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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:
FUEL CELLS
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Figure 1. Principle of Fuel Cell Operation
Electrical Load
electrons e-
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
FUEL CELLS
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Table 1. Fuel Cell Types and Characteristics
2H2O
$
+4e– +4e–
DMFC CH3OH 6H + 3/2 O2
$ 6H + $
$
3H2O
$
2H2O
$
+4e– +4e–
MCFC 2H2 $ 2CO3 =
O2
2H2O 2CO3 =
$
$
$
$
$
FUEL CELLS
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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:
ηth = ΔG x 100
ΔH
FUEL CELLS
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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.
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 )
(c) Efficiency
0.6
Efficiency
0.4
0.2
P ( W / cm2 )
FUEL CELLS
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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.
FUEL CELLS
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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
FUEL CELLS
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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
FUEL CELLS
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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 CELLS
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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).
FUEL CELLS
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12