INTERNATIONAL JOURNAL OF ENERGY RESEARCH

Int. J. Energy Res. (2009)

Published online in Wiley InterScience
(www.interscience.wiley.com). DOI: 10.1002/er.1600

Solid oxide fuel cell (SOFC) technical challenges and solutions

from nano-aspects

Bin Zhu1,2,,y
1
Department of Energy Technology, Royal Institute of Technology (KTH), S-100 44, Sweden
2
GETT Fuel Cell AB, S-10314, Stockholm, Sweden

SUMMARY

The classical (over 100 years) oxygen ion conductor and theory for solid oxide fuel cells (SOFCs) have met critical
challenges, which are caused by the electrolyte material, the heart of the SOFC. Ionic conductivity of 0.1 S cm1 as a basic
requirement limits conventional SOFC electrolyte material, yttrium stabilized zirconia (YSZ) functioning at ca. 10001C.
Such high temperature prevents SOFC technology from commercialization. Design and development of materials
functioning at low temperatures are therefore a critical challenge. State of the art of the nanotechnology remarks a great
potential for SOFCs. Through a review of typical SOFC electrolyte materials and analysis of the ionic conduction theory
as well as constrains and disadvantages in single-phase materials, the need for design, development and theory of new
materials are obvious. Our approach is to design and develop two-phase materials and functionalities at interfaces
between the constituent phases in nanotech-based composites, that is nanocomposites. The nano- and composite
technologies can realize superionic conduction by constructing the interfaces as ‘ion highways’. Manipulation of the
interphases of the nanocomposites can overcome SOFC challenges and thus enhance and improve material conductivity
and FC performance at significantly lower temperatures (300–6001C). Copyright r 2009 John Wiley & Sons, Ltd.

KEY WORDS: low temperature solid oxide fuel cell; nanocomposites; single-phase material; two-phase material;
interfaces; superionic conduction; bulk mechanism; interfacial mechanism

1. INTRODUCTION temperatures (HT) and prevent the SOFC com-

Solid oxide fuel cells (SOFCs) are one of the most
promising fuel cell (FC) technologies. But the
challenges are critical and problems are caused by
the electrolyte materials that function only at high
mercialization. The currently used SOFC material,
yttrium stabilized zirconia (YSZ), was discovered
100 years ago by Nernst [1] and used for SOFCs
in the 1930s [2]. For over half a century, extensive
SOFC R&D based on the YSZ have been

*Correspondence to: Bin Zhu, Department of Energy Technology, Royal Institute of Technology (KTH), S-100 44, Sweden.
y
E-mail: binzhu@kth.se

Contract/grant sponsor: Swedish Agency for Innovation Systems (VINNOVA)

Contract/grant sponsor: Swedish Agency for Energy (STEM)
Contract/grant sponsor: EC FP6 NANOCOFC; contract/grant number: 32308

Received 29 April 2009

Revised 28 June 2009
Copyright r 2009 John Wiley & Sons, Ltd. Accepted 28 June 2009
 B. ZHU
undertaken. An electrolyte conductivity of
0.1 S cm1 is a basic requirement for FCs. The
YSZ reaches 0.1 S cm1 at ca. 10001C, thus
causing the HT SOFC technology. Designing
and development of functional materials at lower
temperatures (LT) are a critical challenge [3] and
therefore there is a world tendency to develop
SOFCs for low temperatures. Many efforts have
been done by using thin-film technologies on YSZ
to reduce the operational temperature [4–7]. But a
thin film electrolyte can not guarantee a long
SOFC life because FC operation involves mass
transport processes which can affect the electrolyte
property in one or another aspect, thus causing
serious degradation. Even if using the thin film
YSZ the operational temperature requires still
above 7001C or so.
State of the art of nanotechnology remarks a
great potential for SOFC or ceramic FC areas,
now moving down from HTs (above 7001C) to
low temperature SOFCs. Nanostructured solid-
state ionic electrolyte, coined as ‘nanoionics’ [8,9],
has recently become one of the hot areas of
research related to nanomaterials, since they can
be used in advanced energy conversion and storage
applications [10], for example SOFCs [11–17].
A more effective way is to develop new materials
with improved performance, for example super-
ionic conduction at LT, say 0.1 S cm1 at
300–6001C [18–20]. The 300–6001C FC technology
is a gap in the worldwide FC R&D. The
300–6001C FCs open many opportunities of
applying new architectures of nanocomposite
that yield high performance and conductivities
resulted from nanomaterials blocks and two-
phase interfaces. The ability to manipulate and
engineer material synthesis and processes at
atomic and molecular level can create radical
new architectures, materials and structures
with unique functionalities and characteristics.
Manipulating interphases of nanotech-based
composites, so-called nanocomposites provide su-
perionic conductivity at significantly LTs (from
10001C to 3001C). Development of 300–6001C
SOFC technology also opens up new market
opportunities since applications of nanotechno-
logy for FCs give a great potential to reach ultra
low cost.
Copyright r 2009 John Wiley & Sons, Ltd.
In the 300–6001C FC the high performance is
attributed to superionic conduction at interfaces in
nanocomposite electrolytes. This interfacial mecha-
nism opens a new scientific disciplinary to
design and develop advanced functionalities and
materials with new opportunities to overcome
SOFC challenges. Our ongoing NANOCOFC (EC
(Turkey)-China Nanocomposites for advanced FC
technology) network, www.nanocofc.org, has
carried out extensively innovative FC R&D based
on multi-functional nanocomposites. This report,
which covers a brief review and analysis of the
SOFC electrolyte materials, the ionic conduction
theory, as well as constrains and disadvantages in
single-phase materials, presents new design and
development of two-phase materials and func-
tionalities, especially in nanotech-based two-phase
materials, that is nanocomposites, and solutions
from nano-aspects in comparison to the conven-
tional materials commonly described in literature.
2. BASIC OF SOFC MATERIALS
It is very important to recognize the current SOFC
electrolytes’ constrains and disadvantages, which
have caused challenges for SOFCs. We may find
solutions based on the understanding of the SOFC
material science and physical properties behind.
Recent SOFC material developments made by
using nanotechnology will also help identifying
problems and solutions.
2.1. Oxygen ion conductivity: structure effects
Currently used SOFC electrolytes are based on
oxides, for example YSZ and ceria with a fluorite
structure (see Figure 1). Zirconium or cerium
atoms in a face-centered pattern contain a cube of
oxygen atoms (purple). Zirconia and ceria oxides
form the same crystal structure. Fluorite has a
simple structure–space group Fm3m. A structural
unit cell contains fully four cerium and eight
oxygen ions, the 1:2 stoichiometry is maintained.
The pure zirconia or ceria are very poor oxygen
ion conductors. The oxygen ion conductivity takes
place by aliovalent doping to create oxygen
vacancies inside their structures. From a phase
structure perspective, stabilized zirconia, for
Int. J. Energy Res. (2009)
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 SOLID OXIDE FUEL CELL
Figure 1. Fluorite structure for SOFC electrolytes.
example YSZ or ion doped ceria is a single-phase
material since the doping or guest phase, usually
8 mol% Y2O3 in ZrO2 or 10–20 mol% Sm2O3 in
CeO2 to form a solid solution that the Y2O3 or
Sm2O3 is fully ‘dissolved’ in the zirconia or ceria
lattice to maintain the host fluorite structure.
The effect of dopant oxides on the ionic con-
ductivity in ZrO2-based or CeO2-based binary
systems has been extensively investigated. The
main dopants used for stabilizing ZrO2 include
trivalent rare-earth or metal oxide: Y2O3, Yb2O3,
Sc2O3, etc.; divalent metal oxide: CaO, MgO, etc.;
while Gd2O3, Sm2O3, La2O3 CaO, MgO, SrO, etc.
used for CeO2. The fluorite is a very open structure
where large contents of dopant oxides can be
dissolved into the lattice, in the same time to create
large amounts of the oxygen vacancies.
For example, when a divalent or trivalent metal
oxide MxOy is doped in the zirconia or ceria
matrix to form a solid solution, the following
defect reactions would occur:
ZrO2 00  
MO ! M Zr=Ce þVO þOO
ZrO2
M2 O3 ! 2M0 Zr=Ce þVO þO
O ð1bÞ
The oxygen ion migration or diffusion can
occur only when the neighboring oxygen site is
a vacancy. The existence of a large number of
octahedral vacancies created by doping in struc-
ture makes it easier for an O2 to migrate from
one site to the neighboring one, in case that the
latter is a vacancy.
Copyright r 2009 John Wiley & Sons, Ltd.
O2-
M4+ (host cation)
M2+ or M3+(aliovalent cation)
Oxygen vacancy
Though high doping concentration results in
high defect (oxygen vacancy) concentration to
facilitate the oxygen ion mobility or conductivity,
after reaching a limit a stronger defect association
takes place, for example
M0 Zr=Ce þVO ! ½M0 Zr=Ce VO  ð1cÞ
2M0 Zr= þVO ½M0 Zr VO M0 Zr  ð1dÞ
This equals to occupation of the oxygen va-
cancy to make the oxygen sublattice ordering, thus
reducing the O2 conductivity. This prevents fur-
ther increasing the material conductivities.
The ionic conduction is described by Arrhenius
equation:
sT ¼ s0 expðEa =kTÞ ð1eÞ
A simple theoretical analysis [21,22] can deduce
Equation (1f ) below, and help us to understand
ð1aÞ
the Arrhenius relation (1e) and ionic conduction
phenomenon.
nz2 e2 gd 2 o0
s0 ¼ ð1fÞ
6k
The advanced ion conductor design is thus to
maximize s0 and minimize Ea. Two parameters
(d, ion mean jump distance and n, mobile ion
concentration) are important to maximize the s0.
From this analysis we may identify the following
Int. J. Energy Res. (2009)
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 B. ZHU

disadvantages and limitations for the single-phase

materials:

(i) Within the structure unit, a strong interaction

between oxygen ions and cations contributes
major part of the high Ea values in the order of
1.0 eV (while o0.5 eV is required for super-
ionic conduction); grain
(ii) s0 is limited by the crystal unit cell at least in
two aspects, (a) n is limited by the degree of
doping resulting in a low concentration, for
example 8 mol% of Y2O3 in YSZ; though the
higher doping can increase the oxygen vacancy
concentration, in the same time the higher
defect (oxygen vacancy) concentration will
reduce the oxygen ion conductivity due to
the defect association; (b) d is limited in a unit
cell, that is of the order of some Angstrom. Grain
boundary

These structural effects put strong limitations

on the conventional SOFC materials, resulting in
high activation energy, low oxygen ion con-
centration, and mobility; thus HT is required to
activate sufficient ionic mobility, for example
10001C for YSZ. Added to these the nonstructural
effects are even more crucial.
2.2. Oxygen ion conductivity: microstructural effects
The basic considerations are as follows:
(i) Ceramic electrolytes are polycrystalline and
consist of grains, grain boundaries, pores, etc.
as shown in Figure 2;
(ii) Grain boundaries (gb) often acting a predo-
minating role have a significant influence on
overall properties;
(iii) Studies of grain boundary behavior are
essential to design ceramic materials and to
control and optimize their properties.
In the majority of oxygen ion conductors, the
smaller the grain size, the higher the resistivity
because of:
(i) inter-grain neck and contact;
(ii) space charge effects that tend to lower oxygen
vacancy concentration near the grain boundaries;
Figure 2. Polycristalline electrolyte from a SEM view.
(iii) insufficient oxygen vacancies in the grain
boundaries [23].
The conductivity of the polycrystalline electro-
lyte is contributed from both grains and grain
boundaries. The grain boundary resistivity in
stabilized zirconia or doped ceria is often in mag-
nitude higher than the grain resistivity, despite the
ion transport activation energy typically ranging
between 1.08 and 1.16 eV, higher than that of the
grain [24]. Figure 3 shows schematically the
situation in the polycrystalline electrolytes, where
continuous grain boundaries’ network with high
resistivity surrounds grains. This indicates that
though the structure of the stabilized zirconia or
doped ceria is optimum for the high ionic con-
ductivity, the polycrystalline nature from the non-
structural effects, the microstructural morphology,
etc., is more important to determine the final
conductivity. The emphasis should be, therefore,
placed on engineering of the grain boundaries by
enhancing the local oxygen vacancy concentration

Copyright r 2009 John Wiley & Sons, Ltd. Int. J. Energy Res. (2009)
DOI: 10.1002/er
 SOLID OXIDE FUEL CELL
Figure 3. A schematic of continuous grain boundaries network that are highly resistant surround grains in the
polycrystalline electrolytes.
at the grain boundary entails then significantly
lowering the grain-boundary resistance in order to
obtain material high conductivity.
2.3. Remarks
State-of-the-art of the current SOFC materials and
oxygen ion conductor/tion in the single-phase
materials may tell us:
(i) Ion doping is a way to generate structural
defects (oxygen vacancies) in structure for
creating the oxygen ion mobility and con-
ductivity; however, the microstructure plays a
crucial role to determine the material final
conductivity;
(ii) Though the fluorite structure has large capa-
city to accept high doping contents, above a
doping level limit, the defect (vacancies)
association occurs to decrease conductivity;
(iii) Because of structural limits and high activa-
tion energy, the sufficient O2 conductivity/
mobility occurs only at HTs, for example
0.1 S cm1 at 10001C for YSZ or 8001C for
doped ceria;
(iv) Grain boundaries or interior contacts between
particles are barriers to limit the ionic
conductivity since the grain boundary con-
ductivity is much lower than (order) that of
Copyright r 2009 John Wiley & Sons, Ltd.
the grain thus blocks the ionic transport.
Engineering of the grain boundaries is a top
option to improve and develop material ionic
conductivity.
2.4. Nano-effects and new principles
However, the situation changes at the nano-level
with new materials, functionalities, and principles.
Recent developments are directed by extensively
using nanotechnology and nano-size materials
for the conventional SOFC electrolytes and sup-
port new scientific principles. These new studies
from nano-aspects have shown the common facts
that the nanostructured ceria-based materials
[12–15] and YSZ [16,17] exhibited strong conduc-
tivity enhancement, due to significantly larger
area of grain-boundary or interface in nanostruc-
tured systems, which increases the concentration
of mobile defects in the space-charge zone [9,10].
The grain-boundary in ionic conduction
suddenly turns from negative/side effect in the
normal-sized (say micrometer level) to positive
effect as promoter in the nano-sized materials.
These new developments obviously disagree
with the mainstream of the current SOFC Science
built on the conventional materials as described
above.
Int. J. Energy Res. (2009)
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 B. ZHU
The different particle size levels may cause
completely different ion transport phenomena. In
the normal particle size the grain boundary blocks
the ion transport ways, thus causing extremely
high resistivity gap between the grains. The ions
migrate from one grain into another forming a
discontinuous path thus causing low ion con-
ductivity (see Figure 3); while in nano-scale, the
situation changes to opposite where the grain
boundaries become ion conduction highways.
Compared to this the grain contribution becomes
less important. In the state-of-the-art of the con-
ventional materials, the approach is to eliminate
the grain boundaries to a minimum level in order
to obtain high material conductivity. Conversely,
in nano-scale grain boundaries in the single phase,
or interfaces and interfacial contacts in the two-
phase materials should be optimized to a max-
imum. An ionic conduction principle presented in
Figure 4 [25] may help to understand the different
phenomena and principles. In the micrometer
level, the O2 ions can migrate through the grains/
structure; while in the nano-scale, the difference of
the sizes between the mobile ions and the grain is
significantly decreased (hundreds of times less than
that in the micrometer level), which causes a
strong expulsion force to resist the O2 migration
while the ion approaching the grain, thus causing a
‘by-path’ for ion pass around the grain, that is
grain boundary or interface path.
The design and development of functionalities
and advanced materials in the mm and nm levels
require thus very different approach, principle
and theory. We need to fully recognize their dif-
ferent scientific natures/characteristics to guide
new material designs, developments and theories.
Nano-structured materials can enhance the con-
ductivity due to strong grain-boundaries’ effects.
However, the nano-sized oxide conductors in the
µm scale
ion grain
nm scale
Figure 4. A principle presentation of the ionic migration
at micrometer and nanometer levels, where grain
boundaries act as side paths for ion pass.
Copyright r 2009 John Wiley & Sons, Ltd.
single-phases are not stable, especially for SOFC
environment at HTs. The nano-structured single-
phase materials, typically YSZ and doped ceria
may not function for SOFCs, where hundreds of
degrees Celsius can easily destroy the nano-
structures in addition to strongly reducing and
oxidizing environments. Moreover, in the nano-
ceria case following side effects can occur [26]:
(a) transition from ionic to e conduction when
the particle turn to the nano-scale,
(b) electronic conductivity (se) increases for
nano-sized particle,
(c) ionic activation energy, Ea is also increased
with decreasing grain sizes.
Thus the single nano-ceria materials for SOFCs
cannot be approved. To develop stable and
functional nano-materials qualified for SOFC
applications is, therefore, a critical challenge and a
tough job.
3. NANOTECHNOLOGY AND
APPROACHES AND ADVANCED
MATERIAL DESIGNS
3.1. Basic of advanced ionic conductors
The basic material design on advanced ionic
conductors can be considered from fast ionic
conduction or superionic conduction theory. The
principle is to design and realize the structure that
can offer long-distance channels or networks for
ionic conduction/transport. From this aspect,
though YSZ or ion-doped ceria are viewed as the
open structure with large feasibility to create
structure defects by ion-doping for ionic conductiv-
ity, it is very much under demands of the superionic
conduction, since the oxygen ion does not migrate in
the long-distance or networking in these materials.
In the two- or multiphase nanocomposite
materials the two-phase co-existence creates the
interfaces and particle surfaces between the con-
stituent phases, where the superionic conduction
takes place. Also, the energy to form defects on
the surfaces or interfaces is significantly lower
than that inside the bulk structure. Thus, low
temperature can activate sufficient ion mobility.
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 SOLID OXIDE FUEL CELL
The interface has, in principle, no bulk structural
limit to create high concentration of mobile ions,
and can thus be very disordered. This implies that
the interfaces have the capacity to contain higher
mobile ion concentration and also longer range
transport channels/networks (from particle to
particle at nanometer level) in the interfaces than
those of the bulk effect occurring within a crystal
(e.g. YSZ) unite cell (at Angstrom level) of the
bulk, thus strongly enhance the conductivity.
3.2. Two-phase architectures and functionalities
of the nanocomposites
Multifunctional nanocomposites for advanced
LTSOFCs are based on developing and modifying
nano-particles’ surface physical and chemical
properties to obtain new desired properties that
the bulk materials do not possess. The surface
effect becomes more significant with the particle
sizes decreasing, especially o10 nm. At this level
atoms mostly concentrated/shifted on the nano-
particle surfaces from the bulk (e.g. at 1 nm level
almost all atoms 490% will stay on the surfaces).
These atoms lack coordination or configuration
with very high surface energy and are thus easily
ready to interact with other material’s atoms to be
stabilized. Such activated or unstable surface
atoms (ions) become highly mobile, resulting in
superionic conduction at interfaces. Clear under-
standing of physics behind the ionic conductivity
would be very helpful for the development of
Figure 5. A schematic of continuous interfaces between the two constituent phases acting as high ionic conducting
ways or network where the interfacial conduction between the two constituent phases are indicated by arrows (after
Reference [27]).
Copyright r 2009 John Wiley & Sons, Ltd.
complex architectures of nanocomposites (shape
and configuration). The superionic conductivity
40.1 S cm1 in the 300–6001C range can be
realized by two-phase nanocomposites with new
architecture by constructing interfaces as ion
highways to result in superionic conduction in
network with continuous paths. This has been
dealt with by a theoretical approach reported
before on the ceria-carbonate (as the 2nd phase)
composites, see Figure 5 [27]. The ion transport
mechanism in interfaces is under study and needs
more investigations both experimentally and
theoretically since there is a lack of knowledge
and theory on this subject. Based on the nano-
science principle, several concepts of the advanced
material architectures may be presented below.
3.2.1. Architecture 1. The concept of ‘nanocom-
posite’ [28–30] by adding a secondary phase as
inclusion can effectively hinder the grain growth of
nanostructures. Nanocomposite approach can
create a nano-core particle with a nano-layer-shell
formed by the 2nd phase, or by interaction (layer/
shell) between the constituent phases, both core
and shell/layer are material components to create
functionalities. This approach can prevent the
nano-functional particles from energetic growth at
HTs and high activity in extreme atmospheres. In
the same time it can create new functions/proper-
ties at interfaces between the two constitute
phases. It is common that nano-sized particle in
single-phase materials can, on one hand, create
Interfacial
paths
Int. J. Energy Res. (2009)
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 B. ZHU

large particle surfaces, but on the other hand the
particles are not stable because of high surface
energy and the active and chemically unbounded
situation. In two-phase materials large use of the
appropriate 2nd phase material/particles can
create interfaces and surfaces with effective func-
tions in two-phase nano-particles while, in the
same time, it can stabilize and modify the surface
properties. The key is to use the appropriate 2nd
phase, which can construct particle–particle and
phase–phase interactions and interfacial electrical
field by fixing the surface configuration and
stabilizing the surface properties. Our recent
achievements on the core-shell ceria-carbonate
electrolytes [31] have demonstrated such advances,
where the core-shelled structure have exhibited a
great thermal stability compared to single-phase
ceria, see Figure 6 [32]. In the same time created
superionic conduction, see Section 3.3, Nanocom-
posite approach makes it possible to apply
nanomaterials to a new field of SOFC R&D, since
the surface energy and diffusion rate of the
nanostructured materials are greatly modified by
accession of the second phase materials, resulting
in suppression of grain growth under HT.
3.2.2. Architecture 2. Nano-wires and long ionic
conduction paths/channels
As one of the attractive nanomaterials with unique
chemical and physical properties, one-dimensional
(1D) nanowires have attracted a lot of interest for
both scientific research and technological applica-
tions [33–36]. Based on the interface conduction
theory, the 1D nanowires structure is supposed to
have a longer continuous interface when forming
the two phase nanocomposite electrolyte, which
indicates it may achieve higher ionic conductivity
compared to nanoparticles, the 3D nanomaterials.
Therefore, application of doped ceria nanowires in
SOFCs field is a challenge and will open up a new
area in nanocomposite electrolyte R&D.

Figure 6. SEM image of: (a) uncoated SDC (samarium doped ceria) annealed at 7001C for 2 h; (b) uncoated SDC
annealed at 7001C for 24 h; (c) SDC/Na2CO3 nanocomposites annealed at 7001C for 2 h; and (d) SDC/Na2CO3
nanocomposites annealed at 7001C for 24 h. Scale bar: 200 nm (after Reference [32]).

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 SOLID OXIDE FUEL CELL

The SDC nanowires structure in the composite Figure 7, where the nano-catalyst particles
can be optimized and better aligned to achieve (5–10 nm range) are highly homogenously distrib-
superionic conductivity. It is certainly a very uted in the composite electrode, resulting in high
potential electrolyte material, since one dimen- catalyst and electrode functions and LTSOFC
sional nanowires structure is supposed to have performances.
longer continuous conductive path at interfaces in Using electron microscopy (EM), the phase
nanocomposite electrolyte, which indicates it may structures of nanoparticles and their interfaces can
achieve higher ionic conductivity compared to the be examined. It also allows physical parameters
3D nanoparticles. It opens a new interesting (such as shape and size) of these nanoparticles to
subject for research. be characterized. With advanced EM techniques
such as high-resolution TEM (HRTEM), electron
3.2.3. Architecture 3. Redox properties in two- energy loss spectroscopy and the selected area
phase materials: The redox property of ceria has electron diffraction it is expected that the ionic
been applied in catalyst field for decades with transport within the particles and their boundaries
successful applications. This property is based on as well as two-phase interfaces can be clarified. All
reversible Ce41-Ce31 process accompanying these microstructural information will be very
oxygen depletion and deposition. The single-phase valuable to help improve the design of materials
ceria alone causes both electrical and mechanical
problems for SOFC applications. The new idea
may be that we could take the advantage of the
Ce41-Ce31, then use two-oxide with redox proper-
ties in the two-phase material architecture. Typical
examples are CeMO2 (M 5 Sm, Gd, Y, Tb, Pr,
Mn, Ca, etc.)-MxOy (M 5 Ti, Bi, V, Co, Ni, Cu,
Fe, etc., x 5 1–3, y 5 1–4) through the redox cycle
between two-phase components to enhance and
adjust the material properties and create new
functions. This architecture has a significant role
in creating functional interfaces. For example, for
electrolyte materials it may create superionic
conduction and mechanical stability; also ceria-
based two-phase material nanocomposites
(nano-particles, nano-rods, and nanotubes) may
be constructed with other H1/O2 conductors in
different configurations/architectures (core–shell,
capping, bonding, and linking). It has been
discovered that a number of ceria-salt composites
possessing dual H1/O2 conduction either
forming intermediate bonding or cationic
vacancies with the salts [37,38]; these are more
considered as an interfacial mechanism [39];
for electrodes, the ceria- two-phase materials
including electronic conductor and catalysts, for
example NiO, CuO, WO3, MoO3, and carbon
nanotubes, act the electrode functions. We have
recently been using the nanocomposite or Figure 7. (a) The SEM picture of a nanocomposite
NANOCOFC approach successfully developed electrode; (b) the TEM image of a nanocomposite
nanocomposite electrode materials, as shown in electrode.

Copyright r 2009 John Wiley & Sons, Ltd. Int. J. Energy Res. (2009)
DOI: 10.1002/er
 B. ZHU
and manufacture of FCs. We are conducting
extensive studies in this field.
3.3. Nanocomposites and interfacial functionalities
Development of synthesis methods (e.g. sol–gel
technique, co-precipitation, combustion, microwave
heating, multi-layer growing, nano-colloid stabiliza-
tion, combinatorial and high-throughput synthesis
and testing, thermal spray, nano-coatings, etc.) are
important to develop the new materials with
controlled microstructure, porosity and bulk and
surface/interface composition with new physical and
chemical properties. New architectures with desired
functionalities may be developed. For example,
nanocomposites by intercalation of polymers and
biopolymers into layered inorganic compounds;
Preparation of stabilized multi-component nano-
structures based on nanosized supported metals and
mixed oxides; well-defined model interface/layered
systems; Self-assembling properties of materials play
important role in fabrication of new compositions
with new physical and chemical properties; Dis-
ordering structures by interactions between surfac-
tant and the 2nd guest phase particles introduced by
nanotechnology. Furthermore, conventional doping
methodology in developing functional nanocompo-
sites is not only used to create structural defects
same as the conventional way, but more importantly
as the particle surface modifier of the nano-
environment to build functionalized interfaces upon
using controlled surface reactions in both hetero-
geneous and homogeneous. Many new nanocom-
posites and functionalized interfaces or interfacial
functionalities will be developed for successful LT,
300–6001C SOFCs, next generation FC R&D [39].
Among all interfacial functionalities, the ionic
conductivity or low temperature, 300–6001C
superionic conduction is most important for
LTSOFC R&D. Unlike the conventional super-
ionic conduction that appears in a single-phase
material accompanying a structural change, the
superionic conduction in the composites is
determined by the interfaces, that is a process
breaks symmetry of matrix by introducing a
structural discontinuity [9]. In contrast with the
bulk, where electroneutrality must be obeyed, at
the interface a narrow charged zone, the so-called
Copyright r 2009 John Wiley & Sons, Ltd.
space-charge zone is tolerable and thermo-
dynamically necessary [40]. The defect concentra-
tions in the space-charge zone are much higher
than that in the bulk, which accounts for higher
ionic diffusivity and mobility than bulk. One effi-
cient method to enhance the space-charge effect is
to decorate the grain boundaries with surface-
active second-phase materials, which is also called
heterogeneous doping process [41]. The ceria-
based composite electrolyte with remarkable ionic
conductivity is a victorious case of superionic
transitions excited by heterogeneous doping pro-
cess, where interface supplies high conductivity
pathways for ionic transportation and conduction.
Though in single-phase materials the nano-
effects can effectively increase the material
conductivity, the Debye length is significantly
decreased to reduce the concentration (number) of
the mobile species in the nano-scale, resulting in no
effect on enhancement of the ionic conductivity.
The nanocomposite approach can overcome the
single-phase material bulk nano-side-effect be-
cause of creating tremendous surfaces/interfaces
where the ionic conduction takes place. In nano-
sized materials, calculations show that the mean
free volume is significantly larger at boundaries,
which enhances the mobility of ions at the
boundary core. The enhanced boundary diffusion
leads to significant enhancement of effective dif-
fusion coefficients of materials with a high
boundary density. In the case of ionic materials,
this boundary mechanism or interfacial mechan-
ism in the two-phase nanocomposites may make
the superionic conduction in the nano-regime.
We have taken as a case study on the ceria-
carbonate two-phase material to discuss interfacial
mechanism. The calculations showed that the
oxygen ion activation energy in such interface is
o0.2 eV (to well meet the superionic conduction
request) [27], while it is around 1.0 eV via the bulk
effect in the single-phase material YSZ or ceria.
The results obtained from the HRTEM analysis
has proven a clear interface in the ceria-carbonate
two-phase nanocomposites between the SDC
(Samarium-doped ceria) and carbonate forming a
core-shelled structure, see Figure 8(a), and such
interface (being usually amorphous) has resulted
in superionic conduction, 0.2 S cm1, a sharp
Int. J. Energy Res. (2009)
DOI: 10.1002/er
 SOLID OXIDE FUEL CELL

advanced technologies, for example industrial

material technology for cost-effective LTSOFCs
[42] and direct alcohol (biomass-base produced)
fuelled 300–6001C FCs [43] are under develop-
ments within the Swedish company GETT FC
AB, KTH and other joint industrial efforts. In
KTH, the existing EXPLORE: future energy
platform established in the Department of Energy
Technology has the FC polygeneration as one of
the most active components. These present an
emerging need on innovative FC R&D and solu-
tions to realize the LTSOFC commercialization.
(a)
(°C)
550 500 450 400 350 300 250 200 150
0.0
-0.5 4. CONCLUSIONS AND SUMMARY
-1.0
-1.5 Classical oxygen conduction and theory in single-
-2.0
-2.5 phase materials encounter critical challenges. State-
-3.0 of-the-art of the conventional SOFC materials
lgs (S/cm)

-3.5
-4.0
-4.5
-5.0
-5.5
-6.0
-6.5
-7.0
-7.5
1.0 1.2 1.4 1.6 1.8 2.0
(b) 1000/T (1/K)
Figure 8. (a) The TEM of core-shelled ceria-carbonate
nanocomposites; (b) temperature dependence of the
conductivities for core-shelled ceria-carbonate nano-
composites (after Reference [31]).
conductivity leap takes place below 3001C, see
Figure 8(b). As a fact melting point of Na2CO3 is
at ca. 8501C, while individual SDC and Na2CO3
are almost nonconductive at 3001C. Evidences
of the interfaces and significantly improved
performance for the ceria-carbonate two-phase
material system proves that interfaces play a
dominant role in this effect. The 3001C superionic
conduction with the same conductivity level as
YSZ at 10001C and advanced two-phase nano-
composites show indeed a breakthrough in the
SOFC materials.
This research area can strongly support new
generation SOFC R&D and eventually present
solutions to realize SOFC commercialization.
Based on the new functional materials several
contains a number of limitations and disadvantages
that do not meet demands of applications. Beyond
the structural limit, nonstructural or microstructure
effects play even more crucial role with negative
effects on the ionic conductivity. Nanotechnology
and nanoeffects discovered in the conventional
2.2 2.4 2.6 materials, for example YSZ and ceria exhibit a
great potential and open up new scientific areas.
However, nano-sized single-phase alone cannot
overcome the challenges that SOFCs face. There
is, therefore, an emerging need to develop new
materials and new Science, where NANOCOFC
and two-phase nanocomposites Science and techno-
logy are greatly highlighted.
Material designs and advanced nanocomposite
architectures integrated by nanotechnology have
unique advantages over conventional single-phase
materials. The two-phase nanocomposite approach
can create a wide range of functional materials, not
limited by structures, as long as the selected two
appropriate phases can create desired functions at
interfaces. However, extensive studies on inter-
facial ionic conduction mechanisms are funda-
mental requirements to circumvent the present
state of the art where the experimental and tech-
nological exploitation of these materials is appar-
ently moving faster than the understanding of
their performance. Fundamental studies are thus
strongly needed.

Copyright r 2009 John Wiley & Sons, Ltd. Int. J. Energy Res. (2009)
DOI: 10.1002/er
 B. ZHU
ACKNOWLEDGEMENTS
This work was supported by the Swedish Agency for
Innovation Systems (VINNOVA) and the Swedish
Agency for Energy (STEM) through GETT Fuel
cell AB industrialization projects and the financial
support form EC FP6 NANOCOFC project (contract
No. 32308). The author would also like to thank
contributions of knowledge to this area from the
NANOCOFC consortium partners and associated
partners.
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