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Int. J. Energy Res. (2009)
Published online in Wiley InterScience
( DOI: 10.1002/er.1600

Solid oxide fuel cell (SOFC) technical challenges and solutions
from nano-aspects

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


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

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

undertaken. An electrolyte conductivity of In the 300–6001C FC the high performance is
0.1 S cm1 is a basic requirement for FCs. The attributed to superionic conduction at interfaces in
YSZ reaches 0.1 S cm1 at ca. 10001C, thus nanocomposite electrolytes. This interfacial mecha-
causing the HT SOFC technology. Designing nism opens a new scientific disciplinary to
and development of functional materials at lower design and develop advanced functionalities and
temperatures (LT) are a critical challenge [3] and materials with new opportunities to overcome
therefore there is a world tendency to develop SOFC challenges. Our ongoing NANOCOFC (EC
SOFCs for low temperatures. Many efforts have (Turkey)-China Nanocomposites for advanced FC
been done by using thin-film technologies on YSZ technology) network,, has
to reduce the operational temperature [4–7]. But a carried out extensively innovative FC R&D based
thin film electrolyte can not guarantee a long on multi-functional nanocomposites. This report,
SOFC life because FC operation involves mass which covers a brief review and analysis of the
transport processes which can affect the electrolyte SOFC electrolyte materials, the ionic conduction
property in one or another aspect, thus causing theory, as well as constrains and disadvantages in
serious degradation. Even if using the thin film single-phase materials, presents new design and
YSZ the operational temperature requires still development of two-phase materials and func-
above 7001C or so. tionalities, especially in nanotech-based two-phase
State of the art of nanotechnology remarks a materials, that is nanocomposites, and solutions
great potential for SOFC or ceramic FC areas, from nano-aspects in comparison to the conven-
now moving down from HTs (above 7001C) to tional materials commonly described in literature.
low temperature SOFCs. Nanostructured solid-
state ionic electrolyte, coined as ‘nanoionics’ [8,9],
has recently become one of the hot areas of 2. BASIC OF SOFC MATERIALS
research related to nanomaterials, since they can
It is very important to recognize the current SOFC
be used in advanced energy conversion and storage
electrolytes’ constrains and disadvantages, which
applications [10], for example SOFCs [11–17].
have caused challenges for SOFCs. We may find
A more effective way is to develop new materials
solutions based on the understanding of the SOFC
with improved performance, for example super-
material science and physical properties behind.
ionic conduction at LT, say 0.1 S cm1 at
Recent SOFC material developments made by
300–6001C [18–20]. The 300–6001C FC technology
using nanotechnology will also help identifying
is a gap in the worldwide FC R&D. The
problems and solutions.
300–6001C FCs open many opportunities of
applying new architectures of nanocomposite
2.1. Oxygen ion conductivity: structure effects
that yield high performance and conductivities
resulted from nanomaterials blocks and two- Currently used SOFC electrolytes are based on
phase interfaces. The ability to manipulate and oxides, for example YSZ and ceria with a fluorite
engineer material synthesis and processes at structure (see Figure 1). Zirconium or cerium
atomic and molecular level can create radical atoms in a face-centered pattern contain a cube of
new architectures, materials and structures oxygen atoms (purple). Zirconia and ceria oxides
with unique functionalities and characteristics. form the same crystal structure. Fluorite has a
Manipulating interphases of nanotech-based simple structure–space group Fm3m. A structural
composites, so-called nanocomposites provide su- unit cell contains fully four cerium and eight
perionic conductivity at significantly LTs (from oxygen ions, the 1:2 stoichiometry is maintained.
10001C to 3001C). Development of 300–6001C The pure zirconia or ceria are very poor oxygen
SOFC technology also opens up new market ion conductors. The oxygen ion conductivity takes
opportunities since applications of nanotechno- place by aliovalent doping to create oxygen
logy for FCs give a great potential to reach ultra vacancies inside their structures. From a phase
low cost. structure perspective, stabilized zirconia, for

Copyright r 2009 John Wiley & Sons, Ltd. Int. J. Energy Res. (2009)
DOI: 10.1002/er


M4+ (host cation)

M2+ or M3+(aliovalent cation)

Oxygen vacancy

Figure 1. Fluorite structure for SOFC electrolytes.

example YSZ or ion doped ceria is a single-phase Though high doping concentration results in
material since the doping or guest phase, usually high defect (oxygen vacancy) concentration to
8 mol% Y2O3 in ZrO2 or 10–20 mol% Sm2O3 in facilitate the oxygen ion mobility or conductivity,
CeO2 to form a solid solution that the Y2O3 or after reaching a limit a stronger defect association
Sm2O3 is fully ‘dissolved’ in the zirconia or ceria takes place, for example
lattice to maintain the host fluorite structure.
The effect of dopant oxides on the ionic con- M0 Zr=Ce þVO ! ½M0 Zr=Ce VO  ð1cÞ
ductivity in ZrO2-based or CeO2-based binary
systems has been extensively investigated. The 2M0 Zr= þVO ½M0 Zr VO M0 Zr  ð1dÞ
main dopants used for stabilizing ZrO2 include
trivalent rare-earth or metal oxide: Y2O3, Yb2O3,
Sc2O3, etc.; divalent metal oxide: CaO, MgO, etc.; This equals to occupation of the oxygen va-
while Gd2O3, Sm2O3, La2O3 CaO, MgO, SrO, etc. cancy to make the oxygen sublattice ordering, thus
used for CeO2. The fluorite is a very open structure reducing the O2 conductivity. This prevents fur-
where large contents of dopant oxides can be ther increasing the material conductivities.
dissolved into the lattice, in the same time to create The ionic conduction is described by Arrhenius
large amounts of the oxygen vacancies. equation:
For example, when a divalent or trivalent metal sT ¼ s0 expðEa =kTÞ ð1eÞ
oxide MxOy is doped in the zirconia or ceria
matrix to form a solid solution, the following
defect reactions would occur: A simple theoretical analysis [21,22] can deduce
ZrO2 00   Equation (1f ) below, and help us to understand
MO ! M Zr=Ce þVO þOO ð1aÞ
the Arrhenius relation (1e) and ionic conduction
ZrO2 phenomenon.
M2 O3 ! 2M0 Zr=Ce þVO þO
O ð1bÞ
nz2 e2 gd 2 o0
The oxygen ion migration or diffusion can s0 ¼ ð1fÞ
occur only when the neighboring oxygen site is 6k
a vacancy. The existence of a large number of The advanced ion conductor design is thus to
octahedral vacancies created by doping in struc- maximize s0 and minimize Ea. Two parameters
ture makes it easier for an O2 to migrate from (d, ion mean jump distance and n, mobile ion
one site to the neighboring one, in case that the concentration) are important to maximize the s0.
latter is a vacancy. From this analysis we may identify the following

Copyright r 2009 John Wiley & Sons, Ltd. Int. J. Energy Res. (2009)
DOI: 10.1002/er

disadvantages and limitations for the single-phase

(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

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

Copyright r 2009 John Wiley & Sons, Ltd. Int. J. Energy Res. (2009)
DOI: 10.1002/er

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 the grain thus blocks the ionic transport.
lowering the grain-boundary resistance in order to Engineering of the grain boundaries is a top
obtain material high conductivity. option to improve and develop material ionic
2.3. Remarks
State-of-the-art of the current SOFC materials and
2.4. Nano-effects and new principles
oxygen ion conductor/tion in the single-phase
materials may tell us: However, the situation changes at the nano-level
with new materials, functionalities, and principles.
(i) Ion doping is a way to generate structural Recent developments are directed by extensively
defects (oxygen vacancies) in structure for using nanotechnology and nano-size materials
creating the oxygen ion mobility and con- for the conventional SOFC electrolytes and sup-
ductivity; however, the microstructure plays a port new scientific principles. These new studies
crucial role to determine the material final from nano-aspects have shown the common facts
conductivity; that the nanostructured ceria-based materials
(ii) Though the fluorite structure has large capa- [12–15] and YSZ [16,17] exhibited strong conduc-
city to accept high doping contents, above a tivity enhancement, due to significantly larger
doping level limit, the defect (vacancies) area of grain-boundary or interface in nanostruc-
association occurs to decrease conductivity; tured systems, which increases the concentration
(iii) Because of structural limits and high activa- of mobile defects in the space-charge zone [9,10].
tion energy, the sufficient O2 conductivity/ The grain-boundary in ionic conduction
mobility occurs only at HTs, for example suddenly turns from negative/side effect in the
0.1 S cm1 at 10001C for YSZ or 8001C for normal-sized (say micrometer level) to positive
doped ceria; effect as promoter in the nano-sized materials.
(iv) Grain boundaries or interior contacts between These new developments obviously disagree
particles are barriers to limit the ionic with the mainstream of the current SOFC Science
conductivity since the grain boundary con- built on the conventional materials as described
ductivity is much lower than (order) that of above.

Copyright r 2009 John Wiley & Sons, Ltd. Int. J. Energy Res. (2009)
DOI: 10.1002/er

The different particle size levels may cause single-phases are not stable, especially for SOFC
completely different ion transport phenomena. In environment at HTs. The nano-structured single-
the normal particle size the grain boundary blocks phase materials, typically YSZ and doped ceria
the ion transport ways, thus causing extremely may not function for SOFCs, where hundreds of
high resistivity gap between the grains. The ions degrees Celsius can easily destroy the nano-
migrate from one grain into another forming a structures in addition to strongly reducing and
discontinuous path thus causing low ion con- oxidizing environments. Moreover, in the nano-
ductivity (see Figure 3); while in nano-scale, the ceria case following side effects can occur [26]:
situation changes to opposite where the grain
boundaries become ion conduction highways. (a) transition from ionic to e conduction when
Compared to this the grain contribution becomes the particle turn to the nano-scale,
less important. In the state-of-the-art of the con- (b) electronic conductivity (se) increases for
ventional materials, the approach is to eliminate nano-sized particle,
the grain boundaries to a minimum level in order (c) ionic activation energy, Ea is also increased
to obtain high material conductivity. Conversely, with decreasing grain sizes.
in nano-scale grain boundaries in the single phase,
or interfaces and interfacial contacts in the two- Thus the single nano-ceria materials for SOFCs
phase materials should be optimized to a max- cannot be approved. To develop stable and
imum. An ionic conduction principle presented in functional nano-materials qualified for SOFC
Figure 4 [25] may help to understand the different applications is, therefore, a critical challenge and a
phenomena and principles. In the micrometer tough job.
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 3. NANOTECHNOLOGY AND
significantly decreased (hundreds of times less than APPROACHES AND ADVANCED
that in the micrometer level), which causes a MATERIAL DESIGNS
strong expulsion force to resist the O2 migration
3.1. Basic of advanced ionic conductors
while the ion approaching the grain, thus causing a
‘by-path’ for ion pass around the grain, that is The basic material design on advanced ionic
grain boundary or interface path. conductors can be considered from fast ionic
The design and development of functionalities conduction or superionic conduction theory. The
and advanced materials in the mm and nm levels principle is to design and realize the structure that
require thus very different approach, principle can offer long-distance channels or networks for
and theory. We need to fully recognize their dif- ionic conduction/transport. From this aspect,
ferent scientific natures/characteristics to guide though YSZ or ion-doped ceria are viewed as the
new material designs, developments and theories. open structure with large feasibility to create
Nano-structured materials can enhance the con- structure defects by ion-doping for ionic conductiv-
ductivity due to strong grain-boundaries’ effects. ity, it is very much under demands of the superionic
However, the nano-sized oxide conductors in the conduction, since the oxygen ion does not migrate in
the long-distance or networking in these materials.
In the two- or multiphase nanocomposite
µm scale materials the two-phase co-existence creates the
interfaces and particle surfaces between the con-
ion grain stituent phases, where the superionic conduction
nm scale takes place. Also, the energy to form defects on
Figure 4. A principle presentation of the ionic migration the surfaces or interfaces is significantly lower
at micrometer and nanometer levels, where grain than that inside the bulk structure. Thus, low
boundaries act as side paths for ion pass. temperature can activate sufficient ion mobility.

Copyright r 2009 John Wiley & Sons, Ltd. Int. J. Energy Res. (2009)
DOI: 10.1002/er

The interface has, in principle, no bulk structural complex architectures of nanocomposites (shape
limit to create high concentration of mobile ions, and configuration). The superionic conductivity
and can thus be very disordered. This implies that 40.1 S cm1 in the 300–6001C range can be
the interfaces have the capacity to contain higher realized by two-phase nanocomposites with new
mobile ion concentration and also longer range architecture by constructing interfaces as ion
transport channels/networks (from particle to highways to result in superionic conduction in
particle at nanometer level) in the interfaces than network with continuous paths. This has been
those of the bulk effect occurring within a crystal dealt with by a theoretical approach reported
(e.g. YSZ) unite cell (at Angstrom level) of the before on the ceria-carbonate (as the 2nd phase)
bulk, thus strongly enhance the conductivity. composites, see Figure 5 [27]. The ion transport
mechanism in interfaces is under study and needs
more investigations both experimentally and
3.2. Two-phase architectures and functionalities
theoretically since there is a lack of knowledge
of the nanocomposites
and theory on this subject. Based on the nano-
Multifunctional nanocomposites for advanced science principle, several concepts of the advanced
LTSOFCs are based on developing and modifying material architectures may be presented below.
nano-particles’ surface physical and chemical
properties to obtain new desired properties that 3.2.1. Architecture 1. The concept of ‘nanocom-
the bulk materials do not possess. The surface posite’ [28–30] by adding a secondary phase as
effect becomes more significant with the particle inclusion can effectively hinder the grain growth of
sizes decreasing, especially o10 nm. At this level nanostructures. Nanocomposite approach can
atoms mostly concentrated/shifted on the nano- create a nano-core particle with a nano-layer-shell
particle surfaces from the bulk (e.g. at 1 nm level formed by the 2nd phase, or by interaction (layer/
almost all atoms 490% will stay on the surfaces). shell) between the constituent phases, both core
These atoms lack coordination or configuration and shell/layer are material components to create
with very high surface energy and are thus easily functionalities. This approach can prevent the
ready to interact with other material’s atoms to be nano-functional particles from energetic growth at
stabilized. Such activated or unstable surface HTs and high activity in extreme atmospheres. In
atoms (ions) become highly mobile, resulting in the same time it can create new functions/proper-
superionic conduction at interfaces. Clear under- ties at interfaces between the two constitute
standing of physics behind the ionic conductivity phases. It is common that nano-sized particle in
would be very helpful for the development of single-phase materials can, on one hand, create


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. Int. J. Energy Res. (2009)
DOI: 10.1002/er

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

Copyright r 2009 John Wiley & Sons, Ltd. Int. J. Energy Res. (2009)
DOI: 10.1002/er

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

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

Copyright r 2009 John Wiley & Sons, Ltd. Int. J. Energy Res. (2009)
DOI: 10.1002/er

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.
550 500 450 400 350 300 250 200 150
-1.5 Classical oxygen conduction and theory in single-
-2.5 phase materials encounter critical challenges. State-
-3.0 of-the-art of the conventional SOFC materials
lgs (S/cm)

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

Copyright r 2009 John Wiley & Sons, Ltd. Int. J. Energy Res. (2009)
DOI: 10.1002/er

ACKNOWLEDGEMENTS 19. Zhu B. Journal of Power Sources 2003; 114:1.
20. Zhu B, Yang XT, Xu J, Zhu ZG, Ji SJ, Sun MT, Sun JC.
Journal of Power Sources 2003; 118:47.
This work was supported by the Swedish Agency for 21. Kingery WD, Bowen HK, Uhlmann DR. Introduction to
Innovation Systems (VINNOVA) and the Swedish Ceramics (2nd edition). Wiley: New York, 1976.
Agency for Energy (STEM) through GETT Fuel 22. Orliukas A, Bohac P, Sasaki K, Gauckler LJ. Solid State
cell AB industrialization projects and the financial Ionics 1994; 72:35.
support form EC FP6 NANOCOFC project (contract 23. Guo X, Ding Y. Journal of the Electrochemical Society
No. 32308). The author would also like to thank 2004; 151:J1.
contributions of knowledge to this area from the 24. Guo X, Sigle W, Fleig J, Maier J. Solid State Ionics
NANOCOFC consortium partners and associated 2002;154–155:555.
partners. 25. Zhu B, Xia CR, Luo XG, Niklasson G. Thin Solid Films
2001; 385:209.
26. Tschöpe A. Solid State Ionics 2001; 139:267.
27. Zhu B, Li S, Mellander BE. Electrochemistry Communica-
REFERENCES tions 2008; 10:302.
28. Chen B, Zhang H, Gilbert B, Banfield JF. Physical Review
1. Nernst W. US Patent 685: 730 filed 24/8/1899. Letters 2007; 98:106103.
2. Baur E, Preis H. Zeitschrift fur Elektrochemie 1937; 43. 29. Liu C, Wu X, Klemmer T, Shukla N, Weller D, Roy AG,
3. Goodenough JB. Nature 2000; 404:821. Tanase M, Laughlin D. Chemistry of Material 2005; 17:620.
4. Charpentier P, Fragnaud P, Schleich DM, Gehain E. Solid 30. Wu NL, Wang SY, Rusakova IA. Science 1999; 285:1375.
State Ionics 2000; 135:373. 31. Wang X, Ma Y, Raza R, Muhammed M, Zhu B.
5. Shao ZP, Sossina MH. Nature 2004; 49:170. Electrochemistry Communications 2008; 10:1617.
6. Huang H, Nakamura M, Su P, Fashing R, Sato Y, 32. Ma Y, Wang XD, Muhammed M, Zhu B. Thermal stability
Prinz FB. Journal of the Electrochemical Society 2007; study of SDC/NaCO3 nanocomposite electrolyte for
154:B20 low-temperature SOFCs. International Journal of Hydrogen
7. Park YI, Chen SP, Won CS, Saito Y, Fritz BP. Journal of Energy, in press.
the Electrochemical Society 2006;153:A431. 33. Xia Y, Yang P, Sun Y, Wu Y, Mayers B, Gates B, Yin Y,
8. Despotuli AL, Nikolaichic VI. Solid State Ionics 1993; Kim F, Yan H. Advanced Materials 2003; 15:353.
60:275. 34. Lee S, Cho S, Cheon J. Advanced Materials 2003; 15:441.
9. Maier J. Nature Materials 2005; 4:805. 35. Hu J, Odom TW, Lieber CM. Accounts of Chemical
10. Arico AS, Bruce P, Scrosati B, Tarascon J, van Schalkwijk W. Research 1999; 32:435.
Nature Material 2005; 4:366. 36. Ma Y, Wang XD, Muhammed M, Zhu B. A novel chemical
11. Hong SH, Zhu J, Mirkin CA. Science 1999; 286:523. synthesis of Sm-doped CeO2 nanowires—low temperature
12. Bellino MG, Lamas DG, Walsoe de Reca NE. Advanced SOFC electrolyte, reported in Hyforum 2008, EC-China
Materials 2006; 18:3005. NANOCOFC Workshop, Changsha, China, 3–5 August
13. Bellino MG, Lamas DG, Walsoe de Reca NE. Advanced 2008.
Functional Materials 2006; 16:107. 37. Zhu B, Liu XR, Zhou P, Yang XT, Zhu ZG, Zhu W.
14. Kim S, Maier J. Journal of the Electrochemical Society Electrochemistry Communication 2001; 3:566.
2002; 149:J73. 38. Huang JB, Mao ZQ, Liu ZX, Wang C. Electrochemistrty
15. Ruiz-Trejo E, Santoyo-Salazar J, Vilchis-Morales R, Communications 2007; 9:2601.
Benı́tez-Rico A, Gómez-Garcı́a F, Flores-Morales C, 39. Zhu B. International Journal of Energy Research 2006;
Chávez-Carvayar J, Tavizón G. Journal of Solid State 30:895.
Chemistry 2007; 180:3093. 40. Jamnik J, Maier J, Pejovnik S. Solid State Ionics 1995;
16. Knöner G, Reimann K, Röwer R, Södervall U, 75:51.
Schaefer HE. Proceedings of the National Academy of 41. Lee J, Adams S, Maier J. Journal of the Electrochemical
Sciences of United States of America 2003; 100:3870. Society 2000; 147:2407.
17. Garcia-Barriocanal J, Rivera-Calzada A, Varela M, 42. Zhu B, Liu XR, Zhu ZG, Zhu W, Ljungberg R.
Sefrioui Z, Iborra E, Leon C, Pennycook SJ, Santamaria J. International Journal of Hydrogen Energy 2008; 33:3385.
Science 2008; 321:676. 43. Mahmut DM, Liu XR, Zhu ZG, Zhu B. International
18. Zhu B. Journal of Power Sources 2001; 93:82. Journal of Hydrogen Energy 2007; 32:796.

Copyright r 2009 John Wiley & Sons, Ltd. Int. J. Energy Res. (2009)
DOI: 10.1002/er