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FUEL CELLS

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of Engineering and Technology
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About This Factfile Summary
This Factfile describes the principles behind
The Institution of Engineering and Technology acts as a
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providing independent, reliable and factual information
performance, systems and applications.
to the public and policy makers. This Factfile aims to
provide an accessible guide to current technologies and
scientific facts of interest to the public.
Contents
For more Factfiles on engineering and technology 3 Principles of Operation
topics please visit www.theiet.org/factfiles 3 Fuel Cell Types
6 Fuel Cell Performance
8 Fuel Cell Systems
The Institution of Engineering 9 Applications
and Technology 12 Endnotes
12 Further Information
The Institution of Engineering and Technology was 12 Appendix
formed on 31 March 2006 through the merger of
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Institution of Incorporated Engineers (IIE).

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First Edition 2001


Second Edition 2003
Third Edition 2006
© The Institution of Engineering and Technology 2006

Cover illustrations:
Top left: Hydrogen fuel cell powering chemical works
in Freeport, Texas by kind permission of The Dow
Chemical Company.
Top right: Portable fuel cell charger by kind permission
of Voller Energy Group PLC.
Bottom: Honda FCX concept vehicle by kind permission
of Honda UK.

FUEL CELLS
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Principles of Operation An alternative classification is based on fuels:

A fuel cell works much like a battery. In both batteries • R


 eformate/air fuel cells, in which the feedstock
and fuel cells two electrodes, an anode and a is hydrogen produced by the in-situ steam-reforming
cathode, are separated by an electrolyte. Whereas and/or partial oxidation of fuels such as methane,
a storage battery contains all the substances in the gasoline (C8H15.4 ) or diesel fuel (C14H22.5 ). The
electrochemical oxidation-reduction reactions involved carbon monoxide (CO) also produced is tolerated
and has, therefore, a limited capacity, a fuel cell is in some cell types but not in others, in which case it
supplied with its reactants externally and operates must be removed from the reformer output prior to
continuously as long as it is supplied with fuel. While being fed to the anode, e.g.
fuel cells have been used in niche applications for
many years, mainly as standby electrical power supply 2 CH3OH (methanol) + H2O (steam) + heat ¶ 5 H2 + CO + CO2
units, recent improvements in their cost and efficiency CH3(CH2) 6CH3 (gasoline) + 6O2 (air) ¶ 9H2 + 4 CO + 4 CO2 + heat
are leading to future uses in the much larger market of
‘zero emission’ vehicles (ZEVs).1 The new generation • H
 ydrogen/air fuel cells, which use stored or
of fuel cells will probably find other applications also chemically generated pure hydrogen as the anode
such as in small (3–10 kW) combined heat and power feedstock.
(CHP) units.
• D
 irect oxidation fuel cells, in which an organic
fuel is directly oxidised at the anode.
Fuel Cell Types
The five basic types of fuel cell2 are classified by the Hydrogen is a favoured anode feedstock because its
electrolyte that they employ. Low temperature types electrochemical oxidation is fast and clean; however it
include the alkaline fuel cell (AFC) and solid polymer is not a primary fuel. If it is not made by fuel reforming,
fuel cell (SPFC); the medium temperature type is the as described above, it must be produced by other
phosphoric acid fuel cell (PAFC) and the two high means, usually the electrolysis of water. This only
temperature types are the molten carbonate fuel cell makes sense in greenhouse gas abatement terms if the
(MCFC) and the solid oxide fuel cell (SOFC). Oxygen electricity comes from a non-fossil fuel source such as
from air is the oxidant (cathode fuel) in all these, but nuclear or a renewable energy source.
a number of fuels can be ‘burned’ at the anode. An
idealised schematic diagram illustrating the structure, Table 1 lists some fuel cells based on these types,
electron and ion flow for the various types of fuel cell is where the solid polymer design, SPFC, appears in the
shown in Figure 1. Proton Exchange Membrane Fuel Cell (PEMFC) and in
the Direct Methanol Fuel Cell (DMFC) with a summary
of fuel cell electrochemical reactions shown in Table 2.

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Figure 1. Principle of Fuel Cell Operation

Electrical Load

electrons e-

Positive ion flow

ANODE -ve H + (PEMFC) CATHODE +ve

H + (PAFC)

ELECTROLYTE

H2 O2
Negative ion flow
Fuel Air (or Oxidiser)

OH- (AFC)

CO32- (MCFC)

O2- (SOFC)
H 2O H 2O
Exhaust Exhaust

Electrolyte

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Table 1. Fuel Cell Types and Characteristics

Type AFC PEMFC DMFC PAFC MCFC SOFC


Electrolyte Aqueous Sulphonated Sulphonated Phosphoric Acid Molten Lithium / Yttria- stabilised
Potassium Organic Polymer Organic Polymer Sodium / Zirconia
Hydroxide (hydrated during (hydrated during Potassium
(30-40%) operation) operation) Carbonate
Operating 60-90 70-100 90 150-220 600-700 650-1000
Temp. oC
Charge Carrier OH– H+ H+ H+ CO3 = O=
Anode Nickel (Ni) Platinum Platinum- Platinum Nickel / Nickel / Yttria-
or precious (Pt) Ruthenium (Pt) Chromium stabilised
metal (Pt, Ru) Oxide Zirconia
Cathode Platinum (Pt) or Platinum Platinum- Platinum Nickel Oxide Strontium
lithiated NiO (Pt) Ruthenium (Pt) (NiO) (Sr) doped
(Pt, Ru) Lanthanum
Manganite
Co-generation None Low Quality None Acceptable High High
Heat for many
applications
Electrical 60 40 – 45 30 – 35 40 – 45 50 – 60 50 – 60
Efficiency %
Fuel Sources H2 Removal of H2 Reformate Water / H2 Reformate H2 , CO, H2 , CO,
CO2 from both with less than Methanol Natural gas Natural gas
gas streams 10ppm CO solution
necessary

Table 2. Summary of Fuel Cell Electrochemical Reactions

Type Fuel to Product of Ion in Product of Fuel to


Anode catalytic electrolyte catalytic Cathode
reaction reaction
AFC H+ O2
2H2 4OH –
$ 4OH –
$
$

4H2O +4e– +2H2O +4e–


PEMFC 4H+ O2
2H2
$ 4H+ $
$

2H2O
$

+4e– +4e–
DMFC CH3OH 6H + 3/2 O2
$ 6H + $
$

3H2O
$

+H2O CO2+ +6e– +6e–


PAFC H+ O2
2H2
$ 4H+ $
$

2H2O
$

+4e– +4e–
MCFC 2H2 $ 2CO3 =
O2
2H2O 2CO3 =
$

$
$

in hydro-carbon fuel +2CO2 +4e– +2 CO2 +4e–


SOFC 2H2 H+ O2
$ 2O = 2O =
$

$
$

in hydro-carbon fuel 2H2O +4e– +4e–

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Fuel Cell Performance Cell Voltage
Electrons generated at the site of oxidation (the anode)
Thermodynamic Efficiency ηth
of a cell are “pushed” towards the cathode by an
The amount of energy available for useful work, arising
electromotive force, or EMF. This force is due to the
from the energy changes of the electrochemical
difference in electric potential energy of an electron at
reaction occurring in a fuel cell under standard
the two electrodes. The quantity of electric work done
conditions of temperature and pressure, is governed by
is proportional to the number of electrons (the quantity
the Gibbs Free Energy equation:
of electric charge) moved and the magnitude of the
potential difference.
ΔG = ΔH - TΔS
Work = (charge) x (potential energy difference)
where ΔG is the Gibbs Free Energy or standard free
energy of formation available for work, ΔH is the
When the fuel cell reactants and products are present
standard enthalpy of formation, T is the absolute
as pure solids or in concentrations of 1.0mole, or as
temperature of 298.15K and ΔS is the entropy change
gases at 1.0bar, the measured cell potential (potential
for the reaction.
energy difference) in volts is the standard potential (E0)
- all values being given at 25oC (298K). The standard
For a hydrogen-oxygen reaction
potential E0 is a quantitative measure of the maximum
cell potential ie open-circuit voltage.
H2 (gas) + ½ O2 (gas) ¶ H2O
For the hydrogen-oxygen fuel cell involving the transfer
the thermodynamic values from tables are:
of two electrons per molecule of water formed:

ΔG = 237.13 kJ/mol and ΔH= 285.13 kJ/mol


2H + + O = ® H2O
for water as a liquid; and
for water as a liquid E0 = 1.23 volts
ΔG = 228.57 kJ/mol and ΔH= 241.82 kJ/mol
and for water as a gas E0 = 1.18 volts
for water as a gas.
This is the voltage for a single cell. Practical fuel cells
The maximum theoretical thermodynamic efficiency,
are built from an interconnected assembly of such
ηth, is the ratio of the Gibbs Free Energy to the
single cells into ‘stacks’ to provide the desired voltage
standard enthalpy of formation:
and power output.

ηth = ΔG x 100
ΔH

= 83.0% (liquid) to 94.5%(gas)

Electrical Efficiency, ηelec


The electrical efficiency (ηelec ) is defined as the ratio of
the maximum of the electrical work done (Welec.max ) on
an electrical load at a measured terminal voltage to the
standard enthalpy of formation.
W
ηelec = elec. max x 100
ΔH

This efficiency is the common measure of cell
efficiency. In practice because of internal resistance of
the cells it is considerably less than the thermodynamic
efficiency.

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Polarisation Figure 2. Fuel Cell Performance
When the cell is under load the efficiency and terminal
voltage decrease because of a number of factors, (a) Performance Curve
including polarisation effects and interconnection
losses between cells in the fuel cell stack. Polarisation 1.0
effects in a cell arise for a number of reasons.

• T he diffusion of ions through the electrolyte results

Voltage (V)
in the building up of concentration gradients thereby
decreasing the rate of transport. The relationship 0.5
between concentration over-voltages and electric
current is approximately linear up to a limiting value,
above which the over-voltages build up rapidly
(Mobility Inhibition/Concentration Polarisation).
• To achieve a self-sustaining reaction the hydrogen
and oxygen must attach to the surface of the cathode 0.0 0.5 1.0 1.5
and this process takes time and limits current flow. J ( A / cm2 )
• Ohmic resistance arising from the transport of
charged particles through the electrolyte.
(b) Power Density
Figure 2 illustrates the performance characteristics of
a Proton Exchange Membrane Fuel Cell. Figure 2(a)
shows the voltage as a function of current density. The 0.6
effects of polarisation can be seen in Figure 2(b) which
P ( W / cm2 )

shows the power density as a function of the current


density. The power losses due to polarisation cause the 0.4
curve to depart from and exist below the ideal power-
current straight line relationship. As the current density
increases from zero the activation power losses, initially 0.2
ohmic losses at the maximum power point, and finally
the mobility inhibition losses causing power shutdown,
determine the location of the curve. Finally, Figure 2(c)
shows efficiency as a function of power density. Note 0.0 0.5 1.0 1.5
that unlike internal combustion engines the efficiency J ( A / cm2 )
increases with decreasing load.

(c) Efficiency

0.6
Efficiency

0.4

0.2

0.0 0.2 0.4 0.6

P ( W / cm2 )

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Fuel Cell Systems Water Management
As an exhaust product water is seen as providing
Fuel Processing
a potentially important added benefit in fuel cell
In practice hydrogen always occurs in combination with
operation in future, given concerns about the adequate
other elements. It is necessary, therefore, to produce
local supplies of pure water for human consumption
it either by electrolysis in the case of water or by
and industrial purposes. In the alkaline fuel cells
separation in a reformer if a hydrocarbon fuel is used
used aboard the space shuttle for example, in seven
as a primary source. The largest quantity of hydrogen
days the fuel cells consume 680 kg of hydrogen and
is produced by the catalytic steam reformation of
produce 864 litres of drinking water. In MCFC and
hydrocarbons. This process uses methane, CH4, as
SOFC cells this water is produced in the form of high
the primary starting material. Methane reacts with
temperature steam, the water concentration needing to
steam at high temperature to give carbon monoxide
be controlled in these cells to avoid electrode carbon
and hydrogen:
deposition. Within SPFC cells water flow has to be
controlled to facilitate ion transportation, all of which
CH4 + H2O ¶ 3H2 + CO
illustrates that water management is an essential part
of the design of a fuel cell plant.
A fuel cell system which includes a fuel reformer can
utilise, in principle, the hydrogen from any hydrocarbon
Temperature Control
fuel from natural gas to methanol. The two primary
A preheating stage, particularly for high temperature
types of reformers being developed for transportation
fuel cells, may be required for start-up. Heat
are steam reformers and partial oxidation reformers.
exchangers are required to ensure the reactants enter
Steam reformers have higher efficiency but partial
the cells at appropriate temperatures for operation,
oxidation reformers are simpler.
again a particularly important requirement for high
temperature cells. The flow rate of the oxidant generally
A high temperature fuel cell can use the carbon
controls the stack temperature.
monoxide as a fuel, but for lower temperature cells
the carbon monoxide is unacceptable and must be
Power Conditioning
removed from the reformer gas stream. This can be
Fuel cell output is in the form of direct current (DC);
achieved by a further reaction with steam, known as
the voltage depending on the stack size. For most
the water-gas shift reaction, the process producing
purposes alternating currents (AC) at higher voltages
more hydrogen:
are required, therefore fuel cell output is transformed
from DC to AC by means of standard power electronics
CO + H2O ¶ H2 + CO2
in an inverter and thence to a higher voltage by means
of a transformer.
or removed by preferential oxidation reactors or by
separation membranes.
Figure 3 shows in schematic form these sub-systems in
a flow diagram of a solid oxide fuel cell-based combined
If the primary fuel contains sulphur a desulphurisation
heat and power scheme for an office building.
process must be included prior to the reformer.

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Figure 3. Flow Diagram of Solid Oxide Fuel Cell System in a Combined Heat and Power Scheme

Steam

Steam
Fuel Processing Steam /
Natural - desulphurisation Water
ANODE
Gas - reforming –
- shift reaction

Inverter

Air / –
CATHODE Air
Oxygen

Flue Gas

Electricity

Water

Applications Stationary Power Fuel Cells


Different fuel cell types have been identified for
Fuel cells find applications in transport, stationary
large-scale stationary power generation, viz. PAFC,
power generation, for supplying both electricity and
MCFC and SOFC and, more recently, PEMFC.
heat in buildings, in space for providing both electricity
and water, and in military areas for providing power
• P
 hosphoric Acid Fuel Cells (PAFC)
to sensors and other electronic equipment. With
PAFC’s have been developed to the first stages
the energy stored per kilogram of fuel cell weight
of commercialisation. Turnkey 200 kW plants
(including fuel) or per litre of volume of fuel being
are available and hundreds have been installed
potentially several orders greater than that stored in
in Europe, USA and Japan. With an operating
batteries, there is interest also in developing small fuel
temperature around 200oC there is potential for hot
cells for future consumer electronic purposes.
water supply as well as electricity depending on the
matching of the heat and electricity load profiles.
Major interests at present, however, focus on fuel
Electrical efficiencies can exceed 40%.
cells for stationary power generation and for
automotive purposes.

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• M
 olten Carbonate Fuel Cells (MCFC’s) is up to 60% and, again when used with combined
MCFC’S offer higher fuel-to-electricity conversion cycle plant, higher overall station efficiencies can be
efficiencies of up to 60%. At operating temperatures obtained. These cells may be able to reform
of around 650oC the waste heat produced can be hydrocarbon fuels internally with no pumps required
used in conventional combined cycle plant for the to circulate hot electrolyte and although still at a
generation of more electricity via steam turbines thus relative early stage of development they are regarded
raising the overall combined station efficiency. An as most promising for generating electricity from
important requirement of MCFC’s is that operation is hydrocarbon fuels.
not affected by carbon monoxide or carbon dioxide
in the fuel gas. At 650oC the carbonate salts of the Given the cost reductions in time associated with
electrolyte are in a liquid state allowing ion transport. maturing technologies allowing fuel cells to be
At the anode the carbonate ions react with the competitive with conventional generation plant, these
hydrogen fuel to produce electrons for the external stationary fuel cells fully developed and deployed
circuit, carbon dioxide and water; the cathode is within the electricity supply industry will have
supplied with oxygen and carbon dioxide and it is significant impacts and advantages compared with
important that the correct amount of carbon dioxide conventional generating plant, viz.
is supplied and re-circulated in order to replenish
the electrolyte. • Emission reduction (NOx, SOx, CO, hydrocarbons)
• Fossil fuel saving through higher efficiencies if
• S
 olid Oxide Fuel Cells (SOFC’s) used to replace older conventional fossil fuel plant
SOFC’s are solid state devices operating at - although modern 60% efficient Combined Cycle
temperatures up to 1000oC with a potentially wider Gas Turbine (CCGT) stations are more efficient than
choice of fuels without having to manage liquid either PEMFC or PAFC
electrolytes. Current is conducted by the passage of • Thermal recovery of high grade heat for CHP schemes
oxygen ions through a solid electrolyte. At the • Planning flexibility in plant size without loss
cathode oxygen is reduced to form oxygen ions; at of efficiency
the anode the transported oxygen ions react with the • High reliability
gaseous fuel to produce electrons for the external • Quietness of operation
circuit and water. Generally fuel flow is used to • Suitability for embedded generation in either high
regulate electrical output and air flow controls the demand or remote areas
temperature. SOFC’s must operate at high
temperatures to enable diffusion of oxygen ions MCFC and SOFC plants are expected to be
through the electrolyte made possible by reason of commercially available in the coming years, initially with
oxygen vacancies in the electrolyte crystalline 20 MW capacity and fuelled by natural gas.
structure. With conventional designs the anode is a
composite of nickel and yttria-stabilised zirconia Automotive Fuel Cells
(YSZ). This composite is an electron conductor (due Both alkaline and phosphoric acid fuel cells have been
to nickel) and also an ionic conductor (due to YSZ). used in demonstration vehicles, but alkaline cells
Nickel, however, catalyses the formation of graphite have an intolerance to carbon dioxide, the electrolytes
from hydrocarbons, thus carbon formation with reacting with the carbon dioxide, and the phosphoric
nickel based anodes is unavoidable for the wider acid cells are too bulky for mobile purposes. The major
range of hydrocarbon fuels available. Research technology for transportation purposes has emerged as
suggests that anodes made from a composite of the low temperature solid polymer fuel cell (SPFC) and,
copper and ceria, or samaria-doped ceria, may in particular, the proton exchange membrane fuel cell.
remove this barrier in the future. Electrical efficiency

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• P
 roton Exchange Membrane Fuel Cells (PEMFC) ruthenium alloy catalyst on the carbon electrodes.
PEMFC’s comprise a thin ion conducting membrane This technology is less advanced and the efficiency
between two platinum coated electrodes and afford and power are generally lower than those of the
a comparatively high power density. The fuel is PEMFC, but this is compensated for by the absence
hydrogen which is supplied to the anode where of a hydrogen tank or a fuel reformer. As with all
hydrogen ions and free electrons are generated. It is fuel cells deriving hydrogen from fossil fuel, the
necessary to control the management of the water in cell emits carbon dioxide, but compared with
the membrane which is essential for the hydrogen internal combustion engines, its higher efficiency,
ion transportation, the water tending to follow the particularly under part load, ensures less carbon
hydrogen ions to the cathode, also at the anode to dioxide being produced. In addition, again as with
ensure the correct hydrogen interaction with the all fuel cells, because there is no combustion there
platinum catalyst and to prevent dehydration. is an absence of NOx emissions. The hydrocarbon-
Platinum catalysts are tolerant to carbon dioxide but fuelled cell has considerable potential for the auto
not to carbon monoxide. Although progress is being industries. It avoids the high cost of hydrogen and
made in alleviating this problem, an approximate the low specific energy density of hydrogen when
guide is that quantities greater than 10 ppm for a compressed. Liquid fuels have not only a much
platinum catalyst or at most 100 ppm for a higher specific energy density, but also the benefits
platinum/ruthenium catalyst result in a degradation of an established distribution system supported by
of performance. This change in output is illustrated in the necessary forecourt engineering knowledge. The
Table 3. The output of a PEMFC can be altered range of hydrocarbon fuels which can be used as
quickly to match varying load demand, thus making it sources of hydrogen include not only methanol but
suitable for automotive purposes where quick start- also natural gas and gasoline. Solid polymer fuel cells
up is required. Stacks of cells are capable of using such fuel sources are currently being tested by
producing 1 kW/litre or 0.7 kW/kg, equivalent to a number of major automobile manufacturers in the
about 28 kW/cubic foot. development of proprietary ‘zero-emission’ engines.

• D
 irect Methanol Fuel Cell (DMFC) • I ntermediate Temperature Solid Oxide Fuel
In order to avoid the necessity of either storing the Cell (ITSOFC)
hydrogen on board a vehicle or reforming it from More recently solid oxide fuel cells operating at 500
another fuel, a solid polymer fuel cell working - 700oC have been suggested with possible use in
directly from methanol has been developed. An transport applications. Such cells using methanol fuel
aqueous, low concentration 3% methanol solution have been demonstrated. Advantages include the
is used with the methanol and water reacting at absence of high temperature fuel reforming and also
the anode to produce carbon dioxide as well as of catalyst poisoning by carbon monoxide, which is
hydrogen ions and free electrons as before. The used here as a fuel.
key to this process is the use of a 50:50 platinum-

Table 3. PEMFC Output with Carbon Dioxide/Monoxide present in the Hydrogen Fuel Gas

Fuel Gas Voltage V Current Density mA/cm2 Power W


H2 0.17 430 100
H2, 25% CO2 0.68 430 96
H2, 25% CO2, 0.3% CO 0.71 215 50

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Endnotes Appendix 1
1
California’s Air board requires ZEVs to form a small An Autumn 2005 DTI call for proposals under the
percentage of the cars brought to market from 2003. Low Carbon Energy Technologies Programme listed the
2
The US industry consortium Fuel Cells 2000 website following priorities for fuel cell research:
(www.fuelcells.org) provides a useful guide to fuel
cell technology. • T o construct and evaluate a novel SPFC stack
>50kWe, power density >1kW/l, pressure <2bar,
CO tolerant to at least 100ppm, and performance
Further Information degradation < 1% over 1000h.
• To construct and evaluate a novel SPFC stack of
• A llison Gas Turbine (1996) Research and ~1kWe, power density ~500W/l and operating at
Development of Proton Exchange Membrane ambient pressure.
(PEM) Fuel Cell System for Transportation • To construct and evaluate a ~20kW SOFC system
Application: Fuel Cell Infrastructure and operating on natural gas.
Commercialisation. • To design, construct and evaluate a compact
• Blomen, L.J.M.J. and M.N. Mugerwa (Eds.) (1993) integrated auxiliary power unit (APU) of ~5kW,
Fuel Cell Systems. New York: Plenum. together with fuel reforming.
• Kendall, K. (2000) “Hopes for a flame free future”, • To construct and evaluate a novel, planar SOFC
Nature, 404: 233-5. stack of ~20kWe, internally reforming natural gas,
• Kendall, K., T.Alston, M.Palin, P.Windibank and M.Price delivering an efficiency >50% (LHV). The stack
(1998) “A 1000 cell SOFC reactor for domestic should be capable of manufacture by a viable (if
cogeneration”, J.Power Sources, 71: 271-4. not yet proven) process, and with materials costs
• Kirk, R.E. and D.F. Othmer (1994) Encyclopedia of <US$300/kW.
Chemical Technology. New York: Wiley. • To design, construct and evaluate a compact,
• Kordesch, K. and G. Simander (1996) Fuel Cells responsive, natural gas fuel processor, scaleable
and Their Applications. Cambridge: Wiley. between ~1kW and ~50kW, and hence suitable for
• Maguire, J. and P.K. Michael (Eds.) (1994) residential through small commercial CHP systems.
European Fuel Cells R and D Review The system should achieve a power density >1kW/l,
(Fuel Cell Information Series). performance degradation <0.5% in 1000h, <10ppm
• Minh, N.Q. and Takahashi, T. (1995) Science and CO output, and a 10,000h operating life.
Technology of Ceramic Fuel Cells. Amsterdam: • To design, construct and evaluate a compact,
Elsevier Science. responsive, liquid fuelled fuel processor, suitable
• Seungdoo Park, J.M.Vohs and R.J.Gorte (2000) for passenger cars, that achieves a power density
“Direct Oxidation of Hydrocarbons in a Solid-oxide >1kW/l, performance degradation <0.5% in 1000h,
Fuel Cell”, Nature, 404: 265-6. <10ppm CO output, and an operating life of
• Stimming, U. (Ed.) (1997) Solid Oxide Fuel Cells. 10,000h.
• Swan, D. and M. Miller (1996) California’s • Initial (exploratory) projects, to develop and evaluate
Statewide Fuel Cell Research, Design and novel hydrogen storage systems that may be suitable
Development Collaboration Plan (Fuel Cell for passenger cars.
Information Series).

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