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Phil. Trans. R. Soc. A (2006) 364, 147–159

doi:10.1098/rsta.2005.1684
Published online 30 November 2005

Engineering porous materials for fuel cell

applications
B Y N. P. B RANDON * AND D. J. B RETT
Faculty of Engineering, Imperial College London, South Kensington campus,
London SW7 2AZ, UK

Porous materials play an important role in fuel cell engineering. For example, they are
used to support delicate electrolyte membranes, where mechanical integrity and effective
diffusivity to fuel gases is critical; they are used as gas diffusion layers, where electronic
conductivity and permeability to both gas and water is critical; and they are used to
construct fuel cell electrodes, where an optimum combination of ionic conductivity,
electronic conductivity, porosity and catalyst distribution is critical. The paper will
discuss these characteristics, and introduce the materials and processing methods used to
engineer porous materials within two of the leading fuel cell variants, the solid oxide fuel
cell and the polymer electrolyte membrane fuel cell.
Keywords: fuel cells; triple phase boundary; porous solids

1. Introduction to fuel cell technology

A fuel cell is a device for directly converting the chemical energy of a fuel into
electrical energy in a constant temperature process. Fuel cells operate on a wide
range of fuels, including hydrogen, and are seen as a clean, high efficiency power
source, and an enabling technology for the hydrogen economy. Potential
applications for fuel cells range from battery replacement in consumer goods
and portable computers, through residential scale combined heat and power
(CHP), to distributed energy generation.
Information on fuel cell types and technology is provided by a variety of books
(e.g. Appleby & Foulkes 1989; Blomen & Mugerwa 1993; Kordesch & Simader
1996; Larminie & Dicks 2000). Useful historical surveys have been provided by
Kordesch (1978) and Appleby (1990). Summaries of the current technological
and commercial status of fuel cells are provided in the Fuel Cell Handbook issued
by the US Department of Energy (US DOE 2002), Proceedings of the Grove Fuel
Cell meetings (Proceedings of the grove fuel cell symposium) and Fuel Cells
Bulletin.
Discussions about the commercialization of fuel cell technology usually
incorporate the five fuel cell types summarized in figure 1 on the basis of the
incorporated electrolyte. Figure 1 reveals that the lower temperature systems,
alkaline fuel cell (AFC), polymer electrolyte membrane fuel cell (PEMFC) and
* Author for correspondence (n.brandon@imperial.ac.uk).
One contribution of 18 to a Discussion Meeting Issue ‘Engineered foams and porous materials’.

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148 N. P. Brandon and D. J. Brett

anode cathode
– +
electrolyte

SOFC (500 –1000°C)

H2O O2 (air)
internal CO2 O2–
reforming
H2, CO MCFC (650°C)
H2O O2 (air)
CO32–
CO2 CO2

external
reforming PAFC (200°C)
H2, CO2 H2O O2 (air)
H+
external
reforming PEMFC (80°C)
O2 (air)
H2, CO2 H2O
H+
(CO removal)

H2 AFC (70°C)
H2O O2 (air)
OH– (CO2 removal)

Figure 1. Summary of leading fuel cell types with typical reactant gases.

phosphoric acid fuel cell (PAFC), essentially operate on H2 fuel, whereas the
higher temperature systems, molten carbonate fuel cell (MCFC) and solid oxide
fuel cell (SOFC), can also electrochemically oxidize CO, which is advantageous
when a hydrocarbon fuel is supplied to the fuel cell. In this paper, we will focus
on the two leading fuel cell technologies under development today, namely
PEMFCs, the leading fuel cell technology for fuel cell engines in transport
applications (operating on pure hydrogen) or battery replacement (operating on
hydrogen or methanol), and SOFCs, the leading fuel cell technology for
stationary power, or CHP applications (operating on natural gas, biofuels or
LPG). Figure 2 provides a schematic illustration of these two fuel cell types,
which are discussed further in the following.

(a ) Polymer electrolyte membrane fuel cells

PEMFCs have high power density, rapid start-up and low temperature
operation (around 80–120 8C), and so are ideal for use in applications such as
transport and battery replacement. The electrolyte used is a proton conducting
polymer, meaning that the reaction product, water, is formed on the cathode side
of the fuel cell. The electrolyte is typically a perfluorinated polymer, though
other hydrocarbon based membranes are under development in an attempt to
reduce cost, and/or to enable operation at temperatures approaching 200 8C. The
catalytically active layer sits adjacent to the membrane, supported on a porous
PTFE treated carbon paper, which acts as current collector and gas diffusion
layer (GDL). For operation on pure hydrogen, platinum is the most active
catalyst, but alloys of platinum and ruthenium are used when higher levels of

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Engineering porous materials 149

LOAD
membrane electrode assembly (MEA) fluid-flow plate (FFP)
positive - electrolyte - negative (PEN) flow channel

cathode
SOFC anode PEMFC

H2

cathodene
O2

anode
me
ele

ca
an

mb
H2 O2
tho
ctr
od

ra
oly
e

de H2 O2 O2
te

2H2 H2 O2 2H2 +-
4e–
– O2 H2 O2
2O2 + - 4H+
2H2O 4e –
+ 4e– 2H2O
4e– 50µm GD
GDL
catalyst 200µm
ca. 1000µm 50µm
10µm
15µm

anode: 2H2 + 2O2– 2H2O + 4e– anode: 2H2 4H+ + 4e–

cathode: O2 + 4e– 2O2– cathode: 4H + O2 + 4e–
+ 2H2O

Figure 2. Fuel cell architecture (single cell) with the SOFC and PEMFC regions and reactions
highlighted.

carbon monoxide are present (CO is a poison in all low temperature fuel cells).
Water management in the membrane and electrodes is critical for efficient
performance, because the membrane must be hydrated, while avoiding flooding
of the electrode pores with water.

(b ) Solid oxide fuel cells

SOFCs operate at elevated temperatures, generally above 800 8C for the all
ceramic high temperature variant, and in the range 500–800 8C for metal-ceramic
intermediate temperature solid oxide fuel cells (IT-SOFCs). The electrolyte is a
dense ceramic, usually yttria stabilized zirconia (YSZ), which is an oxide ion
conductor at elevated temperatures. This means that in an SOFC the reaction
product, steam (and also carbon dioxide if the fuel cell is fed directly on
hydrocarbon fuels), is formed on the anode side of the fuel cell. The cathode is
typically a perovskite material such as strontium doped lanthanum manganite,
often mixed with YSZ in the form of a composite. The anode is a cermet of nickel
and YSZ. The main difference between the high temperature SOFC and the IT-
SOFC lies in: (i) the thickness of the electrolyte, which tends towards 20 mm
thick films for IT-SOFCs, to reduce ionic resistance, and (ii) the interconnect
material, with stainless steel being used at the lower temperatures of the IT-
SOFC, whereas more expensive high chrome alloys, or oxides such as lanthanum
chromite, are needed at higher temperatures. Figure 2 in fact illustrates an anode
supported IT-SOFC geometry, characterized by a relatively thick porous anode
support, but other support materials are used, discussed further in §4. Figure 3
shows an actual microstructure from an anode supported IT-SOFC, showing a

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150 N. P. Brandon and D. J. Brett

20 µm

anode electrolyte

support

active cathode

Figure 3. Example of the microstructure of an anode supported SOFC showing the cathode,
electrolyte and an anode composed of an active catalyst region and anode support region (more
open porosity).

region of the porous anode support, along with the less porous active region
where the electrochemical reactions occur, the dense electrolyte thick film, and
the porous cathode.
SOFCs lend themselves to applications in which their high-temperature heat
can be used. This heat can be used in two basic ways—for heating processes such
as those in industry or in homes, or for integration with turbines in hybrid cycles
for very high efficiency electricity production. Examples in which SOFCs may be
used include decentralized electricity generation of 250 kWe–30 MWe; off-grid
applications of 1–25 kWe, and domestic CHP applications of 1–5 kWe.
Intermediate Temperature SOFCs are also of interest for vehicle auxiliary
power unit (APU) applications, operating on diesel or gasoline. Carbon
monoxide is not a poison for SOFCs, meaning that a wide range of fuels can
be used, together with a simpler, and therefore, cheaper, fuel processor. It is also
possible to recuperate heat from the fuel cell within the fuel reformer, improving
system efficiency when compared to low temperature fuel cells when operating on
hydrocarbon fuels.

2. The role of porous materials in fuel cell technology

Porous materials play two key roles in fuel cell technology. The first is that of
transporting gases to/from the fuel cell electrodes. In PEMFCs porous GDLs
play an important role in forming current collectors, which not only
collect/inject current, but which also enable the transport of gaseous fuels to
the fuel cell electrodes, while rejecting water, the reaction product. In SOFCs,
porous ceramics are commonly used to provide the mechanical support for thin

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Engineering porous materials 151

and delicate ceramic oxide electrolytes, in many cases these porous materials also
play an important role in current collection on the anode or cathode side.
The second vital role of porous materials is within the fuel cell electrodes, be
they anode or cathode. In both PEMFCs and SOFCs, the electrodes play a vital
role in minimizing losses attributable to electrode kinetics, and in some cases
mass transport. This is achieved by maximizing the length of the so-called triple
phase or three-phase boundary (TPB), a term describing the conjunction of a
pore space, an ionically conducting phase, and an electronically conducting
phase, and is a concept introduced further in §5a. In practice this is achieved by
the use of porous composite electrode structures containing both ionically and
electronically conducting materials.

3. Gas diffusion layers for PEMFCs

The GDL, sometimes referred to as the backing layer or diffusion electrode, is a

layer of porous, electronically conducting material that is situated between the
electrocatalyst and flow-field (interconnect) plate (FFP) of both the anode and
cathode in a PEMFC. The GDL has several functions; it facilitates reactant
delivery to the active catalyst area situated under the FFP land area; it conducts
electronic current between the FFP and the electrocatalyst; aids water
management; mechanically supports the membrane electrode assembly (MEA);
serves as an effective thermal conductor, removing heat from the MEA to the
FFP and it buffers the interface between the FFP and the electrocatalyst,
ensuring good electrical and physical contact between the GDL/electrocatalyst
and GDL/FFP, so minimizing the electronic contact resistance. In addition,
some MEA preparations use the GDL as the substrate onto which the catalyst is
deposited before bonding to the membrane electrolyte.
To accommodate these requirements the GDL must have the following
combination of properties. The porosity should be sufficient to ensure effective
reactant delivery but not so much as to compromise the through-plane electronic
conductivity or mechanical properties; porosity values of 75% or higher are
typical. The GDL should suffer minimal electrochemical corrosion and be
compatible with the humid, warm, reducing and oxidizing environment found
within a PEMFC, which is why carbon/graphite is a commonly used material.
The GDL should undergo compression while maintaining mechanical integrity
and not losing porosity.
GDLs are typically in the thickness range of 100–400 mm, the optimal
thickness being a compromise between resilience to pore crushing under
compression (which increases with thickness) and reactant transport to the
electrocatalyst (which decreases with thickness). GDLs come in a variety of
materials including carbon-fibre paper, carbon cloth/felt, carbon filled non-
woven webs or metallic webs. Mathias et al. (2003) have reviewed the materials,
methods of production and characterization techniques of GDLs. The most
commonly employed GDL is carbon-fibre paper. The manufacture of this type of
GDL starts with a polymer (typically polyacrylonitrile (PAN)) that is spun into
fibres that are stabilized in air to form a thermoset. From this point the material
can be processed in a number of ways depending on the desired final product. To
make a carbon-fibre paper, carbonization is first performed at greater than

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152 N. P. Brandon and D. J. Brett

Table 1. Properties of selected carbon-fibre paper type gas diffusion layers.

SIGRACET Toray Spectracorp LyFlex(C332) Ballard

material (GDL-20BA) (TGP-H-060) (2050-A) non-pyrolized (AvCarb P50)

thickness (mm) 220 190 260 333 172

(at 0.7 N cm2)
porosity (%) 83 78 porosity not 79.5, mean not known
known, pore dia.
mean 11.1 mm
pore dia.
28 mm
electrical 10 a 80† a 5.8† b 70 a 251† a 24.1† b 9.7
resistivity† or
resistance
(mU cm)† or
(mU cm2)
bulk density 0.29 0.44 0.48 0.37 0.28
(g cmK3)
tensile strength — 500 — 5.94 1000
(N mK1)
thermal — 1.7a (at 25 8C) — — 1.3a (at 100 8C)
conductivity 21b (at 25 8C)
(W mK1 KK1)
Gas permeability 50 — 45 — —
(cm3 cmK2 sK1)
a
Through-plane.
b
In-plane.

1200 8C in an inert atmosphere; this is followed by papermaking in which the

material is chopped, a binder added and the resultant rolled into a ‘paper’ form;
a resin impregnation allows the material to be moulded to the correct thickness;
the material is finally graphitized at greater than 2000 8C in an inert atmosphere
to convert amorphous carbon into graphite so improving the conductivity of the
material. The resulting carbon–carbon composite is ca 99% converted from
starting polymer and resin binder to carbon. The average pore size of carbon
paper GDLs is typically in the range 10–30 mm. Further processing typically
takes place with impregnation of additives to increase the hydrophobicity of the
layer. This has the effect of expelling product water from the GDL more
efficiently, so avoiding ‘flooding’ of the GDL, which results in severe mass
transport limitation (Ihonen et al. 2004). However, addition of PTFE increases
the contact resistance with the FFP and lowers the porosity of the layer; an
optimal PTFE content of ca 15 wt% as been reported by Paganin et al. (1996)
and 10 wt% of fluorinated ethylene propylene by Lim & Wang (2004). Carbon-
fibre papers produced by similar routes are supplied in various forms by SGL
Carbon Group (SIGRACET, Germany); Toray Industries (Japan); Spectracorp
Materials (USA); Lydall (USA) and Ballard Materials Products (Canada).
Table 1 provides a summary of selected of properties from this class of GDL.
Production of an effective GDL is largely a matter of controlling the structure
and porosity of the material. The vital role of GDL porosity in determining fuel

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Engineering porous materials 153

cell performance has been studied by Chu et al. (2003). They found that it is
important to consider the GDL as having a non-uniformly dispersed porosity,
owing to the spatially varying water content within the structure. As a
consequence, graded porosity of the GDL both in the thickness and laterally
across the layer is expected to improve performance by assisting water removal
and access of gas when reactant becomes depleted in the flow channel. Increased
porosity was found to have little benefit when operating at low current densities
but has a considerable effect when operating at high load.

4. Porous support materials for SOFCs

Depending upon the fuel cell design, porous support materials for SOFCs can be
fabricated either from the anode material, i.e. a cermet of nickel and YSZ such as
that used by Versa Power Systems, Canada, the cathode material, generally
strontium doped lanthanum manganite as used by Siemens Westinghouse, or an
inert ceramic as used by Rolls Royce Fuel Cell Systems. These materials are all
characterized by a relatively coarse microstructure (particle size generally in the
range of 1–20 mm) with porosity in the range of 30–40%. A key characteristic of
all the support materials is that they provide the mechanical support for the
delicate fuel cell electrolyte, meaning that the mechanical properties of the
support are important. The fabrication of mechanically robust support materials,
resistant to thermal and/or oxidation–reduction cycles, and which can withstand
compression loading, or which can be sealed using glass ceramics to metallic
interconnects and/or housings, remains one of the challenges facing many SOFC
developers, and it is this that has in part driven recent interest in metal
supported SOFC concepts (Brandon et al. 2004). All the ceramic-based porous
support materials are fabricated by either tape casting or calendaring in the case
of planar geometries, or by extrusion in the case of tubular or box-section
geometries. Metal supported designs rely on either sintered metal supports
(Matus et al. 2004), woven metal supports (Schiller et al. 2000), or laser drilled
foils (Brandon et al. 2004). Support thickness ranges from 0.2 to 1.5 mm,
depending upon the design and the developer, with metal supports tending to be
thinner than those based on ceramic materials.

5. Fuel cell electrodes

(a ) The triple phase boundary

Much work has been devoted in recent years to developing the concept of the
triple phase boundary (TPB) as a means of understanding the complex interplay
between particle size, pore size distribution and ionic/electronic conductivity, in
fuel cell electrodes. The total length of the TPB within a material is important as
it is only at this region, where the electronically conducting phase, ionically
conducting phase and contiguous pore space combine, that charge transfer
reactions can proceed. This is illustrated schematically for the cathode of a
PEMFC and the anode cermet of a SOFC in figure 4, in which it can be seen that
the following processes are involved:

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154 N. P. Brandon and D. J. Brett

= carbon support = electrolyte (e.g. YSZ, CGO)

(a) = Pt catalyst particle (b) = metal (e.g. Ni) (c) H2(pore)
O2 O2 H2O(pore) 1 H
H 2e–
2H2O H2O 2
4
TPB 4
4H+ O2- 2e– 3 metal
4e–
2
electrolyte
O2–

1 H2 adsorption and dissociation

electrolyte cathode catalyst GDL electrolyte anode cermet 2 H(ads) surface migration and O2– bulk migration to TPB
3 Reaction at TPB
4H + O2 + 4e– 2H2O O2– + H2 H2O + 2e–
4 2e– migration through metal
and H2O diffusion through pore

Figure 4. Schematic view of reaction pathway at: (a) PEMFC cathode; (b) SOFC anode cermet and
(c) close-up of anode cermet TPB.

(i) Transport of electrons to/from the current collector to/from the reaction
site through an electronically conducting phase,
(ii) donation/acceptance of these electrons to/from a species adsorbed on the
electrode surface from the gas phase (in some cases such as PEMFCs this
process is catalysed by high surface area catalysts dispersed within the
porous structure), to form an ionic species, and
(iii) transport of ions to the electrolyte through an ionically conducting phase.

It is therefore clear that it is our ability to both understand and control the
complex interactions between microstructural parameters, electrical properties
and electrocatalytic activity that determines our ability to engineer optimum
porous electrode structures.

(b ) PEMFC electrodes
The low temperature operation of the PEMFC generally limits the type of
catalyst that can be used to highly active precious metals in order to achieve
adequate electrode kinetics. Pt is generally accepted to be the best
electrocatalyst for both anodic and cathodic reactions. However, when operating
on hydrogen with CO contaminants or direct methanol fuel, binary Pt/Ru
anodes are preferred owing to their superior CO tolerance (Ralph & Hogarth
2002); moreover, Pt alloys have been shown to exhibit marginal performance
improvements for the oxygen reduction reaction (Ralph & Hogarth 2002). Design
of effective electrocatalysts is largely a question of maximizing the extent of the
TPB and facilitating reactant ingress to the TPB and product water egress. This
is primarily controlled by the catalyst’s microstructure (porosity), dispersion and
support; although less well understood factors such as electronic effects, particle
size effects and crystal morphology are also important. In the case of the
PEMFC, water management must be considered and, as for the GDL,
hydrophobic additives are commonly introduced to aid water removal. In
addition, factors that define good durability include resistance to particle
agglomeration, tolerance to poisons and contaminants, mechanical and chemical
stability.

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Engineering porous materials 155

The introduction of graphitic carbon supports (carbon blacks) to catalysts for

PEMFCs has led to a major improvement in performance and durability and has
allowed Pt loadings to be significantly reduced (0.2–0.5 mg Pt cmK2). By
depositing Pt particles onto larger carbon particles (typically Pt particles 2–5 nm
and carbon support ca 50–500 nm) the platinum becomes more highly disperse,
less prone to agglomeration and the conductivity of the catalyst layer is
enhanced; the carbon also forms a porous structure (typically 40–60% porosity)
that is conducive to reactant transport into the catalyst layer. Carbon supports
are available from Cabot Corporation (Black Pearls, Vulcan XC72R), Akzo
Nobel (Ketjen Black), Erachem (Ensaco 350) and Denka, among others, and
range in surface area from ca 50–1500 m2 gK1 with Pt loadings typically in the
range 10–50 wt% Pt. Other types of catalyst supports reviewed by Lister &
McLean (2004) include metal catalyst blacks, binary carbon catalyst supports,
conducting polymer supports, carbon ‘nanohorn’ supports and nanostructured
crystalline whiskers (Debe 2003). The effect of the nature of carbon supports and
catalyst loading on PEMFC performance has been reviewed by Tada (2003).
A growing variety of electrocatalyst preparation routes exist. A comprehensive
survey of catalyst layer and MEA fabrication is available from Lister & McLean
(2004), who describe thin film, colloidal, vacuum deposition, electrodeposition
and impregnation techniques; however, much of the detail of catalyst preparation
is proprietary to the manufactures. There are two general methods in which
MEAs are formed, one involves immobilization of the catalyst/support onto one
side of each of the GDLs, which are then pressed to the membrane, this is the so
called catalyst coated substrate method; the other has the catalyst/support
bonded to each side of the membrane, with subsequent pressing of the GDL to
the membrane/catalyst layer (catalyst coated membrane). The range of
proprietary methods generally dictate how the catalyst becomes immobilized
on the GDL or membrane and how various additives are introduced, such as
Nafion and pore formers.
In order to bind the carbon supported catalyst particles and develop the TPB
throughout the structure, the catalyst layer is either impregnated with PTFE
which is brushed with Nafion or more commonly (and effectively) impregnated
with a thin layer of Nafion alone (Lundblad 2004). The latter method is more
hydrophilic and, therefore, more prone to flooding but utilizes more of the
available catalyst due to more effective formation of the TPB. The optimum
amount of Nafion added has been measured to be ca 33 wt% of the catalyst
(Paganin et al. 1996). This amount provides the greatest ionic contact with the
catalyst particles, while minimizing the barrier to electronic conduction and the
blocking of pores.

(c ) SOFC electrodes
A useful analytical simulation of porous composite SOFC electrodes, which
takes into account electronic and ionic transport, mass transport within pores
and electrochemical reactions, has been reported by Costamagna et al. (1998).
The model incorporates a surface area parameter derived from the properties of
binary powder mixtures, and effective conductivities derived from the
characteristics of pure materials modified by percolation theory. The work
showed that the volumetric composition of the electrode, coupled with the

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156 N. P. Brandon and D. J. Brett

Table 2. Summary of anodes prepared to study the effect of particle size on anode conductivity at
room temperature. (All samples contain 60 wt% NiO/40 wt% CGO (Baron 2004).)

conductivity at 258 C
sample NiO d50 (mm) CGO d50 (mm) NiO d50/CGO d50 (S cmK1)

1 15 0.29 51.7 0
2 18 0.29 62.1 0
3 18 0.40 45.0 0
4 18 0.60 30.0 0
5 0.7 0.58 1.2 5660
6 0.7 0.58 1.2 1320
7 1.64 1.00 1.6 3570
8 0.7 1.00 0.7 370
9 3.14 2.00 1.6 1680

particle size, would be expected to strongly influence the electrode resistance,

with the resistance reaching a minimum near the percolation limit of the
electronic conducting phase. This supports experimental evidence where, e.g.
optimum electrode performance has been reported around the percolation
threshold of the electronically conducting phase in Ni-YSZ anodes (Kawada et al.
1990a,b).
This is supported by experimental work such as that by Baron (2004), who has
shown that particle size as well as volume fraction plays a key role in determining
electrode performance. In this work, a range of slurries were prepared by
dispersing NiO and 10 mol% gadolinia doped cerium oxide (CGO) powders of
differing particle size (defined in terms of the d50 value, i.e. the size below which
lies 50% of the total volume of all the particles) in ethanol, together with a PVB
binder, PEG 400 plasticiser and Solsperse 24 000 dispersant. These slurries were
then coated onto CGO electrolytes by doctor blading, dried, and then sintered in
air at 1300 8C. The samples were then reduced in 10% H2/N2 for 0.5 h at 700 8C
and cooled down in the reducing atmosphere. This simulates the operating
environment of the anode material, under which the NiO is reduced to metallic
nickel, introducing further porosity. Electrical conductivity was then measured
at room temperature using a four-point technique.
Table 2 summarizes the result obtained, and it can be seen that when the
particle size of the NiO was large compared to the CGO, an essentially insulating
composite structure was obtained (samples 1–4). Under these conditions the
CGO particles are believed to coat the surface of the electronically conducting Ni
particles, preventing the formation of a percolated electronic pathway. However,
when the particle size is brought closer together, then conductivity can be
measured, with the optimum formulation being that of sample 5. All electrodes
had porosity in the range of 30–40%, with sample 5 having a porosity of 40%, and
a mean pore size of 0.5 mm.
SOFC cathodes are also porous composite structures, in this case a composite
of an electrically conducting oxide and the oxide ion conducting electrolyte.
Frequently the particle size used to fabricate SOFC cathodes is less than that
used to fabricate SOFC anodes (of order 0.2–2 mm) together with a lower sinter
temperature. It has been shown that, for composite SOFC cathodes, optimum

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Engineering porous materials 157

performance occurs around the percolation threshold of the ionically conducting

phase, e.g. in the case of strontium cobalt doped lanthanum ferrite-gadolinia
doped ceria (LSCF-CGO) cathodes (Dusastre & Kilner, 1999). This study used
effective medium percolation theory, modified to account for electrode porosity,
to show that the optimum electrode composition was porosity dependent,
varying from a CGO content around 50 vol% for an electrode of 30% porosity, to
36 vol% for an electrode of 50% porosity.
More recent analysis by Williford & Singh (2004), building on the approach of
Deng et al. (1994, 1995), used computational analysis to study a two layer mixed
ionic–electronically conducting cathode. The authors concluded that a cathode
thickness around 25 mm represented an optimum balance between electro-
catalytic activity and mass transport limitations, though simulations also showed
that in many cases all the electrochemical reactions were confined to a region
within 5 mm of the electrolyte interface. The authors recommend a bi-layer
cathode structure, comprising a 5 mm thick active region adjacent to the
electrolyte comprising 0.25 mm diameter particles, with porosity 45%, pore
diameter 1 mm, surface to volume ratio 1.22!106 cmK1, tortuosity to gas flow
2.22 and solid tortuosity 1.67, coupled with a 25 mm thick outer current
collection layer, with similar characteristics other than the surface to volume
ratio was decreased to 5!104 cmK1 and the solid tortuosity increased to 1.83,
though this recommendation was accompanied by the comment that the analysis
would benefit from a more explicit treatment of material property spatial
variation.
As previously highlighted, as well as influencing electrode activity and
conductivity, the electrode structure also plays an important role in determining
the mass transport characteristics within the electrode. While the relatively low
levels of oxygen depletion on the cathode side of the fuel cell mean that mass
transport limitations in the cathode are generally not an issue, this is frequently
not the case for the anode side of the fuel cell, where fuel depletion through the
fuel cell stack means that mass transfer limitations are likely to be more
prevalent. Baron et al. (2004), for example, have shown that the anode
microstructure can play a significant role in mass transfer unless adequate
attention is paid to optimizing porosity. In this study, losses attributed to mass
transfer within the electrode increased in line with decreasing diffusion
coefficients of the fuel gas, meaning that losses for fuels rich in carbon monoxide
were four times those of hydrogen rich fuels through the same anode
microstructure (being the same ratio as that of the diffusion coefficients of
hydrogen and carbon monoxide).
While the above discussion suggests some design rules for engineering SOFC
electrodes in terms of porosity and particle size, another key aspect relates to the
processing of such materials. For cost reasons, fabrication technologies are
largely restricted to wet ceramic processing routes such as screen printing, slurry
spraying or tape casting, coupled with high temperature sintering to achieve a
robust adherent electrode. The temperature of sintering depends upon the
material choice, but typically varies from around 1300–1400 8C for anode
sintering, down to 1000–1200 8C for cathode sintering. These processes are
frequently used to produce a bi-layer structure comprising a fine grained active
composite region some 10–20 mm thick, with a larger grained more porous
current collecting region. Particle size is generally of the order of 0.2–5 mm, with

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158 N. P. Brandon and D. J. Brett

a typical porosity in the range 30–45%. Several authors have also reported the
fabrication of functionally graded cathodes, in which composition and/or pore
structure is varied throughout the cathode. These structures have been produced
by a variety of techniques including using screen printing (Hart et al. 2001),
slurry spraying/coating (Hart et al. 2002; Holtappels & Bagger 2002; Xia et al.
2002) and combustion chemical vapour deposition (Liu et al. 2004).
However, it remains challenging to cost-effectively produce the optimum
electrode microstructures predicted by modelling work, and to retain these
structures during prolonged operation over many thousands of hours.
Furthermore, there remain uncertainties in a number of the parameters required
by these models, in particular electrode kinetic parameters, and quantified
descriptions of electrode pore structure. Certainly, there remain opportunities to
both better understand and predict the behaviour of solid oxide fuel cell
electrodes, as well as opportunities to better control the deposition parameters to
meet these design criteria.

6. Conclusions

Porous materials play a key role in the development of fuel cell technology. The
function of these materials includes the transport of gases to and from the active
sites, the mechanical support of the fuel cell structure, and the support of highly
electrochemically active electrodes. While understanding of the key parameters
influencing the performance of these materials in an operating fuel cell is
increasing, our ability to engineer reliable, low cost, durable porous materials,
which can withstand a wide range of operating and fault conditions remains a
challenge facing the fuel cell community, and is an area where there remains
significant opportunities for collaboration between engineers, chemists and
materials scientists.

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