (600 C), so they also generate steam that can be used to generate more
power. They have a lower operating temperature than the SOFC, which means they
don't need such exotic materials. This makes the design a little less expensive.
All fuel cells have the same
basic operating principle.
Fuel cells consist of an electrolyte material which is sandwiched
in between two thin electrodes (porous anode and cathode).
The input fuel passes over the anode (and oxygen over the
cathode) where it catalytically splits into ions and electrons.
The electrons go through an external circuit to serve an electric
load while the ions move through the electrolyte toward the
oppositely charged electrode.
At the electrode, ions combine to create by-products, primarily
water and CO
2
. Depending on the input fuel and electrolyte,
different chemical reactions will occur.
An input fuel is catalytically reacted
(electrons removed from the fuel elements)
in the fuel cell to create an electric current.
Basic Configuration
PEMFC
Animation of PEMFC
U
PEM FUEL CELL SYSTEM
COMPONENTS
Natural
Gas or
hydrocarbon
Fuel
Processor
Heat
and
Water
DC
Power
Fuel
Cell
Stack
Hydrogen
Power
Conditioner
AC
Power
Air
SUSTAINABLE Transport
U
Four primary types of fuel cells
They are based on the electrolyte employed:
Phosphoric Acid Fuel Cell
Molten Carbonate Fuel Cell
Solid Oxide Fuel Cell
Proton Exchange Membrane Fuel Cell
Phosphoric Acid Fuel Cells
-PAFCs
The most mature fuel cell technology in terms of system
development and commercialization activities.
Has been under development for more than 20 years
Has received a total worldwide investment in the
development and demonstration of the technology in
excess of $500 million.
The PAFC was selected for substantial development a
number of years ago because of the belief that, among the
low temperature fuel cells,
It was the only technology which showed relative tolerance
for reformed hydrocarbon fuels and thus could have
widespread applicability in the near term.
PAFC Design and Operation
The PAFC uses liquid phosphoric acid as the
electrolyte.
The phosphoric acid is contained in a Teflon bonded
silicone carbide matrix.
The small pore structure of this matrix preferentially
keeps the acid in place through capillary action.
Some acid may be entrained in the fuel or oxidant
streams and addition of acid may be required after
many hours of operation.
Platinum catalyzed, porous carbon electrodes are
used on both the fuel (anode) and oxidant (cathode)
sides of the electrolyte.
Fuel and oxidant gases are supplied to the backs of the porous
electrodes by parallel grooves formed into carbon or carbon-
composite plates.
These plates are electrically conductive and conduct electrons
from an anode to the cathode of the adjacent cell.
In most designs, the plates are "bi-polar" in that they have
grooves on both sides - one side supplies fuel to the anode of
one cell, while the other side supplies air or oxygen to the
cathode of the adjacent cell.
The byproduct water is removed as steam on the cathode (air
or oxygen) side of each cell by flowing excess oxidant past the
backs of the electrodes.
This water removal procedure requires that the system be
operated at temperatures around 375
o
F (190
o
C).
At lower temperatures, the product water will dissolve in the
electrolyte and not be removed as steam. At approximately
410
o
F (210
o
C), the phosphoric acid begins to decompose.
The byproduct water is removed as steam on the cathode
(air or oxygen) side of each cell by flowing excess oxidant
past the backs of the electrodes.
This water removal procedure requires that the system be
operated at temperatures around 375
o
F (190
o
C).
At lower temperatures, the product water will dissolve in
the electrolyte and not be removed as steam. At
approximately 410
o
F (210
o
C), the phosphoric acid begins
to decompose.
Excess heat is removed from the fuel cell stack by
providing carbon plates containing cooling channels every
few cells.
Either air or a liquid coolant, such as water, can be passed
through these channels to remove excess heat.
Electrochemical reactions in PAFC
At the anode:
Hydrogen is split into two hydrogen ions (H
+
), which
pass through the electrolyte to the cathode, and
two electrons which pass through the external circuit
(electric load) to the cathode.
At the cathode:
the hydrogen, electrons and oxygen combine to form
water.
Electrochemical reactions in PAFC
PAFC Performance Characteristics
PAFC power plant designs show electrical efficiencies in
the range from 36% (HHV) to 42% (HHV).
The higher efficiency designs operate with pressurized
reactants.
The higher efficiency pressurized design requires more
components and likely higher cost.
PAFC power plants supply usable thermal energy at an
efficiency of 37% (HHV) to 41% (HHV).
A portion of the thermal energy can be supplied at
temperatures of ~ 250
o
F to ~ 300
o
F.
However, the majority of the thermal energy is supplied at
~150
o
F.
Good and Bad of PAFC
Tolerant of CO and
CO
2
, permit use of
reformed fuels
Good proton
conductivity at higher
temperatures
Most favorable for
larger scale operation
Poor catalytic
performance of
Cathode (activation
potential ~0.25 V)
Expensive catalyst
Limited materials of
construction
Water management
requires fuel re-
circulation
Molten Carbonate Fuel Cells - MCFC
A molten carbonate salt mixture is used as its
electrolyte.
They evolved from work in the 1960's aimed at
producing a fuel cell which would operated directly on
coal.
While direct operation on coal seems less likely today,
The operation on coal-derived fuel gases or natural gas
is viable.
Molten Carbonate Salt
used as Electrolyte in MCFC
A molten carbonate salt mixture is used as its electrolyte.
The composition of the electrolyte (molten carbonate salt
mixture) varies, but usually consists of lithium carbonate
and potassium carbonate.
At the operating temperature of about 650
o
C (1200
o
F), the
salt mixture is liquid and a good ionic conductor.
The electrolyte is suspended in a porous, insulating and
chemically inert ceramic (LiAlO
3
) matrix.
Reactions in MCFC
Anode Reactions
The anode process involves a reaction between hydrogen and
carbonate ions (CO
3
=
) from the electrolyte.
The reaction produces water and carbon dioxide (CO
2
) while releasing
electrons to the anode.
Cathode Reactions
The cathode process combines oxygen and CO
2
from the oxidant
stream with electrons from the cathode to produce carbonate ions
which enter the electrolyte.
The need for CO
2
in the oxidant stream requires a system for collecting
CO
2
from the anode exhaust and mixing it with the cathode feed
stream.
Reactions
in MCFC
Description of reactions in MCFCs
The anode process involves a reaction between hydrogen
and carbonate ions (CO
3
=
) from the electrolyte.
The reaction produces water and carbon dioxide (CO
2
)
while releasing electrons to the anode.
The cathode process combines oxygen and CO
2
from the
oxidant stream with electrons from the cathode to produce
carbonate ions which enter the electrolyte.
The need for CO
2
in the oxidant stream requires a system
for collecting CO
2
from the anode exhaust and mixing it
with the cathode feed stream.
As the operating temperature increases,
the theoretical operating voltage for a fuel cell decreases and
with it the maximum theoretical fuel efficiency.
On the other hand, increasing the operating temperature
increases the rate of the electrochemical reaction and
Thus increases the current which can be obtained at a given
voltage.
The net effect for the MCFC is that the real operating voltage is
higher than the operating voltage for the PAFC at the same
current density.
The higher operating voltage of the MCFC means that more
power is available at a higher fuel efficiency from a MCFC than
from a PAFC of the same electrode area.
As size and cost scale roughly with electrode area, this
suggests that a MCFC should be smaller and less expensive
than a "comparable" PAFC.
As size and cost scale roughly with electrode area, this
suggests that a MCFC should be smaller and less expensive
than a "comparable" PAFC.
The MCFC also produces excess heat at a temperature which
is high enough to yield high pressure steam which may be fed
to a turbine to generate additional electricity.
In combined cycle operation, electrical efficiencies in excess of
60% (HHV) have been suggested for mature MCFC systems.
The MCFC operates at between 1110F (600C) and 1200F
(650C) which is necessary to achieve sufficient conductivity of
the electrolyte.
To maintain this operating temperature, a higher volume of air
is passed through the cathode for cooling purposes.
As mentioned above, the high operating temperature of
the MCFC offers the possibility that it could operate
directly on gaseous hydrocarbon fuels such as natural gas
The natural gas would be reformed to produce hydrogen
within the fuel cell itself.
The need for CO
2
in the oxidant stream requires that CO
2
from the spent anode gas be collected and mixed with the
incoming air stream.
Before this can be done, any residual hydrogen in the
spent fuel stream must be burned.
Future systems may incorporate membrane separators to
remove the hydrogen for recirculation back to the fuel
stream.
At cell operating temperatures of 650
o
C (1200
o
F) noble
metal catalysts are not required.
The anode is a highly porous sintered nickel powder,
alloyed with chromium to prevent agglomeration and creep
at operating temperatures.
The cathode is a porous nickel oxide material doped with
lithium.
Significant technology has been developed to provide
electrode structures which position the electrolyte with
respect to the electrodes and maintain that position while
allowing for some electrolyte boil-off during operation.
The electrolyte boil-off has an insignificant impact on cell
stack life.
A more significant factor of life expectancy has to do with
corrosion of the cathode.
The MCFC operating temperature is about 650
o
C
(1200
o
F).
At this temperature the salt mixture is liquid and is a good
conductor.
The cell performance is sensitive to operating
temperature.
A change in cell temperature from 650
o
C (1200
o
F) to
600
o
C (1110
o
F) results in a drop in cell voltage of almost
15%.
The reduction in cell voltage is due to increased ionic and
electrical resistance and a reduction in electrode kinetics.
Good and Bad of MCFC
Works well with
reformed fuels
Internal reforming
reactions possible
Highly corrosive
environment - severe
materials problems
Must recycle CO
2
Cathode reactions not
well understood -
anomalous kinetics are
hard to control
Very sensitive to sulfur
Solid Oxide Fuel Cells
The Solid Oxide Fuel Cell (SOFC) uses a ceramic, solid-phase
electrolyte which reduces corrosion considerations and
eliminates the electrolyte management problems associated
with the liquid electrolyte fuel cells.
To achieve adequate ionic conductivity in such a ceramic,
however, the system must operate at about 1000
o
C (1830
o
F).
At that temperature, internal reforming of carbonaceous fuels
should be possible, and the waste heat from such a device
would be easily utilized by conventional thermal electricity
generating plants to yield excellent fuel efficiency.
Good and Bad of SOFC
Compatible with
wide range of fuels
Internal reforming is
easily achieve
Cell fabrication
(materials problems)
Thermal cycling
Resistance of
electrolyte
PEMFC: Proton Exchange
Membrane Fuel Cell
The cell uses one of the simplest reactions of any fuel cell.
Four Basic Elements in a PEMFC
Anode: the negative post of the fuel cell, has several jobs.
It conducts the electrons that are freed from the hydrogen
molecules
so that they can be used in an external circuit.
It has channels etched into it that disperse the hydrogen gas
equally over the surface of the catalyst.
Cathode: the positive post of the fuel cell,
has channels etched into it that distribute the oxygen to the
surface of the catalyst.
It also conducts the electrons back from the external circuit to
the catalyst,
where they can recombine with the hydrogen ions and oxygen
to form water.
Four Basic Elements in a PEMFC
The electrolyte is the proton exchange membrane.
This specially treated material, which looks something like ordinary
kitchen plastic wrap,
only conducts positively charged ions.
The membrane blocks electrons.
The catalyst is a special material that facilitates the
reaction of oxygen and hydrogen.
It is usually made of platinum powder very thinly coated onto
carbon paper or cloth.
The catalyst is rough and porous so that the maximum surface
area of the platinum can be exposed to the hydrogen or oxygen.
The platinum-coated side of the catalyst faces the PEM.
PEMFCs operate at a fairly low temperature (about
176
o
F~80
o
C),
It means they warm up quickly and don't require
expensive containment structures.
Constant improvements in the engineering and
materials used in these cells have increased the
power density to a level where a device about the
size of a small piece of luggage can power a car.
Fuel cell working
Problems with Fuel Cells
The fuel cell uses oxygen and hydrogen to produce electricity.
The oxygen required for a fuel cell comes from the air.
In fact, in the PEM fuel cell, ordinary air is pumped into the cathode.
The hydrogen is not so readily available, however.
Hydrogen has some limitations that make it impractical for use in
most applications.
For instance, you don't have a hydrogen pipeline coming to your
house, and you can't pull up to a hydrogen pump at your local gas
station.
Hydrogen is difficult to store and distribute, so it would be much more
convenient if fuel cells could use fuels that are more readily available.
This problem is addressed by a device called a reformer.
A reformer turns hydrocarbon or alcohol fuels into hydrogen, which is
then fed to the fuel cell.
Good and Bad of PEMFC
Low temperature
operation
Used in Gemini
spacecraft
Small compact
modules
Very sensitive to CO
Perfluorosulfonic
acid membranes are
very costly
Water management
is difficult
Good and Bad of Alkaline Fuel
Cells
Operate well at low
temperature
No significant materials
problems
Catalysis at cathode
(oxygen reduction) has
relatively small
activation barrier
Successful in Space
Vehicles
Requires water
removal from
electrolyte
Cannot tolerate
carbon dioxide or
carbon monoxide in
the hydrogen fuel
Cannot tolerate ppm
level of CO
2
in air