Applications of Nanomaterials in Fuel Cells: June 2014

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Applications of Nanomaterials in Fuel Cells
Chapter · June 2014

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7 Applications of
Nanomaterials in
Fuel Cells
Shangfeng Du and Bruno G. Pollet
CONTENTS
7.1 Introduction to Fuel Cells.............................................................................. 113
7.2 Benefits of Nanometer Size Effects............................................................... 117
7.2.1 Nanomaterials for Fuel Cell Electrodes............................................ 117
7.2.1.1 Electrocatalysts in Low-Temperature Fuel Cells................ 118
7.2.1.2 Catalyst Support in Low-Temperature Fuel Cells............... 127
7.2.1.3 Electrodes in SOFCs........................................................... 131
7.2.2 Enhanced Ionic Conductivity and Structural Stability for
Electrolyte.......................................................................................... 132
7.2.2.1 Electrolyte for PEMFCs and DMFCs................................. 132
7.2.2.2 Electrolyte for SOFCs......................................................... 134
7.3 Membrane Electrode Assembly..................................................................... 136
7.3.1 Novel MEAs for Low-Temperature Fuel Cells.................................. 136
7.3.2 A Nonelectrolyte-Separator SOFCs.................................................. 138
7.4 Current Limitations in Nanomaterials for Fuel Cells.................................... 139
7.4.1 Fabrication of MEAs and Fuel Cells................................................. 140
7.4.2 Disadvantages of Nanomaterials....................................................... 140
7.4.2.1 Poor Durability in Fuel Cells.............................................. 140
7.4.2.2 Toxicity from Nanomaterials.............................................. 141
7.5 Conclusions.................................................................................................... 141
Acknowledgment.................................................................................................... 142
References............................................................................................................... 142
7.1 INTRODUCTION TO FUEL CELLS

Although fuel cells were invented in the middle of the nineteenth century (Yeager
1961), they did not find the first application until space exploration in the 1960s with
the alkaline fuel cell or the so-called Bacon fuel cell (Whittingham et al. 2004).
During the past two decades, a confluence of driving forces has created a sustained
and significant worldwide effort to develop fuel cell materials and systems. These
driving needs include the demand for efficient energy systems for transportation, the
desire to reduce greenhouse gases, CO2 and particulate emissions and other negative
113
114 Nanotechnology for Sustainable Manufacturing
environmental impacts, and the demand for high-energy density power sources for
portable electronic applications. Fuel cell technologies are now approaching com-
mercialization, especially in the fields of portable power sources—distributed
and remote generators of electrical energy. Due to the high level of interest in fuel
cells during the past decade or so, there have been numerous summary articles and
symposia focused on the technology state of the art. In this chapter, we present a
series of nanomaterials that deal with applications related to fuel cell development.
Fuel cells are direct electrochemical fuel to electrical energy conversion devices
and offer higher efficiency (50%–70%) compared with conventional technologies
Downloaded by [University of Birmingham], [Shangfeng Du] at 07:38 10 July 2014
such as internal combustion engines (~35% efficiency). If the waste heat of the fuel
cell is also used, fuel efficiencies of 90% are possible. Fuel cells consist of an electro-
positive anode, where oxidation occurs to fuels (hydrogen, methanol, ethanol, meth-
ane, etc.), an electronegative cathode, where reduction occurs (to oxygen, air, etc.),
and an electrolyte (e.g., a proton-conducting polymer membrane, ionic conductive
doped ceria), where ions carry the current between the electrodes. The scheme of
the reactions and processes that occur in the various fuel cell systems is depicted in
Figure 7.1. Tables 7.1 and 7.2 list the characteristics for the various fuel cell systems
(Brodd et al. 2004).
Fuel cells can be roughly divided into low-temperature (ca. <200°C) and high-
temperature (ca. >450°C) fuel cells. Alkaline fuel cell (AFC), polymer electrolyte
membrane fuel cell (PEMFC, also known as proton exchange membrane fuel cell
under the same acronym), direct methanol fuel cell (DMFC), and phosphoric acid
Electrical current
Load
Fuel Air, O2
e– e–
H2 O2
AFC H2O OH–
H2 O2
PEMFC H+ H2O
CH3OH O2
DMFC CO2 H+ H2O
H2 O2
PAFC H+ H2O
H2, CO O2
MCFC H2O, CO2 CO32– CO2
H2, CO O2
SOFC H2O, CO2 O2–
Excess fuel or Unreacted O2/N2

reaction gas Electrolyte or reaction gas
Anode Cathode
FIGURE 7.1 Operation scheme of typical fuel cells.
Applications of Nanomaterials in Fuel Cells 115
TABLE 7.1
Types of Fuel Cells
Advantages Disadvantages Applications
Alkaline fuel cell (AFC)
Mechanically rechargeable; Limited activated life; pure H2 only Military and space
low-cost KOH electrolyte suitable fuel
Polymer electrolyte membrane fuel cell (PEMFC)

Polymer electrolyte; low Expensive catalysts; CO a strong Automotive; stationary

temperature; quick start-up poison; oxygen kinetics are slow; applications
intolerant of impurities; high-cost
electrolyte; pure H2 only suitable
fuel; limited life; water management
essential
Direct methanol fuel cell (DMFC)

Direct fuel conversion; High catalyst loadings; water Portable electronic devices
improved weight and management essential; low overall
volume; polymer electrolyte efficiency; methanol hazardous
Phosphoric acid fuel cell (PAFC)

Higher fuel efficiency H2 only suitable fuel; anode CO Distributed generation
catalyst poison; O2 kinetics
hindered; high-cost catalysts; limited
life
Molten carbonate fuel cell (MCFC)

High efficiency; fuel Materials problems and life; low Electric utility; large
flexibility; high-grade heat sulfur tolerance; high ohmic distributed generation
available electrolyte; need to recycle CO2;
limited life
Solid oxide fuel cell (SOFC)

High efficiency; high grade High fabrication costs; severe Auxiliary power; electric
heat available; no materials constraints utility; large distributed
electrolyte management; generation
fuel flexibility; tolerant of
impurities
Source: Brodd, R.J. et al., Chemical Reviews, 104, 4245–4269, 2004.
fuel cell (PAFC) are typical low-temperature fuel cells. Molten carbonate fuel cell
(MCFC) and solid oxide fuel cell (SOFC) belong to the high-temperature fuel cell
class. In general, low-temperature fuel cells (AFC, PEMFC DMFC, and PAFC) fea-
ture a quicker start-up, which makes them more suitable for portable applications,
especially PEMFCs have recently gained momentum for application in transporta-
tion and as small portable power sources. However, they require as fuel relatively
pure hydrogen (minimum 99.999%), and consequently an external fuel processor,
TABLE 7.2
Typical Characteristics of Various Fuel Cell Systems
Anode Cathode Operating
Type Composition Composition Electrolyte Temperature (°C)
AFC Carbon/platinum Carbon/platinum Aqueous KOH Ambient–100
catalyst catalyst
PEMFC Carbon/platinum Carbon/platinum Acidic polymer Ambient–90
catalyst catalyst
DMFC Carbon/platinum Carbon/platinum Acidic polymer 60–90

catalyst catalyst
PAFC Carbon/platinum Carbon/platinum Phosphoric acid 150–220
catalyst catalyst in SiC matrix
MCFC Porous Ni Porous NiO Molten Li2CO3 550–700
in LiAlO–2
SOFC Ni-YSZ Strontia-doped YSZ 600–1000
lanthanum manganite
perovskite
Source: Brodd, R.J. et al., Chemical Reviews, 104, 4245–4269, 2004.
which increases the complexity and cost and decreases the overall efficiency. They
also require a higher loading of the precious metal catalysts (Garcia-Martinez 2010).
In contrast to low-temperature fuel cells, MCFC and SOFC are more flexible regard-
ing fuel because they can reform various fuels (methanol, ethanol, natural gas, gaso-
line, etc.) inside the cells to produce hydrogen, still offering advantages for stationary
applications, and especially for cogeneration. They are also less prone to catalyst
poisoning by carbon monoxide and carbon dioxide (Brandon et al. 2003). However,
their slower start-up limits them to more stationary applications (Baxter et al. 2009).
In parallel to the development of classic fuel cells, a new and promising type of
fuel cell, the microbial fuel cell (MFC), or biological fuel cell, is currently under
intensive research. MFC produces electricity from microbially catalyzed anodic oxi-
dation processes. The greatest potential of MFC lies in the use of wastewater as fuel,
which allows combining waste treatment and energy recovery. However, MFC still
severely suffers from the short active lifetimes (typically 8 hours to 7 days) (Minteer
et al. 2008) and limited power generation (Zhao et al. 2009), which make it far from
being used in practical applications. Recently, Barton and Schröder summarized the
development and recent work done on MFCs, and more details can be found in their
recent reviews (Barton et al. 2004; Harnisch et al. 2010).
Among the various types of fuel cells, PEMFC, DMFC, and SOFC are actively
under research and development as they employ solid electrolytes that could make
the operation and maintenance of fuel cells easier. However, even like this, their
commercialization is still hampered by high cost, poor durability issues, and oper-
ability problems that are directly linked to severe materials challenges and systems
issues. In low-temperature PEMFCs and DMFCs, the high cost originates from the
expensive Nafion® membrane and notable Pt catalyst used; and the poor durability is
due to the degradation of membrane and catalyst performance, as well as the insta-
bility of catalyst support. While in SOFC, the reason leading to high cost is the high
operating temperature, resulting in the expensive interconnect and sealing materials
used; and the microstructure decline, carbon deposition, and sulfur poisoning to cat-
alysts are the main factors affecting SOFC durability. These are the main drawbacks
limiting the commercial exploitation of these devices. To solve these problems, the
bottleneck on materials must be fixed. So, fuel cell progress always attracts a lot of
interests in the development of high performance materials with novel design and
preparing technologies, in which nanomaterials have played a critical role. For exam-
ple, in low-temperature fuel cells, nearly half of the cost of the fuel cell is linked to
the electrocatalyst cost. To reduce the cost, in PEMFCs and DMFCs, Pt catalyst with
novel nanostructure and high performance have been developed to reduce the load-
ing amount of Pt, or directly by using less expensive alternative nanostructured elec-
trocatalysts, such as N-doped carbon nanotube (CNT) (Dai et al. 2009) or iron-based
catalysts (Dodelet et al. 2009). Regarding high-temperature SOFCs, to decrease the
operating temperature to intermediate range (450–600°C) for a low system cost and
an improved durability, nanocomposite electrodes and electrolyte were developed,
such as samaria doped ceria (SDC) nanowires (NWs)/Na2CO3 nanocomposites elec-
trolyte (Ma et al. 2010) or gadolinium doped ceria (GDC) anode with ionic NW
nanoarchitectures (Laberty-Robert et al. 2007).
In this chapter, we discuss fuel cell materials that have been recently achieved by
nanotechnology, especially focusing on their applications in electrodes and electro-
lytes in PEMFCs, DMFCs, and SOFCs.
7.2 BENEFITS OF NANOMETER SIZE EFFECTS

Nanomaterials are becoming increasingly important in the field and hence have
attracted great interest in recent years. The variety of nanometer size effects in fuel
cell materials can be divided into two types: (1) trivial size effects, which rely solely
on the increased surface-to-volume ratio and (2) true size effects, which also involve
the strong influence of surface properties on overall behavior, and the possibility of
tailoring electrochemical and other properties when the dimensions of fuel cell sys-
tems are confined. There is a significant effect of spatial confinement and the surface
on the physicochemical characteristics due to small particle size. New nanomaterials
may allow fundamental advances in fuel cell performance.
7.2.1 Nanomaterials for Fuel Cell Electrodes

Nanostructured fuel cell electrodes increase the surface area (per unit weight) of cat-
alysts and enhance the contact between fuels and catalysts, which leads to improved
system efficiency. The preparation of nanoscale electrocatalysts for fuel cells typi-
cally starts from colloidal nanomaterial precursors, for example, colloidal platinum
(Pt) sols.
7.2.1.1 Electrocatalysts in Low-Temperature Fuel Cells

The concern about the limited resources of Pt and its high price (Berger 1999) has
made the research on the improvement of Pt catalysts a quite hot research topic for
the past 20 years in low-temperature PEMFCs and DMFCs (Chen et al. 2010; Jaouen
et al. 2011). To reduce the costs, the Pt loading must be decreased while maintaining or
improving fuel cell performance. Already, nanomaterials are having more and more
impacts on processing methods in the development of low-temperature fuel cells, the
dispersion of precious metal catalysts, the development and dispersion of nonprecious
catalysts, as well as the fabrication of membrane electrode assemblies (MEAs).
At the moment, Pt-based catalysts are still the most active materials for
low-temperature fuel cells fed with hydrogen, reformate, or methanol (Chen et al.
2010). The oxygen reduction reaction (ORR) limits the fuel cell performance, espe-
cially in PEMFCs. A few routes are being actively investigated to improve the elec-
trocatalytic activity of Pt-based catalysts. They consist mainly of alloying Pt with
transition metals (e.g., Ni and Co) or tailoring the Pt particle size. One of the present
approaches to increase the catalyst dispersion involves the deposition of Pt nanopar-
ticles on a carbon black (CB) support. A typical high-resolution scanning electron
microscopy image of Pt/C catalyst is shown in Figure 7.2. Kinoshita (1990) observed
that the mass activity and specific activity for oxygen electroreduction in acid elec-
trolytes varies with the Pt particle size according to the relative fraction of Pt surface
atoms on the (111) and (100) faces (Figure 7.3). The mass-averaged distribution of
the surface atoms on the (111) and (100) planes passes through a maximum (~3 nm),
whereas the total fraction of surface atoms at the edge and corner sites decreases
rapidly with an increase of the particle size. On the other hand, the surface-averaged
distribution for the (111) and (100) planes shows a rapid increase with the particle
size, which accounts for the increase of the experimentally determined specific
activity with the particle size.
Both CO2 and CO are present in hydrogen streams obtained from reforming.
These molecules are known to adsorb on the Pt surface under reducing potentials.
Adsorbed CO-like species are also formed on Pt-based anode catalysts in DMFCs.
Such a poisoning of the Pt surface reduces the electrical efficiency and the power
FIGURE 7.2 A typical high-resolution scanning electron microscopy image of platinum (Pt)
catalysts deposited on Vulcan XC-72 carbon black. (Fang, B. et al., Journal of the American
Chemical Society, 131, 15330–15338, 2009a.)
1 0.4
MAD (100 + 111) = (100 + 111) N(t)

Mass activity at 0.9 V
60
0.8
0.3
(A g –1 Pt)
N (edge + corner) N(t)
40
0.6
20
0.2
0.4 0
0 10 20 30 40 50 60
Pt particle size (nm) 0.1

0.2
0 0
0 10 20 30 40 50 60
Particle diameter (nm)
(a)
0.8 1
SAD (100 + 111) = (100 + 111) N(s)

120
0.6 0.8
N (edge + corner) N(s)
Spec. Act. at 0.9 V
80
(μA cm–2)
0.4 0.6
40
0.2 0.4
0
0 10 20 30
Pt particle size (nm)
0 0.4
0 10 20 30 40
Particle diameter (nm)
(b)
FIGURE 7.3 Calculated mass-averaged (a) and surface-averaged distributions (b) as a func-
tion of particle size in Pt particles with cubo-octahedral geometry. N(t) and N(s) indicate the
total number of atoms and the number of atoms on the surface, respectively. The variation
of mass activity (a) and specific activity (b) for oxygen reduction in acid electrolyte versus
particle size is shown in the inset. (Arico, A.S. et al., Nature Materials, 4, 366–377, 2005;
Kinoshita, K., Journal of the Electrochemical Society, 137, 845–848, 1990.)
density of the fuel cell (Devanathan 2008). The electrocatalytic activity of Pt against,
for example, CO2/CO poisoning is known to be promoted by the presence of a s econd
metal, such as Ru, Sn, or Mo (Chang et al. 2010; Schmidt et al. 1997). The mecha-
nism by which such synergistic promotion of the H2/CO and methanol oxidation
reactions is brought about has been much studied and is still debated. Nevertheless,
it turns out that the best performance is obtained from Pt–Ru electrocatalysts with
mean particle size 2–3 nm. As in the case of ORR, the particle size is important for
structure-sensitive reactions such as CH3OH and CO electrooxidation.
Therefore, we cannot keep improving the catalytic performance of electrocatalysts

by continually reducing the nanoparticle size. In this case, to lower the loading amount
of expensive Pt, novel nanostructured electrocatalysts, such as M@Pt core-shell struc-
tures and M core decorated with Pt cluster are good options and have attracted many
efforts. In addition to the generally recognized small size, recent trends reveal that
shape also plays an important role in enhancing the electrocatalytic activity of Pt
nanomaterials (Tian et al. 2007; Wang et al. 2011b). For instance, zero-dimensional
(0-D) electrocatalysts Pt nanocube (Fang et al. 2009b; Murray et al. 2010), polyhedron
and truncated cube (Fang et al. 2010; Herrero et al. 2010), and one-dimensional (1-D)
electrocatalysts nanowires (Du 2010; Sun et al. 2011a; Xia et al. 2009) and nanotube
(Alia et al. 2010; Gorzny et al. 2010) have all been synthesized for fuel cell applications.
7.2.1.1.1 Pt-Based 0-D Nanoelectrocatalysts

Wang et al. synthesized Pt nanocube, polyhedron and truncated cube by reaction of
platinum(II) acetylacetonate with oleic acid and oleylamine in the presence of trace
amount of Fe(CO)5 (Wang et al. 2008). They found that 7-nm Pt nanocubes with rich
(100) facets were much more active than the other shaped Pt nanoparticles in H2SO4
solution, which was due to different adsorptions of sulfate ions on Pt (111) and (100)
facets. To eliminate the impact from sulfate ions, You et al. (2009) measured the
electrocatalytic activities in perchloric acid (HClO4) for three planes, (100), (111),
and (110), which are prepared by utilizing electron beam lithography. The data sug-
gest a division of labor between (100) and (111) nanofacets. For example, the (110)
facets adsorb oxygen well but cannot reduce efficiently, while the (111) facets can
reduce oxygen but cannot easily absorb it. Another important finding was given by
Tian et al. (2007), who found that single-crystalline Pt THH (tetrahexahedral) nano-
spheres enclosed by 24 high-index facets such as (730), (210), and (520) surface have
a large density of atomic steps and dangling bonds, which exhibited much enhanced
specific activity and stability for electrooxidation of small organic fuels than the
commercial E-TEK Pt/C catalysts.
Alloying Pt with transition metals also enhances the electrocatalysis of O2
reduction. In low-temperature fuel cells, Pt–Fe, Pt–Cr, and Pt–Cr–Co alloy elec-
trocatalysts were observed to have high specific activities for oxygen reduction
as compared with that on Pt (Stamenkovic et al. 2007; Wang et al. 2011b). This
enhancement in electrocatalytic activity has been ascribed to several factors
such as interatomic spacing, preferred orientation, or electronic interactions. The
state-of-the-art Pt–Co–Cr electrocatalysts have a particle size of 6 nm (Mukerjee
et al. 1995; Wang et al. 2011b). The synthesis of nanocubes with oleic acid and
oleylamine has also been expanded to the Pt-based alloy catalysts, for example,
(100)-terminated Pt3M nanocubes (M = transition metals Mn, Co, Fe, and Ni).
Generally, they show a higher catalytic activity than their spherical counterparts
toward oxygen reduction, formic acid oxidation, and methanol oxidation. By modi-
fying the synthesis procedure, Fang et al. also prepared (111)-terminated Pt3Ni
nanoctahedra (as shown in Figure 7.4). The electrochemical experiments demon-
strated that ORR activity strongly depends on the terminal facets of Pt3Ni nano-
cubes. The {111}-facet-terminated nanoctahedra are significantly more active than
the {100}-bounded nanocubes.
(a) (b) (d) (e)
40 nm
<111>
(c) 2.23 Å
100 nm 50 nm 2 nm
(f ) (g) (i) (j)

0>
40 nm
4Å
<10
1.9
(h)
100 nm 50 nm 2 nm
FIGURE 7.4 (See color insert.) (a–e) Images for Pt3Ni nanoctahedra. (f–j) Images for Pt3Ni
nanocubes. (Fang, J.Y. et al., Nano Letters, 10, 638–644, 2010.)
More research work is needed to explain the complexities of facet effect.

Nonetheless it is clear that controlling the shape of nanocatalyst is an effective way
to improve ORR activity and to develop highly active electrocatalysts used under
real conditions.
7.2.1.1.2 Nonprecious 0-D Nanoelectrocatalysts

Another solution to overcome the predicament of Pt catalysts is to replace them
with nonprecious catalysts. The research on these materials has been studied for
over 50 years, but they were insufficiently active for the high efficiency and power
density needed for fuel cell applications (Binder et al. 1969; Bohm 1970). Recently,
several breakthroughs occurred that have increased the activity and durability of
nonprecious electrocatalysts, which can now be regarded as potential competitors to
Pt-based catalysts (Jaouen et al. 2011).
Recently, MeNxCy catalysts have been receiving increased attention due to their
reasonable activity and remarkable selectivity toward ORR. For example, a break-
through of volume-specific activity from 2.7 to 99 A/cm3 was achieved by the
Dodelet group in Canada (Lefèvre et al. 2009). They produced microporous carbon–
supported iron-based catalysts with active sites believed to contain iron cations coor-
dinated by pyridinic nitrogen functionalities in the interstices of graphitic sheets
within the micropores. Very recently, by replacing microporous carbon with zeolitic-
imidazolate framework, they successfully improved the catalyst performance and
reached a power density of 0.75 W/cm2 at 0.6 V, tested at cathode in H2–O2, which is
a meaningful voltage for PEMFC operation, comparable with that of a commercial
Pt-based cathode tested under identical conditions (Proietti et al. 2011). However, the
stability for such a catalyst was still much lower than the corresponding Pt catalysts.
A remarkable improvement of stability was achieved by Zelenay et al. (2011). The
most stable nonprecious metal catalysts derived from polyaniline, iron, and cobalt
showed an 18 μA/h loss in average current density at 700-hour fuel cell performance
test at a constant cell voltage of 0.4 V. The presence of the graphitized carbon phase
in an active catalyst was suggested to play a role in hosting ORR-active sites and
enhancing stability of the polyaniline-derived catalysts. Despite the promising attri-
butes of these catalysts, both their activity and stability are insufficient to satisfy
practical requirements. Undoubtedly, the combination of a better understanding of
the nature of the active site and introduction of new materials and synthetic methods
will be beneficial in improving the performance of this kind of catalyst.
7.2.1.1.3 1-D Nanostructures
The high surface energy brings contemporary 0-D nanoparticles better catalytic
activity, but also relatively low stability, especially under the acidic conditions of the
fuel cell, such as the presence of Ru in DMFC anode catalyst makes it less stable to
permanent oxidation and solubilization in operating DMFCs (Yu et al. 2007a). In
light of these shortfalls of contemporary 0-D nanoparticles, the use of 1-D nanoma-
terials in the development of electrocatalysts has become an excellent choice with
which to solve many of the technological challenges that face the development of
fuel cells.
From a structural perspective, the asymmetry of 1-D structure suppresses physical
ripening processes and thus these nanomaterials are inherently stabilized from dis-
solution and Oswald ripening, which are known as one of the three primary break-
down mechanisms of carbon-supported 0-D Pt and Pt alloy nanoparticles (Chen
et al. 2007; Garbarino et al. 2009). And, anisotropic 1-D nanostructures also possess
advantageous path-directing effects, which greatly enhance their electron transport
properties (Yan et al. 2004). A previous study of metallic NWs in devices has shown
that single-crystalline NWs can maintain resistances commensurate with those of
their bulk counterparts (Tian et al. 2005).
In recent years, many techniques have been proposed in the preparation and char-
acterization of Pt-based NWs, but only several of them have actually been used for
practical fuel cells, for which the history and development has been discussed in our
and Wong’s early reviews in detail (Du 2012; Koenigsmann et al. 2011). Template
preparation has been the earliest technique explored for synthesizing Pt-based NWs
for fuel cell catalysts, ever since the use of SBA-15 template nanoreactor from 2003
producing the NW network for anode materials in DMFCs (Choi et al. 2003). Since
then, a range of templates have been investigated on this preparation method for fuel
cells; from porous silicate (Park et al. 2008; Sun et al. 2006) to anodized aluminum
oxide (AAO) (Liu et al. 2004a, 2009b; Lux et al. 2006; Ponrouch et al. 2010; Zhang
et al. 2009; Zhao et al. 2006, 2007; Zhong et al. 2008) and then polymer template
(Choi et al. 2008), even the fuel cell electrolyte Nafion membrane (Liang et al. 2010b,
2007). Generally, the preparation of NWs using these templates involves three steps:
infiltration of the pores with an appropriate precursor through a vapor- or solution-
based approach, conversion of this precursor to the desired material, and recovery
of the NWs by selectively removing the template. If a sacrificial component (e.g., Cu
or Ag) was simultaneously used with Pt to generate NW, after removing this sacrifi-
cial component, a porous NW could be obtained. For example, Figure 7.5 shows Pt
porous NW array prepared by electrodepositing Pt-Co alloy NWs in AAO and then
dealloying the Cu component (Zhang et al. 2009). In case of a 1-D nanostructure, for
(a) (b)
(111)
(200)
(220)
(311)
30 nm 30 nm
FIGURE 7.5 TEM micrographs showing the crystalline features of as-prepared nanoporous
Pt-Co alloy nanowires by (a) 5-minute and (b) 15-hour dealloying, respectively. The dealloy-
ing was carried out in 10 wt% H3PO4 at 45°C. (Liu, L.F. et al., Nano Letters, 9, 4352–4358,
2009b.)
example, silver NWs or tobacco mosaic virus used as template, a porous Pt-based
nanotube could also be obtained (Alia et al. 2010; Chen et al. 2007; Gorzny et al.
2010). In both cases, the high specific area from the porous nanostructure, together
with the anisotropic 1-D feature, could lead to relative higher activity and durabil-
ity than contemporary 0-D nanoparticle electrocatalysts. In addition to a template
method, an electrospinning method has also been used for preparing Pt-based NWs
(Kim et al. 2008, 2009a,b, 2010). However, irrespective of template-based method or
electrospinning technique, only polycrystalline nanostructures were obtained for the
produced Pt-based NWs. Although the excellent catalytic performance was obtained
due to their 1-D feature, the existing lattice boundary and defect sites still result in
a relative low catalytic stability, because these regions evince surface Pt atoms with
lower coordination numbers and thus are more susceptible to decomposition and
prone to irreversible oxidation (Shao et al. 2007; Yu et al. 2007b). Moreover, the
template-based and electrospinning methods are technically complicated, owing to
the requirement for template or ligand removal to obtain pure products. This limits
their applications to some extent.
Apart from the advantages of the 1-D feature as that from polycrystalline NWs,
single-crystalline Pt-based NWs give more benefits. First, the anisotropic growth of
1-D nanostructures typically results in the preferential display of low-energy crystal
facets to minimize the surface energy of the systems (Cademartiri et al. 2009). In
terms of Pt, the low energy (100) and (111) facets are most active for oxygen-reduction
and thus the preferential display of these low-energy facets would be highly advan-
tageous for catalysis (Subhramannia et al. 2008). Furthermore, single-crystalline
Pt-based NWs possess largely pristine surfaces with long segments of crystalline
planes (Seal et al. 2007) and maintain fewer surface defect sites (Williams 2001),
leading to much high stability as compared with 0-D morphologies or polycrys-
talline 1-D nanostructures. More recently, wet chemical methods were success-
fully employed to grow single-crystalline Pt NWs for fuel cell applications. In
2007, Xia and coworkers (Lee et al. 2007, 2008) demonstrated the direct growth of
single-crystalline Pt <111> NW arrays onto a gauze made of Pt or W for methanol
oxidation by modified polyol process, combining with the decreased reaction rate
obtained by the introduction of a trace amount of Fe2+ or Fe3+. Poly(vinyl pyrrol-
idone) (PVP) was used as a surfactant, and the reaction was carried out at 110°C
without any heat treatment, which is typically used for carbon-supported Pt cata-
lysts. TEM images show these NWs had a diameter of ~5 nm, a length up to 200 nm
and the growth direction along <111> axis (Figure 7.6). However, the large amount
of PVP (molar ratio of PVP to Pt larger than 5) used was very difficult to be removed
completely from the sample, especially in a highly dense Pt-NW array, which could
hinder the accessibility of the catalytic surface by the fuel molecules and therefore
cause a decrease in the catalytic performance. To avoid the influence of PVP, Zhang
et al. and Gong et al. replaced ethylene glycerol with oleylamine as the reducing
agent, and Pt-Fe and Pt-Mn ultrathin NWs with a diameter of 2–3nm were success-
fully prepared (Gong et al. 2011; Zhang et al. 2011a).
Another important improvement was given by Sun et al. (2007, 2008a,b, 2009a,
2010, 2011a). To decrease the reaction rate, the reaction was changed from 80°C to
room temperature with formic acid used as reducing agent. Single-crystalline Pt
<111> NWs were successfully grown in aqueous solution at room temperature, with-
out using any templates, protecting groups, inducing-growth catalysts, or organic sol-
vents. The as-prepared Pt NWs had diameters of approximately 4–10 nm and lengths
up to a 100 nm. Using carbon spheres as support, the packed arrays of Pt NWs were
densely covered on the surface of carbon spheres. These Pt-NW/C nanostructures
were measured as cathode catalysts in PEMFCs. The results showed, for ORR, a
50% higher mass activity of 120 A/g Pt and threefold better specific activity of 275
μA/cm2 Pt than those of the state-of-the-art Pt nanoparticle catalysts (PRIMEATM
5510 from W.L. Gore and Associates) (Sun et al. 2008a). The 1-D single-crystalline
(a) (b)
0.23 nm 0.23 nm
<111> <111>
2 nm 2 nm
(c) (d)
100 nm 100 nm
FIGURE 7.6 SEM and high-resolution TEM images of Pt nanowires on Pt (a, c) and W (b, d)
gauzes. (Lee, E.P. et al., ACS Nano, 2, 2167–2173, 2008.)
nanostructure could also be prepared without support, where a multiarmed starlike

NW was obtained (Sun et al. 2011a). It showed a very high catalytic durability toward
methanol oxidation reaction (MOR) and ORR, due to the detachment of catalysts
from the supports (e.g. carbon corrosion in Pt/C) is successfully eliminated for this
kind of catalysts.
7.2.1.1.4 Core–Shell Configuration

Although single-crystalline 1-D Pt-based NWs possess high catalytic durability and bet-
ter performance as compared with 0-D nanoparticles, the loading amount of e xpensive
noble metal electrocatalyst is still very high due to the relative large diameters. To effi-
ciently reduce the loading amount, recent developments in the field of fuel cell catalysts
include the synthesis of new core–shell nanostructures by spontaneous deposition of
Pt submonolayers on metal and other supports (e.g., C, Ni, Ag, or MoO) (Arico et al.
2005; Brankovic et al. 2001; Eichhorn et al. 2009; Stamenkovic et al. 2007; Tedsree
et al. 2011) or dealloying from a bimetallic alloy precursor (e.g., Pt-Mo, Pt-Ag, Pt-Ni,
Pt-Cu, or Pt-Cu-Co) to form a Pt-rich shell (Eichhorn et al. 2009; Peng et al. 2010;
Strasser et al. 2007; Wang et al. 2011a). Apart from the economic benefits, this configu-
ration is also attractive in terms of the highly enhanced reactivity (Eichhorn et al. 2009;
Strasser et al. 2010; Tedsree et al. 2011). It has been demonstrated that platinum-rich
shell exhibits compressive strain, which results in a shift of the electronic band struc-
ture of Pt and weakening chemisorption of oxygenated species, resulting in a very high
reactivity toward ORR, as shown in Figure 7.7 (Strasser et al. 2010). Furthermore, this
mechanism is not restricted to Pt, and it can be expanded to other expensive noble met-
als. For example, an Ag-Pd core–shell nanocatalyst with the shell containing between
1 and 10 layers of Pd atoms. The Pd shell contains terrace sites and is electronically
promoted by the Ag core, leading to significantly enhanced c atalytic properties (Tedsree
et al. 2011). Further advances concern a better understanding of the surface chemistry
in electrocatalyst nanoparticles and the effects of strong m
etal–support interactions that
influence both the dispersion and electronic nature of Pt/Pd sites.
If we keep reducing the Pt loading amount in Pt-rich shell, subnanometer Pt clus-
ters or even single atoms could possibly be achieved. Recent theoretical and experi-
mental results demonstrated that subnanometer clusters have better catalytic activity
and/or selectivity than nanometer-sized particles (Remediakis et al. 2005; Vajda et al.
2009). Of course, fabrication of practical and stable single-atom catalysts remains a
significant challenge because, typically, single atoms are too mobile and easy to sinter
under realistic reaction conditions. And, this is also the reason why a 3-nm Pt-based
catalyst nanoparticle is usually preferred in low-temperature fuel cell catalysts. A
very important finding on this topic was given by Zhang et al. (2007), who demon-
strated that Pt electrocatalysts can be stabilized against dissolution under potential
cycling regimes by modifying with Au clusters. The Au clusters are two to three
monolayers thick and 2–3 nm in diameter, conferring activity by raising the Pt oxi-
dation potential. There were insignificant changes in the activity and surface area of
Au-modified Pt over the course of potential cycling between 0.6 and 1.1 V in over
30,000 cycles, in contrast to sizable losses observed with the pure Pt catalyst under
the same conditions. Nevertheless, a synergy is achieved here by hybrid clusters with
nanoparticles, which is a little bit similar to the shift of the electronic band structure
Pt shell
1
2
Pt–Cu core
acore
2 nm ashell
(a) (b)
0.12
0.10
0.08
ORR activity (eV)
0.06 Pt25Cu75
Pt50Cu50
0.04 Pt75 Cu25
Pt25Cu75
0.02
0.00 Pt50Cu50
Pt75Cu25 Pt
–0.02
–4 –3 –2 –1 0
Strain (ashell – aPt)/aPt (%)
(c)
FIGURE 7.7 (See color insert.) (a) Subangstrom resolution image of a Pt-Cu dealloyed
nanoparticle (∼4 nm). (b) Scheme of a simple two-phase structural model for the dealloyed
state of a bimetallic particle. (c) Experimental and predicted relationships between electro-
catalytic oxygen reduction reaction (ORR) activity and lattice strain (annealing temperatures
of 950°C [blue] and 800°C [red]). The dashed line is the predicted density functional theory
(DFT) of the ORR activity. (Strasser, P. et al., Nature Chemistry, 2, 454–460, 2010.)
in the core–shell configuration mentioned in the preceding discussion in some degree.

This means that if a support is thoroughly designed, the metal clusters or even single
atoms could be anchored and stabilized by synergy with the support. For example,
with FeOx as oxide support, by a simple chemical coprecipitation method followed by
heat treatment, Qiao et al. (2011) successfully synthesized a novel catalyst that con-
sists of only isolated single Pt atoms uniformly dispersed on FeOx nanocrystallites of
high surface area. The Pt single-atom catalyst exhibits very high activity and stability
for both CO oxidation and preferential oxidation of CO in H2. The authors attributed
this improvement to more vacant d orbitals of the single Pt atoms. The electron trans-
fer from Pt atoms to the FeOx surface is responsible both for the strong binding and
stabilization of single Pt atoms and for providing positively charged Pt atoms, which
(a) 2 5 nm Pt (b)
5–17 nm Pt-Fe3O4
Mass activity (mA/mg Pt)

0
‒2
‒4
‒6
‒8
20 nm
0.1 0.2 0.3 0.4 0.5 0.6 0.7
Potential (V vs. Ag/AgCl)
FIGURE 7.8 (a) TEM image of 5−12-nm Pt-Fe3O4 NPs and (b) oxygen reduction reaction
mass activities for 5-nm Pt and 5−17-nm Pt-Fe3O4 NP catalysts measured in 0.5 M H2SO4
with the rotating disc electrode rotation speed at 1600 rpm and sweeping rate at 10 mV/s.
(Sun, S.H. et al., Nano Letters, 9, 1493–1496, 2009b.)
ultimately account for the excellent catalytic activity of the Pt/FeOx catalysts. For fuel
cell applications, this synergy between Pt and FeOx was also found in monodisperse
dumbbell-like Pt-Fe3O4 nanoparticles (Sun et al. 2009b), where the nanoparticle size
is tunable from 2 to 8 nm for Pt and from 6 to 20 nm for Fe3O4. This structure shows
a 20-fold increase in mass activity toward ORR compared with the single-component
Pt nanoparticles and the commercial 3-nm Pt particles, as shown in Figure 7.8. This
synergy is not restricted to Pt and FeOx, for example, Abruna et al. (2010b) demon-
strated that the decoration with a small amount of Pt also enhanced the stability and
electrocatalytic activity of Pd-Co@Pd nanoparticles toward ORR. By this approach,
if a support could be found with the same synergy function and a good stability in
acidic fuel cell environments, the Pt loading could be expected to be reduced to an
extremely low level and the barrier of cost could be then resolved.
7.2.1.2 Catalyst Support in Low-Temperature Fuel Cells

We know that fuel cell performance is essentially governed by the electrocatalyst
support materials as they strongly influence the electrocatalyst performance, durabil-
ity, and efficiency. It is well known that carbonaceous support materials suffer from
carbon corrosion (oxidation) especially at high potentials over time. Thus, alternative
low-cost, high-performing, and noncorrosive electrocatalyst support materials are
urgently required.
7.2.1.2.1 Carbon-Based Nanostructures

The use of carbon materials as catalyst supports for precious metals started from
1960s (Chang et al. 2010), but unlike the hot research efforts on electrocatalysts,
only recently the study experienced a rapid increase on catalyst support, due to the
continuous advancements in nanotechnologies and fuel cells. The main require-
ments of suitable supports for fuel cell catalysts are high surface area, good electrical
conductivity, suitable porosity to allow good reactant flux, and acceptable stability
(e.g., corrosion resistant) in acidic fuel cell environment. The high availability and
low cost make CBs the most used support for low-temperature fuel cell catalysts.
Conventionally, highly conductive CBs of turbostratic structures with high sur-
face areas, such as Vulcan XC-72R (Cabot Corp., 250 m2/g), Shawinigan (Chevron,
80 m2/g), Black Pearl 2000 (BP2000, Cabot Corp., 1500 m2/g), Ketjen Black (KB
EC600JD & KB EC600J, Ketjen International, 1270 m2/g and 800 m2/g, respectively),
and Denka Black (DB, Denka, 65 m2/g), are currently used as low-temperature fuel
cell electrocatalyst supports to ensure large electrochemical reaction surfaces. They
are usually submitted to chemical activation to increase anchoring centers for cata-
lysts (to increase metal loading and dispersion). The disadvantage of these materials
is the presence of a high amount of micropores (<2 nm), where supply of a fuel may
not occur smoothly and the activity of the catalyst may be limited. Moreover, the
corrosion of CB by oxygen during the cycling processes of fuel cells strongly reduces
the electrocatalytic activities of the catalysts (Antolini 2009; Hartl et al. 2011).
Recent studies have revealed that the physical properties of the carbon support
can greatly affect the electrochemical properties of the fuel cell catalyst. It has been
reported that carbon materials with both high surface area and good crystallinity
cannot only provide a high dispersion of Pt nanoparticles but also facilitate electron
transfer, resulting in better performance (Antolini 2009; Antolini et al. 2009; Hartl
et al. 2011). On this basis, novel nonconventional carbon materials have attracted
much interest as electrocatalyst support because of their good electrical and mechan-
ical properties and their versatility in pore size and pore distribution tailoring. These
materials present a different morphology than CBs both at the nanoscopic level in
terms of their pore texture (e.g., mesoporous carbon) and at the macroscopic level
in terms of their form (e.g., microsphere). The examples are supports produced
from ordered mesoporous carbons (OMCs) (Chang et al. 2007; Xia et al. 2008),
carbon aerogels (Moreno-Castilla et al. 2005), carbon nanohorns (Sano et al. 2006;
Yoshitake et al. 2002), carbon nanocoils (Fuertes et al. 2007; Hyeon et al. 2003),
carbon nanofibers (Hwang et al. 2007), CNTs (Wong et al. 2009), graphene, and
graphene oxide (Sun et al. 2011b). Some of these works are summarized in Antolini’s
(2009) recent review. Among these novel nanostructures, because of the high sur-
face area and proper porosity, the mesoporous carbons (MC, e.g., OMC and carbon
aerogels), CNTs, and graphene are expected to be the most suitable for the prepara-
tion of catalytic particles and for efficient diffusion and transport of reactants and
by-products.
The high surface area and high amount of mesopores of OMCs and carbon gels
allow high metal dispersion and good reactant flux (Chang et al. 2007). So, catalysts
supported on these carbons showed higher catalytic activity than the same catalysts
supported on CB. It has to be remarked that the synthesis methods of OMCs and
carbon aerogels are simple and not too expensive. However, suitable carbon sup-
ports must possess high mesoporosity in the pore size range of 20–40 nm for a
high accessible surface area. Indeed, the Nafion binder solution, which is generally
used in electrode preparation, is constituted by ionomers that do not enter or may
occlude pores narrower than 20 nm (Yang et al. 2010), so that catalyst nanoparticles
deposited in such pores are not in contact with the proton conductor and/or the fuel.
For this reason, the presence of mesopores with pore size <20 nm supports the gas
flow, but decreases the active surface area of the catalyst. As a consequence, the elec-
trochemical activity of these MCs could be lower than that of microporous carbons.
On the basis of their high versatility in pore size and pore distribution tailoring,
among the MCs, carbon gels seem more promising than OMCs.
Among the new carbon materials, CNTs are the most investigated as catalyst
support for low-temperature fuel cells (Antolini 2009; Wong et al. 2009). They
normally possess an outer diameter of 10–50 nm, an inside diameter of 3–15 nm
(pore size), and a tube length of 10–50 μm. The high crystallinity of CNTs makes
these materials highly conductive; the high specific surface area (SSA) and high
amount of mesopores result in a high metal dispersion and a good reactant flux in
tubular structures (Wong et al. 2009). Moreover, CNTs have a positive effect on
Pt structure, resulting in a higher catalytic activity and a higher stability than CBs
(Zhang et al. 2010a). A problem for the commercialization of CNTs is their higher
cost compared with that of CBs. During synthesis of the catalyst using this sup-
port, Pt particles (2–5 nm size) present on the pore mouths of CNTs will take part
in the chemical reaction. However, there is a great possibility for the existence of
Pt particles inside the nanotube, depending on Pt particle size (Wong et al. 2009).
These particles will take little part in the chemical reaction. The number of the Pt
particles inside the tube will be more when the tube length of CNT increases. So,
a decrease in the Pt active area and the electrochemical activity of the catalyst has
to be expected.
Graphene, a single-layer graphite with closely packed conjugated hexagonal lat-
tices, is recognized as the basic building block of all dimensional graphitic materials
(Geim et al. 2007). Also, graphene nanoribbons can be prepared by longitudinal
unzipping of CNTs (Tour et al. 2009). So, graphene not only possesses all advantages
of CNTs as catalyst supports, for example, high electrical conductivity and huge
SSA, but also avoids the drawback of catalyst particles existing inside the nanotube.
Furthermore, the large size of graphene (layer diameter >1 μm) can also eliminate
the possible health problems caused by CNT pollution. Thus, graphene has been
exploited as the support of Pt catalyst. For example, Liu et al. (2009a) compared the
SSA, electrocatalytic activity for ORR, and stability of the Pt nanoparticles sup-
ported on the functionalized graphene sheets (Pt-FGS) and CBs (E-TEK). Pt-FGS
showed not only larger SSA and higher ORR activity but also excellent stability
after 5000 cyclic voltammetry cycles. These improved properties were attrib-
uted to the smaller aggregation of Pt particles immobilized on graphene. In addi-
tion, Pt nanoparticles were supported on graphene nanoplatelets, and this catalyst
also showed a good electrochemical durability (two to three times that of the Pt/
CNT or E-TEK Pt/C) (Wang et al. 2010b,c, 2011c). Beside Pt nanoparticles, the
graphene-supported Pt-on-Pd bimetallic nanodendrites (Wang et al. 2010a) (shown
in Figure 7.9) and Pt-Ru nanoparticles (Dong et al. 2010) were also prepared for
methanol and ethanol oxidations. Compared with CB, graphene strongly enhanced
the oxidation efficiencies of both methanol and ethanol.
By comparing MCs, CNTs, and graphene, taking into account the cost of the mate-
rials, the complexity of the synthesis methods, and the versatility in pore size and pore
1000 nm 50 nm
FIGURE 7.9 TEM image of the Pt-on-Pd bimetallic nanodendrites supported on graphene
sheets. (Wang, E.W. et al., ACS Nano, 4, 547–555, 2010a.)
distribution tailoring, the MCs seem to have more changes to substitute CBs as fuel
cell catalyst substrate (e.g., as microporous layer). On the other hand, CNTs or gra-
phene, for their high electronic conductivity, due to their unique structure, and their
high stability during long-term tests in acidic media, ascribed to the strong metal–
carbon interactions, seem to be more suitable than MCs for use as a support for fuel
cell catalysts. The stability in fuel cell conditions of MC-supported catalysts is similar
to that of CB-supported catalysts, but can be increased by graphitization of the MCs.
Apart from pure carbon materials, nitrogen-doped carbon material is recognized
as a good support for Pt catalysts. Data suggest that nitrogen functional groups intro-
duced into a carbon support appear to influence at least three aspects of the catalyst/
support system (Zhou et al. 2010): (1) modified nucleation and growth kinetics dur-
ing catalyst nanoparticle deposition, which results in smaller catalyst particle size
and increased catalyst particle dispersion; (2) increased support/catalyst chemical
binding (or tethering), which results in enhanced durability; and (3) catalyst nanopar-
ticle electronic structure modification, which enhances intrinsic catalytic activity.
N-doped carbon-based nanostructures have much more effect in fuel cell applica-
tions; this includes the research on mesoporous N-doped carbon (Ma et al. 2009;
Yang et al. 2011), N-doped CNTs (Chen et al. 2011; Dai et al. 2009), and N-doped
graphene (Geng et al. 2011; Lin et al. 2010; Ramaprabhu et al. 2010; Song et al. 2010;
Tang et al. 2009). For example, N-doped graphene can be synthesized by chemical
vapor deposition (CVD) of methane in the presence of ammonia as reported by Dai
et al. (Liu et al. 2010b). Compared with the commercialized Pt catalysts, this mate-
rial showed higher electrocatalytic activity, longer-term stability, and improved tol-
erance to CO for ORR. Considering the low price and high electrocatalytic activity,
N-doped graphene can be used as an efficient ORR catalyst for fuel cells. However,
all these researches only performed the electrical measurement in KOH, their per-
formance in PEMFCs and DMFCs is still unknown.
From the perspective of the replacement of CBs with MCs or CNTs as catalyst
supports, or to directly use N-doped carbon materials as catalyst for ORR, further
tests in fuel cells have to be performed to evaluate the electrochemical activity and
the long-term stability of the catalysts supported on these new promising materials.
7.2.1.2.2 Noncarbonaceous Supports

An example of the alternative approach for avoiding the use of CBs is the fabrication
of porous silicon catalyst support structures with a 5-μm pore diameter and a thick-
ness of about 500 μm (Miu et al. 2010). These structures have high SSA, and they
are of interest for miniature low-temperature fuel cells. A finely dispersed, uniform
distribution of nanometer-scale catalyst particles deposited on the walls of the silicon
pores creates, in contact with the ionomer, an efficient three-phase reaction zone
capable of high-power generation in DMFCs (Manthiram et al. 2008).
Another group of noncarbonaceous support is tungsten carbide (WC) (Binder
et al. 1969) and metal oxides, for example, ZrO2, TiO2, indium oxides, alumina,
silica and tungsten oxide, ceria, and conducting polymer materials (Abruna et al.
2010a; Antolini 2009; Antolini et al. 2009; Miu et al. 2010). It has been demonstrated
some of these materials are highly stable to oxidative decomposition compared to
currently used CBs. Furthermore, the low catalytic ability of WC can effectively
enhance the reactivity and durability of Pt catalysts (Hara et al. 2007; Liang et al.
2010a). However, the greater difficulty in the preparation limits its application.
7.2.1.3 Electrodes in SOFCs
Due to the fact that SOFCs operate at high temperatures, the particle size of ceramic
electrocatalysts is more than one order of magnitude larger than Pt catalysts used in
low-temperature fuel cells. Even like this, nanostructured electroceramic materials
are increasingly used in intermediate-temperature SOFCs (IT-SOFCs) (Brett et al.
2008). For example, SOFC microstructured components fabricated by starting with
nanosized particles possess different electrocatalytic and ion-conduction properties
from the typical polycrystalline materials (Schoonman 2003). Nanosized yttria-
stabilized zirconia (YSZ) and ceria-based (gadolliunium, samaria, and yttria-doped
ceria) powders permit a reduction of the firing temperature during the membrane-
forming step in the cell fabrication procedure because their sintering properties dif-
fer from those of polycrystalline powders (Ormerod 2003; Ruiz-Morales et al. 2010).
Furthermore, by decreasing the particle size in the electroceramics, the quantum
confinement effect causes an increase in the band gap and, thus, favors the occur-
rence of a purely ionic domain. For example, nanocrystalline ceria, which is charac-
terized by mixed electronic ionic conduction properties, promotes the charge transfer
reactions at the electrode–electrolyte interface (Brett et al. 2008; Suzuki et al. 2009).
Besides reduced particle size by using nanocrystalline materials, the SOFC
electrode performance can also be improved by novel nanostructured design.
It has been demonstrated that the electrode microstructure and the SOFC per-
formance have a close correlation (Suzuki et al. 2009). The dual-scale porous
SSC(Sm0.5Sr 0.5CoO3)-GDC and NiO-GDC electrode for SOFCs can be synthe-
sized with a foam-like thin film template (Liu et al. 2005). This porous struc-
ture contains large pores (0.8–1.5 μm) for rapid gas transport and small pores
(approximate 2.5 and 35 nm) for fast electrochemical reactions (Figure 7.10).
Highly porous and nanostructured SOFC cathodes consisting of nanograins of
about 50 nm have also been fabricated using a combustion CVD process, and for
which a very low interfacial polarization resistance (1.09 Ωcm 2 at 500°C) was
achieved (Liu et al. 2004b). To increase the cathode/electrolyte interfacial area
500 nm
10 μm 1 μm
(a) (b)
FIGURE 7.10 (a, b) SEM images of a dual-scale porous NiO-GDC anode film fired at
800°C for 2 hours. The inset in (b) shows the nanostructure of the porous wall. (Liu, M.L.
et al., Advanced Materials, 17, 487–491, 2005.)
density and to lower the polarization resistance present at the cathode/electrolyte

interface, Yoon et al. (2009) introduced a binary vertically aligned nanocomposite
interlayer of (LSCO)0.5(CGO)0.5 between the cathode and electrolyte to achieve a
high-efficiency thin film SOFC. Cathode with very low polarization resistance
was also prepared by cobaltite nanotubes (Bellino et al. 2007). Laberty-Robert
et al. (2007) optimized electrical properties of GDC by creating nanoarchitectures
interconnectivity established between the <10 nm crystallites in CGO aerogels for
rate-critical applications. The high degree of network yields an electroceramic that
responds as though it contains no grain boundaries and that exhibits long-range
pathways for ionic diffusion.
7.2.2 Enhanced Ionic Conductivity and Structural

Stability for Electrolyte
7.2.2.1 Electrolyte for PEMFCs and DMFCs
The electrolyte is an essential component of the fuel cell assembly. It is a quintessen-
tial nanomaterial in PEMFCs and DMFCs, with hydrophilic pores of around 10 nm
in size through which protons are transported (Figure 7.11) (Buratto 2010). The most
common polymer electrolyte membrane (PEM) material is the perfluorosulfonic
polymer (e.g., Nafion), which is composed of a hydrophobic Teflon backbone and
side chains terminated with hydrophilic sulfonic acid (SO3H) groups, because of its
excellent proton conductivity and electrochemical stability. Several decades of PEM
research have resulted mostly in a phenomenological understanding of membrane
performance. Nafion, despite its high cost and hydration requirement that restricts
operation to 80°C, continues to be the most widely studied and employed membrane
for PEMFCs (Devanathan 2008). Furthermore, even with the extensive experimental
database on Nafion membrane structure and molecular transport, a deep understand-
ing of the water network and proton transport processes is still evolving.
PEM cross-section
H+
5 nm
FIGURE 7.11 Schematic cross-section of a polymer electrolyte membrane (PEM). The

proton-conducting channels are depicted in white. (Buratto, S.K., Nature Nanotechnology,
5, 176, 2010.)
Nafion suffers from several drawbacks such as methanol crossover and mem-
brane dehydration. In a Nafion film, the hydrophilic pores form by phase separation
of the side chains from the polymer backbone. The performance of the proton-
conducting channels in these films is strongly dependent on the environmental
conditions. At high temperature and low relative humidity, the p roton-conducting
channels shrink and the conductivity decreases markedly. This means that under
high-temperature conditions—where the catalysts in the electrodes perform at
their best—the membrane performs at its worst. Therefore, to optimize the per-
formance of fuel cells, it is useful to design a membrane with high conductivity at
high temperature and low humidity. The research is usually carried out in nano-
technologies by two ways: modifying the Nafion membrane and using alternative
materials.
Various relationships between membrane nanostructure and transport character-
istics, including conductivity, diffusion, permeation, and electroosmotic drag, have
been observed (Arico et al. 2005; Paddison 2003). Fully or partially perfluorinated
membranes can overcome some of the shortcomings of Nafion (Devanathan 2008).
Modification of side chain and backbone length (Di Noto et al. 2010; Paddison
2003) or addition of inorganic fillers (Chan et al. 2011; Laberty-Robert et al. 2011;
Spurgeon et al. 2011) and heteropoly acids (Herring et al. 2007; Ramani et al. 2005)
may help retain water at low humidity. However, the effect of fillers on membrane
morphology is not well understood.
Among the alternative materials to Nafion, one important finding was made by
Moghaddam and colleagues (Buratto 2010; Moghaddam et al. 2010). They reported
a new silicon-based proton exchange membrane with high proton conductivity over
a wide range of relative humidity and temperature. Key to achieving these advan-
tages is fabricating a silicon membrane with pores of diameters around 5–7 nm,
adding a self-assembled molecular monolayer on the pore surface, and then cap-
ping the pores with a layer of porous silica. The silica layer reduces the diameter of
the pores and ensures their hydration, resulting in a proton conductivity that is two
to three orders of magnitude higher than that of Nafion at low humidity. A MEA
constructed with this proton exchange membrane delivered an order of magnitude
higher power density than that achieved previously with a dry hydrogen feed and an
air-breathing cathode. Other research on alternative membranes includes materials
based on aromatic backbone polymers (Park et al. 2010) and polystyrene sulfonic
acid membranes (Jones et al. 2003).
However, most of the research products are only demonstrated in l aboratory-scale

tests; real-life tests of novel membranes during prolonged operation at elevated
temperatures, low humidities, and oxidizing conditions are required to r igorously
evaluate the membranes proposed as alternatives to Nafion. Furthermore, inte-
grated experimental, theoretical, and computational studies that link proton
transfer, hydrogen bonding, molecular transport, membrane morphology, and
mechanical properties are needed for rational development of the next generation
of PEMs.
7.2.2.2 Electrolyte for SOFCs

SOFCs use an ion-conducting ceramic material as an electrolyte. The most estab-
lished technology is based on an YSZ electrolyte, which requires the cell to operate
between 800°C and 1000°C. These high operating temperatures demand expensive
materials for fuel cell interconnectors, cause thermal stresses, and require long start-
up times and large energy inputs to heat the cell up to the operating temperature.
Therefore, if SOFCs could be designed to give a reasonable power output at interme-
diate temperatures (IT, 400–700°C), tremendous benefits might result. However, in
the attempt to reduce the operating temperature, the increasing electrolyte resistivity
becomes one of the problems to overcome, since the ion-transport mechanism in
ceramic electrolytes is a thermally activated process. However, two approaches on
the development of nanomaterials for SOFC electrolyte can be followed: decreasing
the electrolyte thickness to nanoscale and using alternative nanomaterials that have
better ionic conductivity in the IT range than YSZ.
The thin electrolyte SOFCs usually have a configuration with electrode support,
and the electrolytes are typically less than 25 μm thick (De Jonghe et al. 2003). For
electrolyte less than ~100 nm thick, applications are mainly limited to micro-SOFC
(μ-SOFC) (Takagi et al. 2011). Scaling-up remains a significant challenge because
large-area membranes are susceptible to mechanical failure, while for optimum cell
performance the nanostructured electrolyte must have a fully dense structure to min-
imize reactant crossover. Atomic layer deposition has been considered as a promis-
ing fabrication method (Prinz et al. 2011). Shim et al. (2007) prepared freestanding
60-nm YSZ films on amorphous Si3N4, and maximum power density of 270 mW/cm2
was observed at 350°C. By depositing microfabricated metallic grids to function
as mechanical supports, Tsuchiya et al. (2011) successfully deposited a scalable
54-nm-thick 8 mol% YSZ electrolyte film for μ-SOFCs, from which a power density
of 155 mW/cm2 was achieved at 510°C. Some details of a platinum-grid-supported
5 × 5 mm μ-SOFC is shown in Figure 7.12.
Regarding the alternative materials with high ionic conductivity, one way is
focused on composition by materials optimization for both new and conventional
electrolyte materials or by exploring new compounds that support fast oxide ion or
proton conductivity. This topic was recently reviewed by Malavasi et al. (2010) in
their publication. Another broad area attracting increasing attention is nanomaterials
or nanoionics for the electrolyte. These systems are characterized by size effects,
short diffusion lengths, a high density of interfaces (e.g., grain boundaries), and, in
some cases, enhanced transport properties. More detailed discussions are found in
(a) (b)
100 μm
(c) (d) 200
Power density (mW cm–2)

0.8
510 °C
Pt anode 0.6
Voltage (V)
467 °C
100
0.4
YSZ 0.2 451 °C
0.0 0
0 200 400 600 800 1,000
100 nm LSCF
Current density (mA cm–2)
FIGURE 7.12 (See color insert.) Platinum-grid-supported 5 × 5 mm micro-solid oxide

fuel cell (μ-SOFC): (a) Optical micrographs taken from the cathode side at 480°C; (b) SEM
micrograph of slightly buckled freestanding membranes before testing; (c) cross-sectional
micrograph of μSOFCs after testing; (d) current voltage sweep of platinum-grid-supported
5 × 5 mm μSOFC at three different temperatures. (Reprinted by permission from Macmillan
Publishers Ltd. Tsuchiya [Nature Nanotechnology] [M. et al. 2011.], Copyright 2011.)
reviews by Maier (2005), Chadwick et al. (2006), and Arico et al. (2005), in which
an important finding was given by Santamaria et al. (2008). They reported an eight-
order-of-magnitude enhancement of YSZ conductivity in epitaxial heterostructures
consisting of two-unit-cell-thick YSZ thin films sandwiched between two thicker lay-
ers of strontium titanate (SrTiO3, STO). The origin of this huge enhancement in con-
ductivity and associated decrease in activation energy (from 1.1 to 0.6 eV) is thought
to lie in the YSZ/STO interfaces, in which the number of mobile ions increases, as
does the volume through which they can move. This interface has been investigated
by means of energy loss spectroscopy, showing that epitaxial growth between YSZ
and STO leads to a modified interface with a highly disordered oxygen plane. This
effect is a little similar to the synergy effect between alloyed catalysts and catalyst
with support from low-temperature fuel cells (Qiao et al. 2011; Zhang et al. 2007).
It is expected these kinds of novel processing strategies could lead to exciting new
technologies based on nanostructured low-temperature oxide ion conductors and thus
represent a potentially fruitful avenue of research.
7.3 MEMBRANE ELECTRODE ASSEMBLY

7.3.1 Novel MEAs for Low-Temperature Fuel Cells
Within the low-temperature fuel cells, the supported or unsupported catalyst is inti-
mately mixed with the electrolyte ionomer (e.g., Nafion) to form a composite cata-
lyst layer. The benefit of this approach is an enhancement of the interfacial region
between catalyst particles and ionomer, extending the triple-phase boundary (or
three-phase reaction zone). However, as discussed in MC supports, the large size
range at 20–200 nm of the ionomer makes it very difficult to soak deeply in the small
pores of the active layer. Thus, the reaction area is limited to an interface between
catalyst particles distributed on the outer surface of carbon (or themselves in the
unsupported case) agglomerates and the ionomer (as shown in Figure 7.13), resulting
in a very low catalyst utilization with a typically value 20%–30%.
So, much research has been carried out to improve the catalyst utilization ratio,
such as by reducing catalyst loading for a thinner active layer. One important contri-
bution is by 3M Corporation for the Pt-coated nanostructured whisker supports, as
shown in Figure 7.14 (Arico et al. 2005; Debe 2006; Garcia-Martinez 2010). Part of
the MEA is a nanostructured thin film catalyst based on platinum-coated nanowhis-
kers. The approach uses highly oriented, high-aspect-ratio single-crystalline whis-
kers of an organic pigment material. This support permits suitable specific activity
of the applied catalysts and aids processing and manufacturing. The electrocata-
lytic activities so obtained are comparable to catalyst–ionomer inks.
Secondary pores Primary pores

(40–300 nm) (20–40 nm)
Polymer
electrolyte
(PFSI)
e–
H+ Backing
layer
O2
0 z 1
Carbon grains Pt-particles
(20–40 nm), (2–3 nm)
forming agglomerates
(bounded by PTFE)
FIGURE 7.13 Schematic of a conventional composite (carbon-supported catalyst,

ionomer) catalytic electrodes for PEMFCs (z ~ 10 μm). (Debe, M.K., Nanostructured Thin
Film Catalysts (NSTFC) for Next Generation PEM Fuel Cells, University of Minnesota,
Minneapolis, MN, 2006.)
PEM GDL
3 µm 200 nm 2 µm
(a) (b) (c)
FIGURE 7.14 3M Corporation platinum (Pt)-coated nanostructured whisker supports

(0.25 mg/cm2), in plane view (a) and 45° view (b). The nanostructured film of the membrane
electrode assembly (c) shows the Pt-coated nanowhiskers sandwiched between the polymer
electrolyte membrane (PEM) and the gas diffusion layer (GDL). (Debe, M.K., Nanostructured
Thin Film Catalysts (NSTFC) for Next Generation PEM Fuel Cells, University of Minnesota,
Minneapolis, MN, 2006.)
200 nm 200 nm
(a) (b)
FIGURE 7.15 Gas diffusion electrode with a platinum-nanowire array grown on a gas dif-
fusion layer surface, at plane view (a) and side view (b).
In our group, we developed gas diffusion electrodes (GDEs) with a thin Pt-NW
catalyst layer (Du 2010), with a thickness about 0.5–1 μm. The single-crystalline
Pt-NW array was directly grown on a gas diffusion layer (GDL) surface by using a
reducing precursor of formic acid at room temperature in aqueous solution, without
using any templates, organic solvents, or induced-growing catalysts. The catalyst
synthesis process is the same as used by Sun et al. 2007 mentioned earlier, but by
replacing the carbon support with GDL surface, the GDE can be fabricated by just
one simple step without the catalyst-ionomer ink and coating process for fabricating
the catalyst electrode. Figure 7.15 shows the SEM images of the Pt-NW-based GDE.
The measurement in hydrogen/air single cell showed a higher power density than the
state-of-the-art E-TEK GDE 120E-W. A good adhesion between the Pt NWs with
support was also confirmed by the sonication treatment. A higher p erformance and
better durability were also obtained by testing a DMFC cathode (Du et al. 2011b).
This high performance and good durability of the Pt-NW electrodes, in a ddition to
the simple and cheap manufacture process, may offer a large potential in practical
applications. However, as a completely novel approach, it has been demonstrated that
a new procedure was necessary to fabricate MEAs from these GDEs in fuel cells,
such as changing the electrolyte ionomer loading amount (Du et al. 2011a). More
work on process optimization needs to be done before it can be put into practical
applications.
7.3.2 A Nonelectrolyte-Separator SOFCs

As we mentioned in Section 7.1, fuel cells are constructed with three functional
components: anode, electrolyte, and cathode. In SOFCs, to decrease the high oper-
ating temperatures, many efforts have also been made by reducing the thickness
of the electrolyte and nanoscale membranes have previously been fabricated, as
discussed in Section 7.2.2.1. Even like this, the interfaces between the electrolyte
and the electrodes (anode and cathode) produce major polarization losses. The
electrolyte acts as a bottleneck that limits the improvement of fuel cell perfor-
mance and thus delays its commercialization. Of course, if the electrolyte can be
eliminated, all these problems can then be ignored. Zhu et al. (2011a,b,d) reported
the nonelectrolyte-separator fuel cell (NEFC), creating a fuel cell from a single
homogenous layer.
The layer is made from a mixture of ionically conducting materials of (Na/K)2CO3–
Ce0.8Sm0.2O2−δ (NKSDC) (Li et al. 2010a, 2011) and nanoparticles of a LiNiZn(CuFe)-
based oxide and has both ionic and semiconducting properties. Moreover, when
hydrogen and air are supplied to either side of the layer, the composite can act as a
catalyst for both the oxidation of hydrogen and the reduction of oxygen. On one side,
hydrogen is broken down into protons and electrons, a function similar to that of the
anode of a typical fuel cell; whereas on the other, electrons are received through an
external circuit and oxygen from the air is split into negative oxygen ions, just like a
fuel cell’s cathode. Water is then thought to be generated through the direct combina-
tion of protons and oxygen ions on the surface of the particles.
A schematic of the device working principles was given by the team, as shown
in Figure 7.16. It works quite similar to dye solar cells (Oregan et al. 1991). A p–n
junction may be formed within the LiNiCuZn(Fe) materials to keep an effective
charge separation, where doping of NiO and ZnO shows p- and n-type conductiv-
ity, respectively. NKSDC and LiNiCuZn(Fe) form percolating paths among differ-
ent phases. It can thus guarantee both ionic (H+ and O2−) and electronic (n and p)
conduction in a continuous network throughout the component to support current
transferring paths and continuous outputs; the electrons and holes do not pass
through the component(s) but move to the corresponding current collectors because
of the p–n junction and its operating principle, the same as in the solar cell. The
exact mechanism of the underlying processes is still unclear, but the team showed
that the one-layer fuel cells could convert hydrogen and air into electricity and
water producing a power output of more than 680 mW/cm2 at 550°C (Zhu 2003; Zhu
et al. 2011a,c,d).
e‒
e‒
H2 O2
H2O H2 O
Current collector 100 nm TKK-NMC 10/15/2010

x 50,000 5.0kV SEI SEM WD 6.4 mm 10:07:40
(a) (b)
Percolative
conducting phase Non-percolated
conducting particle
Po2ʹ Po2ʹʹ
O2–
H+
O2– conductive H+ conductive phase

ceria phase
(c)
FIGURE 7.16 (a) Schematic of the configuration for a single-component n onelectrolyte-

separator fuel cell device; (b) SEM image of the cross section of the LiNiCuZn (Fe) oxide–
SDC single-component device; and (c) the working principles behind the fuel cell. (Zhu, B.,
Journal of Power Sources, 114, 1–9, 2003; Zhu, B. et al., Electrochemistry Communications,
13, 225–227, 2011a; Zhu, B. et al., Journal of Power Sources, 196, 6362–6365, 2011c.)
7.4 CURRENT LIMITATIONS IN NANOMATERIALS FOR

FUEL CELLS
Notwithstanding the importance of nanomaterials in the progress of fuel cell devel-
opment, there are still some issues needed to be solved before these nanomaterials
can be really put to practical applications, and the performance of practical fuel cells
remains limited by scale-up, stack housing design, gas manifold, and sealing. Some
of them can be overcome by the methods mentioned in the preceding discussion.
7.4.1 Fabrication of MEAs and Fuel Cells

Although progress has been achieved in the direct electrochemical oxidation of alcohol
and hydrocarbon fuels, fuel cells are still mostly fed by hydrogen (Arico et al. 2005).
The achievements with electrocatalysts in low-temperature fuel cells are mostly lim-
ited to the performance measured by ex situ electrochemistry measurement, for exam-
ple, cyclic voltammetry, rotating disk electrode, and half-cell measurement in lab test
(Du 2012; Jaouen et al. 2011). The tests in practical fuel cells usually suffer from the
very low quantity of the products obtained due to the large difficulty on scale-up,
caused by the high cost and the limitation of the fabrication method. For example, in
the preparation of electrocatalysts by template electrodeposition methods (Alia et al.

2010; Ponrouch et al. 2010) or organic solvent methods (Eichhorn et al. 2009; Lee
et al. 2008), large quantities of organic solvents and special precursors are used, as
well as the sacrificed template and the complex process, leading to very high costs; the
large difficulty in fabricating nanoscale electrolyte membranes in IT-SOFC limits the
applications only in μ-SOFC in lab research (Takagi et al. 2011; Tsuchiya et al. 2011).
Another major challenge is the MEA fabrication using these novel nanomaterials.
They usually possess quite different features when compared to the conventional Pt or
Pt/C nanoparticle electrocatalysts, offering these nanomaterials some special advan-
tages, for example, high reactivity and stability, but also unusual shapes, structures, or
other features, such as the nonisotropic NWs resulting in a thick catalytic layer with
loose structures (Cademartiri et al. 2009; Choi et al. 2003; Du 2012); the intrinsic
feature of the preparation methods for core–shell structure limit their feasibility to be
used for making supported electrocatalysts (Eichhorn et al. 2009; Strasser et al. 2010),
thus a high catalyst loading amount is necessary in MEA fabrication. Innovative solu-
tions for common problems are urgently needed in practical applications.
Indeed, novel approaches for MEA fabrication could be a solution to tackle these
important issues. For example, simple procedure and configurations, low preparation
cost, and easy scale-up process could make them promising techniques. However,
3M electrodes can still not eliminate the drawbacks from the spherical nanocatalysts
(e.g., easily aggregated to each other and Ostwald ripening of the small nanoparticles).
While Pt-NW-based GDE and NEFC are completely new approaches, the optimiza-
tion of the process for commercial applications still needs a very long time (Du et al.
2011a), and their long-term durabilities in real operating conditions are still unknown.
7.4.2 Disadvantages of Nanomaterials
7.4.2.1 Poor Durability in Fuel Cells
For nanomaterials, apart from the benefits brought by large SSA and high surface
reactivity, the high surface energy also leads to drawbacks including low thermody-
namic stability and high surface reactions. The low thermodynamic stability makes
nanomaterials form aggregates in preparation and during operation (Du 2012), and
the high surface reaction results in low stability of the whole MEA system, such as the
dissolution and Oswald ripening of the electrocatalyst (Yu et al. 2007a), and the risk of
secondary reactions involving electrolyte decomposition between the electrodes and
the electrolyte caused by the large SSA of the nanocatalysts (Guo et al. 2008).
7.4.2.2 Toxicity from Nanomaterials

When we mention fuel cell technology, we usually emphasize their advantages as
a clean technology, for example, environmental-friendly by reducing carbon emis-
sions. Unfortunately, very little research has been focused on health and safety risks
caused by nanoparticles in fuel cell systems or on their threats to the environment.
However, in the fabrication and operation, these nanomaterials can be released to
the environment and thus induce toxic problems to human body, the fauna, and
flora. Among the nanomaterials used in fuel cell systems, many have been shown
to induce toxicity problems, in particular metal nanocatalysts (Valiyaveettil et al.
2011), catalyst supports (e.g., CNT and carbon fiber) (Carriere et al. 2008; Porter
et al. 2011) in low-temperature fuel cells, ceria, or zirconia-based nanoparticles
(Lanone et al. 2009; Zhang et al. 2010b, 2011b) in SOFCs. Nanoparticles are small
enough to penetrate human and animal cell membranes and defenses, yet they are
large enough to cause trouble by interfering with normal cell processes. For exam-
ple, the mean life span of nematodes was significantly decreased by 12% even at
the exposure level of 1 nmol (p < .01) to nanoceria (8.5 nm) (Zhang et al. 2011b).
Pt nanoparticles can induce hatching delays as well as a concentration-dependent
drop in heart rate, touch response, and axis curvatures (Valiyaveettil et al. 2011). In
the nanomaterial production and processing, the operator may be exposed to these
nanoparticles by skin contact or breathing. In operation, these nanoparticles could
detach from the support and then be released to the environment along with output
water or gases.
Although detailed mechanisms are still not very well understood and stud-
ied, it has been shown that the toxicity of nanomaterials is determined by their
size, shape, structure, composition, concentration, origin, and many other fac-
tors (Reijnders 2008), such as ceria nanoparticles synthesized in biocompatible
media that could also be used as antioxidant in the treatment of medical disorders
(Karakoti et al. 2008). Thus, the toxicity of nanomaterials to human and environ-
ment can be greatly eliminated by some approaches in production and process-
ing as well as in operations. For example, in the fabrication of integrated Pt-NW
electrodes, catalytic electrodes were directly achieved on GDL surfaces by simply
one reduction step from precursor in aqueous solutions (Du 2010), whereby there
is no risk to produce free nanoparticles like Pt nanocatalyst, CB, or catalyst ink,
which are commonly used in MEA manufacturing process today and might be
environmentally and health hazardous based on previous studies on asbestos and
chrysolite (Xia et al. 2003). So, by the direct growth approach, the potential envi-
ronmental and health issues that might arise from such nanoparticles produced in
labs can be avoided.
7.5 CONCLUSIONS
Moving from bulk materials to the nanoscale can significantly change electrode
and electrolyte properties and consequently their performance and durability in fuel
cells. On one hand, nanomaterials show favorable and promising properties such as
enhanced kinetics and activity, which are simply a consequence of a reduction in
size, for example, when nanoparticulate electrodes or electrocatalysts lead to higher

electrode/electrolyte contact areas and hence higher rates of electrode reaction; in
other cases the effects may be more subtle, involving internally nanostructured mate-
rials or nanostructures with particular morphologies, for example, nanotubes. On
the other hand, nanomaterials also bring disadvantages such as low thermodynamic
stability, high surface reaction, as well as possible toxicity issues. The remaining
challenges include (1) a better understanding of various nanosize effects and then
developing new theories, (2) investigating fine details regarding the surface features
of nanomaterials, (3) designing optimized hybrid nano/microstructures and surface
modifications, (4) searching for new synthetic routes and new material systems, and
(5) moving nanomaterials from lab to fuel cells in practical applications. Solving
these challenges will require researchers from a wide range of disciplines, including
materials chemistry and surface science, as both are necessary to elucidate the role
and effect of nanomaterials. The development of novel nanomaterials will play an
important role in improving fuel cell performance and durability and breakthroughs
are urgently required to bring this green and sustainable energy device into real prac-
tical applications.
ACKNOWLEDGMENT
This work was supported by the Fellowships from Advantage West Midlands (AWM)
Science City Research Alliance (SCRA) awarded to Shangfeng Du.
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7.1 INTRODUCTION TO FUEL CELLS

Excess fuel or Unreacted O2/N2

Polymer electrolyte membrane fuel cell (PEMFC)

Polymer electrolyte; low Expensive catalysts; CO a strong Automotive; stationary

Direct methanol fuel cell (DMFC)

Phosphoric acid fuel cell (PAFC)

Molten carbonate fuel cell (MCFC)

Solid oxide fuel cell (SOFC)

Source: Brodd, R.J. et al., Chemical Reviews, 104, 4245–4269, 2004.

DMFC Carbon/platinum Carbon/platinum Acidic polymer 60–90

Source: Brodd, R.J. et al., Chemical Reviews, 104, 4245–4269, 2004.

7.2 BENEFITS OF NANOMETER SIZE EFFECTS

7.2.1 Nanomaterials for Fuel Cell Electrodes

7.2.1.1 Electrocatalysts in Low-Temperature Fuel Cells

MAD (100 + 111) = (100 + 111) N(t)

Pt particle size (nm) 0.1

SAD (100 + 111) = (100 + 111) N(s)

Spec. Act. at 0.9 V

Therefore, we cannot keep improving the catalytic performance of electrocatalysts

7.2.1.1.1 Pt-Based 0-D Nanoelectrocatalysts

(a) (b) (d) (e)

(f ) (g) (i) (j)

More research work is needed to explain the complexities of facet effect.

7.2.1.1.2 Nonprecious 0-D Nanoelectrocatalysts

nanostructure could also be prepared without support, where a multiarmed ­starlike

7.2.1.1.4 Core–Shell Configuration

in the core–shell configuration mentioned in the preceding discussion in some degree.

Mass activity (mA/mg Pt)

7.2.1.2 Catalyst Support in Low-Temperature Fuel Cells

7.2.1.2.1 Carbon-Based Nanostructures

7.2.1.2.2 Noncarbonaceous Supports

density and to lower the polarization resistance present at the cathode/electrolyte

7.2.2 Enhanced Ionic Conductivity and Structural

FIGURE 7.11 Schematic cross-section of a polymer electrolyte membrane (PEM). The

However, most of the research products are only demonstrated in l­ aboratory-scale

7.2.2.2 Electrolyte for SOFCs

(c) (d) 200

Power density (mW cm–2)

YSZ 0.2 451 °C

FIGURE 7.12 (See color insert.) Platinum-grid-supported 5 × 5 mm micro-solid oxide

7.3 MEMBRANE ELECTRODE ASSEMBLY

Secondary pores Primary pores

FIGURE 7.13 Schematic of a conventional composite (carbon-supported catalyst,

(a) (b) (c)

FIGURE 7.14 3M Corporation platinum (Pt)-coated nanostructured whisker supports

7.3.2 A Nonelectrolyte-Separator SOFCs

Current collector 100 nm TKK-NMC 10/15/2010

O2– conductive H+ conductive phase

FIGURE 7.16 (a) Schematic of the configuration for a single-component n­ onelectrolyte-

7.4 CURRENT LIMITATIONS IN NANOMATERIALS FOR

7.4.1 Fabrication of MEAs and Fuel Cells

the preparation of electrocatalysts by template electrodeposition methods (Alia et al.

7.4.2.2 Toxicity from Nanomaterials

size, for example, when nanoparticulate electrodes or electrocatalysts lead to higher

American Chemical Society 132:2183–2195. DOI: 10.1021/ja906975z.

nanostructure could also be prepared without support, where a multiarmed starlike

7.2.2 Enhanced Ionic Conductivity and Structural

However, most of the research products are only demonstrated in l aboratory-scale

FIGURE 7.16 (a) Schematic of the configuration for a single-component n onelectrolyte-

7.4 CURRENT LIMITATIONS IN NANOMATERIALS FOR