J Am. Cwam Joc. %[?

I 563-88(1995)

Ceramic Fuel Cells

Nguyen Q. Minh*
AiResearch Los Angeles Division, Allied-SignalAerospace Company, Torrance, California 90504-6099

A ceramic fuel cell is an all solid-state energy conversion
device that produces electricity by electrochemically com-
bining fuel and oxidant gases across an ionic conducting
oxide. Current ceramic fuel cells use an oxygen-ion conduc-
tor or a proton conductor as the electrolyte and operate at
high temperatures (>6OO0C). Ceramic fuel cells, commonly
referred to as solid-oxide fuel cells (SOFCs), are presently
under development for a variety of power generation appli-
cations. This paper reviews the science and technology of
ceramic fuel cells and discusses the critical issues posed by
the development of this type of fuel cell. The emphasis is
given to the discussion of component materials (especially,
ZrO, electrolyte, nickel/ZrO, cermet anode, LaMnO, cath-
ode, and LaCrO, interconnect), gas reactions at the elec-
trodes, stack designs, and processing techniques used in the
fabrication of required ceramic structures.
I. Introduction
F UEL CELLS are a radically new and fundamentally different
way of making electrical power from a variety of fuels. A
fuel cell is an energy conversion device that produces electricity
(and heat) by electrochemical combination of a fuel with an
oxidant. A fuel cell consists of two electrodes (the anode and
cathode) separated by an electrolyte (Fig. I). Fuel (e.g., hydro-
gen) is fed to the anode where it is oxidized and electrons are
released to the external (outer) circuit. Oxidant (e.g., oxygen)
is fed to the cathode where it is reduced and electrons are
accepted from the external circuit. The electron flow (from the
anode to the cathode) through the external circuit produces
direct-current electricity. The electrolyte conducts ions between
the two electrodes. Practical fuel cells are not operated as single
units; rather, they are connected in electrical series to build volt-
age. A series of cells is referred to as a stack. A component,
variously called a bipolar separator or an interconnect, connects
the anode of one cell to the cathode of the next cell in a stack
(Fig. 2 ) . Fuel cell stacks can be configured in series, parallel,
both series and parallel, or as single units, depending on the
particular application.
The key feature of a fuel cell is its high energy conversion
efficiency. Because a fuel cell converts the chemical energy of
the fuel directly to electrical energy without the intermediate of
thermal energy, its conversion efficiency is not subject to the
Carnot limitation. Compared with conventional methods of
power generation, fuel cells offer several advantages: substan-
tially higher conversion efficiency, modular construction, high
efficiency at part load, minimal siting restriction, potential for
cogeneration, and much lower production of pollutants.
The principles of fuel cell operation were first reported by Sir
William Grove in 1839.’ His fuel cell used dilute sulphuric acid
as the electrolyte and operated at room temperature. Ceramic
fuel cells came much later and began with Nernst’s discovery of
solid-oxide electrolytes in 18992and the operation of the first
ceramic fuel cell at 1000°C by Baur and Preis in 1937.’ Since
that time, ceramic fuel cell technology has made excellent tech-
nical progress. Multikilowatt fuel cells, based on stabilized zir-
conia electrolyte, have been operated for thousands of hours
and have shown excellent performance. Recently, ceramic fuel
ELECTROLYTE
AND HEAT
CATHODE
Fig. 1. Schematic diagram of fuel cell operation.

N. Dudney--contributing editor
T R
INTERCONNECT

Manuscript No. 195584. Received June 18, 1992; approved October 9, 1992.
‘Member, American Ceramic Society. Fig. 2. Fuel cell components.

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564 Journal of the American Ceramic Society-Minh
cell research and development has received much attention,
reflecting widening interest in this technology.
Ceramic fuel cells have several distinct advantages over other
types of fuel cells, e.g., use of nonprecious materials, no liq-
uids involved in the fuel cell, and invariant electrolyte. The use
of a solid electrolyte in ceramic fuel cells eliminates material
corrosion and electrolyte management problems. Ceramic fuel
cells are generally operated at high temperatures ( >600"C).
The high operating temperature promotes rapid reaction kinet-
ics, allows reforming of hydrocarbon fuels within the fuel cell
(internal reforming), and produces high-quality byproduct heat
suitable for use in cogeneration or bottoming cycle. Thus,
power systems based on ceramic fuel cells can be simple and
are more efficient than many other technologies. Furthermore,
because all the components are solid, ceramic fuel cells can be
fabricated in very thin layers, and cell components can be con-
figured into unique shapes unachievable in fuel cell systems
having a liquid e l e ~ t r o l y t e This
. ~ feature permits cell designs
with additional performance improvements.
On the other hand, ceramic fuel cells place stringent require-
ments on materials. Ceramic fabrication processes need to be
developed to incorporate the materials into practical stack con-
figurations. At present, the key technical challenge is develop-
ment of suitable materials and fabrication of ceramic structures.
Engineering ceramic powders and developing forming and pro-
cessing methods play a key role in ceramic fuel cell technolo-
gies. This paper reviews the principles of ceramic fuel cell
operation, materials for cell components, and various aspects of
fuel cell design and fabrication. Emphasis is given to the dis-
cussion of material properties, cell reactions, and fabrication
processes critical in the development of ceramic fuel cells.
11. Cell Component Requirements
The principal components of a ceramic fuel cell stack are the
electrolyte, the anode, the cathode, and the interconnect. Each
component serves several functions in the fuel cell and must
meet certain requirements. Each component must have the
proper stability (chemical, phase, morphological, and dimen-
sional) in oxidizing and/or reducing environments, chemical
compatibility with other components, and proper conductivity.
The components for ceramic fuel cells must, in addition, have
similar coefficients of thermal expansion to avoid separation or
cracking during fabrication and operation. The electrolyte and
interconnect must be dense to prevent gas mixing, whereas the
anode and cathode must be porous to allow gas transport to the
reaction sites.
In addition to the above requirements, other desirable prop-
erties for the cell components from practical viewpoints are
high strength and toughness, fabricability, and low cost. Also,
for certain cell designs, the components for a ceramic fuel cell
must be amenable to limited fabrication conditions since the
process conditions cannot be selected independently for each
component. For example, if the components are built up one by
one, the temperature of sintering for each successive compo-
nent must be lower than that of the preceding component to
avoid altering the microstructure of the preceding component.
If the components are formed in the green state, then all compo-
nents must be sintered under the same firing conditions. Fur-
thermore, the components of a ceramic fuel cell must be
compatible not only at the operating temperature but also at the
much higher temperatures at which the ceramic structures are
fabricated.
111. Types of Ceramic Fuel Cells
In theory, any gases capable of electrochemical oxidation
and reduction can be used as fuel and oxidant in a fuel cell.
However, hydrogen is currently the most common fuel for use
in ceramic fuel cells. Hydrogen has high electrochemical reac-
tivity and can be derived from common fuels such as hydrocar-
bons, alcohols, or coal. Oxygen is the most common oxidant
Vol. 76, No. 3
for ceramic fuel cells since oxygen is readily and economically
available from air. An electrolyte for a fuel cell based on the
electrochemical combustion of hydrogen (to produce water) is
either an oxygen-ion conductor or a hydrogen-ion (proton) con-
ductor. (Although a hydroxide-ion conductor is also possible, it
will be referred to as a proton conductor in this paper for simpli-
fication reasons.) Thus, the present generation of ceramic fuel
cells can be classified into two types: those based on oxygen-
ion conductor and those based on proton conductor. Figures 3
and 4 show the reactions in an oxygen-ion-conductor fuel cell
and a proton-conductor fuel cell, respectively. The major dif-
ference between the two types is the side in the fuel cell in
which water is produced (the oxidant side in proton-conductor
fuel cells and the fuel side in oxygen-ion-conductor fuel cells).
Also, certain gases, such as carbon monoxide, can be used as
fuel in oxygen-ion-conductor fuel cells but not in proton-con-
ductor fuel cells. To date, only oxides are being considered for
ceramic fuel cell electrolytes. Since fuel cells are commonly
identified by the type of electrolyte used, ceramic fuel cells are
therefore referred to as solid-oxide fuel cells (SOFCs).
IV. Ceramic Fuel Cells Based on Oxygen-Ion Conductors
The most advanced SOFCs are those based on oxygen-ion-
conducting stabilized zirconia electrolyte. The conductivity
requirement for the electrolyte determines the operating tem-
perature of this SOFC (about 1000°C). The other materials
commonly used for this type of SOFC are nickelistabilized zir-
conia cermet for anodes, doped lanthanum manganite for cath-
odes, and doped lanthanum chromite for interconnects.
(1) Materials for Cell Components
( A ) Electrolyte: ( a ) Stabilized Zirconia: Stabilized zir-
conia (ZrO,), especially yttria-stabilized zirconia, is the most
common electrolyte in SOFCs because the material possesses
an adequate level of oxygen-ion conductivity and exhibits
desirable stability in both oxidizing and reducing atmospheres.
The properties of stabilized zirconia have been extensively
studied.'-' Several reviews on the subject are available.x-'('
ZrO,, in its pure form, does not serve as a good electrolyte,
primarily because its ionic conductivity is too low. At room
temperature, ZrO, has a monoclinic ( m ) crystal structure. The
monoclinic structure changes to a tetragonal ( t ) form above
1170°C and to a cubic fluorite structure above 2370°C. The
tetragonal-monoclinic transformation is associated with a large
volume change (3% to 5%) (contraction on heating and expan-
sion on cooling). The cubic phase exists up to the melting point
of 2680°C. However, the addition of certain aliovalent oxides
stabilizes the cubic fluorite structure of ZrOz from room tem-
perature to its melting point an+d,at the same time, increases its
oxygen vacancy concentration. This enhances the ionic con-
ductivity and leads to an extended oxygen partial pressure
range of ionic conduction, making stabilized ZrO, suitable for
use as an electrolyte in SOFCs. (This extended oxygen partial
pressure range covers the conditions, 1 to lo-'' atm (10' to
lo-" Pa), to which a SOFC electrolyte is exposed in the fuel
cell during operation.) The most commonly used stabilizing
oxides or dopants are CaO, MgO, Y20,, Sc,O,, and certain
rare-earth oxides. These oxides exhibit a relatively high solu-
bility in ZrO, and are able to form the fluorite structure with
ZrO, which is stable over wide ranges of composition and
temperature.
Stabilization of ZrOz is accomplished by direct substitution
of divalent or trivalent cations of appropriate size for the host
lattice cation Z P . This substitution not only stabilizes the
cubic fluorite structure but also creates a large concentration of
oxygen vacancies by charge compensation according to the fol-
lowing equation (written for Y,O, stabilization using Kroger-
Vink notation):
March 1993 Ceramic Fuel Cells 565

CATHOOE
EXHAUST
OVERALL R E A C T I O N

Fig. 3. Schematic diagram of reactions in ceramic fuel cells based on oxygen-ion conductor^.^

OUTER
CIRCUIT

CATHOUE

OXIOANT
02, H 2 0 CATHOOE
EXHAUST
OVERALL REACTION
HZ + %02 +HzO
Fig. 4. Schematic diagram of reactions in ceramic fuel cells based on proton conductors.

The high oxygen vacancy concentration gives rise to a high
oxygen-ion mobility. Oxygen-ion conduction takes place in sta-
bilized ZrO, by movement of oxygen ions via vacancies. Over a
wide range of temperature, the ionic conductivity of stabilized
ZrO, is independent of oxygen partial pressure over several
orders of magnitude (Fig. 5).5,” Under these conditions, the
ionic transport number is very close to unity (i.e., negligible
electronic conduction). The electrical conductivity of stabilized
ZrO, has been measured by numerous investigators. The ionic
conductivity of stabilized ZrO, depends on dopant concentra-
tion. Figure 6 shows, as an example, variation of conductivity
with dopant concentration for various doped ZrO,. ” Isothermal
plots of conductivity exhibit a maximum. This maximum con-
ductivity is obtained at or near the minimum quantity of dopant
required to fully stabilize the cubic fluorite phase. The conduc-
tivity then decreases with further increase in dopant concentra-
tion, and this trend is accompanied by an increase in activation
energy for conduction. The decrease in conductivity at higher
dopant concentration is believed to be due to defect order-
ing,vacancy clustering, or electrostatic interaction.’’
In general, fully stabilized ZrO, is preferred as SOFC elec-
trolyte material in order to have maximum conductivity. The
use of fully stabilized Zr02 also avoids the problems of phase
transformation associated with partially stabilized materials
during cell operation. The conductivity of fully stabilized ZrOz
as a function of temperature follows Arrhenius-type behavior.
Table I lists the conductivity data for stabilized ZrO, doped with
various rare-earth oxides. Although stabilization of ZrO, with
Y203does not yield the highest conductivities, Y,O,-stabilized
ZrO, (YSZ) is most frequently used as SOFC electrolyte
because of availability and cost.
In SOFCs, YSZ is used in the form of polycrystalline thin
films or layers. It is well established that ionic conductivity
(resistivity) of polycrystalline ceramics depends on the micro-
structures, especially grain boundaries, of the samples. The
grain-boundary effect on the conductivity is mainly due to the
566 Journul of the American Ceramic Society-Minh Vol. 76, No. 3

1000°C, grain-boundary effects, such as conductivity

I and grain-size effect,?' are believed to be negligible.
Y S Z must be fabricated into fully dense layers for use as a
18 18 mol% YOl SOFC electrolyte. A common fabrication method is the particu-
late approach. This involves compaction of Y S Z powder into
33 33 mol% YO, the desired shape and densification at elevated temperature. In
15 moi% CaO general, densification of materials consolidated by the particu-
0
late approach is dependent on material and processing factors,
such as powder characteristics (reactivity, purity, morphology),
6 1 4616rnol%YOt5 particle packing (green density), and processing conditions
(temperature, time, atmosphere). Ideally, fine (high surface
area) spherical particles with narrow size distribution are desir-
able because they result in high reactivity and high packing
density and, therefore, enhanced densification of powders (into
sintered bodies with uniform microstructure) at low sintering
10-4 temperature. Recent advances in powder synthesis and pro-
0 4 8 12 16 20 24 28
- LOG OXYGEN PARTIAL PRESSURE. ATM
cessing have indicated that Y S Z powders with such chardcteris-
tics can be prepared and have been processed into dense layers
Fig. 5. Ionic conductivity of stabilized ZrOzas a function of oxygen under conditions suitable for SOFC fabrication. For example,
partial pressure ( T = lOOO"C).' Y S Z powders of submicrometer size (nanocrystalline size) have
been formed into a green body (about 50% green density) and
fired to 95% of theoretical density in air at 1 125°C.22ZrO, pow-
10' I I ders are generally prepared from chloride precursors and, there-
fore, may contain chloride residue. The presence of a
significant amount of chloride (1 wt%) can raise the sintering
temperature of the material as much as 150°C.23,24 If necessary,
laundering techniques can be used to remove the chloride
impurity. 23m
SOFCs, similar to other advanced ceramic structures, are
brittle and susceptible to fracture caused by flaws which are
introduced in the fuel cell during various stages of fabrication
and service. Fracture in the electrolyte allows fuel and oxidant
to come into contact (cross leakage), thus reducing cell perfor-
mance and efficiency. Significant fuel and oxidant cross leak-
age can render the fuel cell inoperative. An electrolyte with
I high fracture toughness is therefore desirable. A tough electro-
lyte is less sensitive to the presence of flaws and imparts better
fracture resistance to the fuel cell during fabrication and opera-
tion. Several approaches have been taken to improve the
104 I ' I mechanical properties of the Y S Z . These approaches are based
4 8 12 16 20
MOL% M203 01 MO
on improvement of fracture resistance of the electrolyte by
toughening." The Y S Z electrolyte has been toughened by
Fig. 6. Variation of ionic conductivity of stabilized ZrO?with dopant introducing inclusions of rn-ZrO,. However, the addition of m-
concentration ( T = 807"C).12 ZrO, has been found to degrade the conductivity of Y S Z to a
level unacceptable for SOFC application.2h Fine particles of
partially stabilized ZrO, (PSZ)26and A1,0327-29 have also been
Table I. Conductivity Data for Stabilized ZrO, Doped with added to Y S Z . These additives increase the fracture toughness
Rare-Earth Oxides* of the Y S Z electrolyte without significantly affecting the con-
ktlvdtlon energy
ductivity of the material. MgO has also been used to improve
Dopdnt Conipo\ition Conductivity (lo0o"C)
( M 0,) (mol'7u M,O,) ( X 10 ' 12 ' Lm ') (kJ/mol) the mechanical properties of YSZ." To date, only limited tests
have been performed on these toughened Y S Z electrolytes.
y20, 8 10 0 96
15 14 104 Because of its high toughness and strength, t-ZrO, has
Nd,O,
Sm*O, 10 58 92 been proposed as a SOFC electrolyte. For comparison, the
Yb,% 10 I1 0 82 toughness of Y S Z ranges between 2 to 3 MPa.m"*, whereas
SC20, 10 25 0 62 that of t-ZrO, is about 6.5 MPa.m"*. At temperatures below
*Reference 9 500"C, the bulk conductivity of t-ZrO, is greater than that for
Y S Z . This suggests the possibility of its use as electrolytes in
SOFCs operated at low temperatures. However, there are two
presence of impurities or second phases introduced via the raw main concerns regarding SOFCs based on t-ZrO,
materials or during the fabrication process. Impurities tend to electrolyte: mechanical integrity and aging effect. In general,
segregate at grain boundaries and at the external surface during t-ZrO, electrolytes can suffer mechanical degradation after
processing and subsequent heat treatment of the ceramic. l 4 long-term exposures at fuel cell operating temperatures. This
Complex impedance measurements have been used extensively degradation results from the growth and subsequent transforma-
to determine the bulk and grain-boundary resistivities of poly- tion of the metastable tetragonal phase.34t-ZrO, also shows pro-
crystalline stabilized Zr0,.'5-'x In general, the influence of nounced conductivity a g i r ~ g . ~The
~ , ~aging
' behavior in t-ZrO, is
grain boundaries on the conductivity of stabilized ZrO, can be a result, in part, of enhancement of the grain-boundary
considerable at low and intermediate temperatures ( <700°C). blocking effect. The segregation of impurities to the grain
At higher temperatures, grain boundaries have a small influ- boundaries during aging is one mechanism responsible for this
ence, especially when the sample is prepared from powders effect.
without the presence of a significant amount of impurities or (b) Other Electrolyte Materials: Among the known oxy-
additives. Therefore, for SOFCs using Y S Z electrolyte at gen-ion conductors, stabilized bismuth oxide (Bi,O,) shows the
March 1993 Ceramic Fuel Cells
highest ionic conductivity at comparable temperatures. In cer-
tain composition ranges, the conductivities of stabilized Bi,O,
exceed l o - ' fl-'.cm-' at 700°C and 1 0 - 2 R - ' . c m - ' at 500"C,
1 to 2 orders of magnitude higher than that of stabilized
Zr0,.37-39 This greater ionic conductivity of stabilized Bi,O,
offers the possibility of its use as electrolytes in SOFCs oper-
ated at lower temperatures (<1000"C). The main drawback of
this material is its smaller oxygen partial pressure range of ionic
conduction. Stabilized Bi,O, is easily reduced under low oxy-
gen partial pressure and decomposes into bismuth metal at oxy-
gen partial pressure of about atm Pa) at 600"C.4"
Therefore, practical use of stabilized Bi,O, as SOFC electrolyte
is questionable.
Similar to ZrO,, ceria (CeO,) doped with CaO, Y,O,, and
various rare-earth oxides is an excellent oxygen-ion conduc-
tor.4' Doped CeO, shows a higher conductivity and a lower con-
duction activation energy when compared to stabilized ZrO,.
Doped CeO, has been proposed as a potential candidate for
SOFC e l e ~ t r o l y t e .However,
~~ the material undergoes large
departures from stoichiometry at elevated temperatures in a
reducing atmosphere with accompanying electronic conductiv-
ity. Thus, the electronic conductivity of doped CeO, must be
minimized under reducing conditions if CeO, is to be a useful
SOFC electrolyte. A dopant concept has been attempted to
improve the ionic domain of Ce0,.43Certain dopants have been
found to improve the ionic domain boundary to lo-,' atm
(lo-'' Pa) at 700°C. Another approach to suppress the reduc-
tion of CeO, under reducing conditions is to coat CeO, with a
stabilized ZrO, l a ~ e r . In ~ .this
~ ~case, the stability of CeO, is
dependent on the partial pressure of oxygen at the ZrO,/CeO,
interface.&The oxygen partial pressure at the interface, in turn,
depends on the transport characteristics, especially the elec-
tronic conductivity, of CeO,. High electronic conductivity (in
addition to high ionic conductivity) of the CeO, side ensures
high oxygen partial pressure at the interface and, thus, high
thermodynamic stability.46
Development of other materials, especially those possessing
sufficient ionic conductivities at intermediate temperatures
(600" to SOOT), has received much interest recently. A replace-
ment of YSZ by a reduced-temperature oxygen-ion conductor
in SOFCs would greatly reduce material and fabrication prob-
lems and improve cell reliability during prolonged operation.
Several doped perovskite (ABO,) solid electrolytes have been
identified.47-5"The identification of these perovskites has been
based on the empirical relationship between the activation
energy for oxygen-ion conduction and the free volume of lattice
The observed trend between the activation energy
and the free volume has been used to develop a free volume
maximization algorithm which permits the identification of cat-
ions in the perovskite A and B sites to maximize the free
volume for ionic transport through the lattice. As an example,
some of the identified perovskite electrolytes are
BaCe,,Gd, ,O,, CaAI,,Ti, ,03,and SrZr,,,Sc, ,03.To date,
only preliminary work has been conducted on cells with reduc-
ed-temperature perovskite electrolytes.
( B ) Anode: ( a ) NickellYttria-Zirconia Cermet: Be-
cause of the reducing conditions of the fuel gas, metals can be
used as SOFC anode materials. Since the composition of the
fuel changes during the operation of the fuel cell, suitable met-
als must be non-oxidized not only at the fuel inlet conditions
but also at the more oxidizing conditions of the fuel outlet. At
the 1000°C operating temperature of YSZ-based SOFCs, suit-
able metals are limited mainly to nickel, cobalt, and noble met-
als. Nickel is most commonly used because of its low cost
(when compared with other metals, such as cobalt, platinum,
and palladium). To maintain the porous structure of nickel over
long periods at 1000°C and to provide other desired properties
for the anode, nickel metal is often dispersed on the surface of a
YSZ support. The YSZ support is added to the anode formula-
tion in the form of powder or fibet5' The functions of the YSZ
support in the anode are to support the nickel-metal particles,
inhibit coarsening of the metallic particles at the fuel cell
567
operating temperature, and provide an anode thermal expansion
coefficient acceptably close to those of the other cell compo-
nents. The YSZ support is considered as "inactive" although
the support may play an important role in dictating the catalytic
activity of the anode.
The electrical conductivity of nickeVYSZ cermet is strongly
dependent on its nickel content. The conductivity of the ccrmet
as a function of nickel content shows the S-shaped curve pre-
dicted by percolation theory (Fig. 7 ) . 5 2 . 5The
3 percolation
threshold for the conductivity is at about 30 vol% nickel. This
percolation behavior can be explained by the presence of two
conduction mechanisms through the cermet: an electronic path
through the nickel phase and an ionic path through the YSZ
phase. Below 30 vol% nickel, the conductivity of the cermet is
similar to that of YSZ, indicating an ionic conduction path
through the YSZ phase. Above 30 vol% nickel, the conductiv-
ity is about 3 orders of magnitude higher, corresponding to a
change in mechanism to electronic conduction through the
nickel phase. This is supported by the fact that the conductivity
of the nickel/YSZ cermet containing more than 30 vol% nickel
decreases with increasing temperature, and the activation
energy for conduction is similar to that of pure nickel (5.38
kJ/mol). The conductivity of the cermet is also dependent on its
microstructure (support surface area). At the same nickel vol-
ume percent, a support with lower surface area has better nickel
coverage, resulting in improved nickel particle-to-particle con-
tact, thus higher conductivity for the cermet.
Since nickel has a higher thermal expansion coefficient than
YSZ, there are concerns about thermal expansion mismatch
between the anode and the electrolyte. A significant degree of
mismatch in thermal expansion coefficients of the SOFC com-
ponents can result in large stresses, causing cracking or delami-
nation during fabrication and ~peration.'~The thermal
expansion coefficient of nickel/YSZ cermet increases linearly
with the nickel content (Fig. 8).54~.5c The cermet containing
more than 30 vol% nickel has a higher thermal expansion coef-
ficient than the YSZ electrolyte (about 10.5 >( 10 ' cmi
(cm.K)). Various means have been developed to tolerate and
minimize the thermal expansion mismatch. For example,
improving the fracture toughness of the electrolyte has been
attempted to provide sufficient tolerance of stresses generated
by thermal expansion mismatch." Control of critical pro-
cessing flaws is another effective means to increase fracture
resistance of the electrolyte. Varying the thickness and thick-
ness ratio of the cell components can be used to tolerate thermal
expansion mismatch.54Minor constituents have been added to
102 J I
0 10 20 30 40 50 60
VOL% NICKEL
Fig. 7. Conductivity of nickel/ZrOL cermet as a function of nickel
content (T = lOOO"C)."
568 Journal ojthe American Ceramic Sociew-Minh
the anode formulation to match the anode thermal expansion
with the other cell components.
The SOFC anode cermet is commonly made from YSZ and
NiO powders. The NiO is then reduced in situ to nickel metal
when exposed to the fuel in the fuel cell. Examples of SOFC
anode microstructures after air firing and after hydrogen reduc-
tion are shown in Fig. 9. Figure 9 shows that the reduced anode
is more porous as a result of oxygen loss due to conversion of
NiO to nickel. For a thin air-fired NiOiYSZ layer (e.g., 100 p m
thick), it takes only minutes to complete the NiO reduction at
1000°C. During the reduction, the conductivity of the anode
generally reaches a maximum very quickly then falls off slowly
until a steady state is obtained.52The maximum occurs when
enough NiO is reduced to form a conducting nickel-metal
matrix, and the fall-off corresponds to loss of nickel particle
contact as the particles shrink due to further NiO reduction.
Sintering of nickel particles is a major concern in long-term
operation of the SOFC anode at 1000°C. Nickel sintering
results in loss of active surface area and reduced conductivity of
the anode, leading to degradation of cell performance. Since
nickel particles are high-surface-area solids, there will always
be a thermodynamic driving force to decrease free energy, i.e.,
to minimize surface area. Thus, the sintering behavior of the
VOL% Ni
Y 0 15 30 51 72 100
a
k-
0
U
w
U disadvantages of most of these materials are thermal expansion
0
0
z ductivity. At present, doped lanthanum manganite (LaMnO,) is
0
z
(0
B ture of LaMnO, may undergo atomic distortion leading to
VOL% NiO
Fig. 8. Thermal expansion coefficient of cerniet anode as a function
of NiO (or nickel) ont tent.'^
Fig. 9. SOFC anode microstructures: ( A ) after air firing and (B) after hydrogen reduction
Vol. 76, No. 3
nickel/YSZ anode is strongly dependent on the wetting proper-
ties of the nickel on the YSZ. In general, the rate of anode sin-
tering is dependent on the nickel particle-size distribution, with
an increase in the rate as the width of dispersion increases. The
rate of sintering also increases as the nickel content in the anode
increases. To date, not much information has been published in
the open literature concerning the sintering behavior of the cer-
met anode.
( h ) Other Anode Materials: Cobalt is another suitable
SOFC anode material since the metal can withstand the fuel
environment and remains non-oxidized. Cobalt/stabilized ZrOz
cermet anodes have been used in SOFCs.'" Compared with
nickel, cobalt has the advantage of high sulfur tolerance; how-
ever, cobalt is not commonly used because of its high cost.
Also, the oxidation potential of cobalt is higher than that of
nickel metal, thus requiring a less complete fuel combustion.
Recently, ruthenium/stabilized ZrOz cermets have been tested
as SOFC anode^.^' Ruthenium has the advantages of better
resistance to sintering and higher reforming activity. Other
materials, such as conductive oxides, have also been proposed
as possible SOFC anode materials.sx"' Recently, mixed con-
ducting oxides based on Y,O,-ZrO,-TiO, solid solutions have
been investigated as SOFC electrode Character-
ization of the materials in terms of their electrical and electro-
chemical performance has been
( C ) Catlzode: ( a ) Doped Lanthanum Manganite: Be-
cause of the high operating temperature (1000°C) of the YSZ-
based SOFC, only noble metals or electronic conducting oxides
can be used as cathode materials. Noble metals, such as plati-
num, palladium, or silver, are unsuitable for practical applica-
tions because of prohibitive cost (and insufficient long-term
stability due to vaporization of silver). Several doped oxides
and mixed oxides have been proposed and The
mismatch, incompatibility with the electrolyte, and lack of con-
most commonly used.
LaMnO, is a p-type perovskite oxide. The perovskite struc-
orthorhombic or rhombohedra1 unit cells. Undoped LaMnO,
is orthorhombic at room temperatureh5and shows an ortho-
rhombic-rhombohedra1 crystallographic transition at about
387"C."'."' At high temperatures, the material can have oxygen
excess, stoichiometry, or deficiency depending on oxygen par-
tial pressure.h"-"' For example, at 1 200°C, the oxygen stoichi-
ometry of LaMnO, ranged from 3.079 to 2.947 under oxygen
March 1993
partial pressures of 1 to 10 'I ho atm (10' to 10-".b')
Pa).6x[n oxi-
dizing atmospheres, LaMnO, has oxygen excess and the
amount of excess oxygen varies with temperature. In reducing
atmospheres, the material becomes oxygen deficient. Under
very reducing conditions, LaMnO, dissociates into La,O, and
MnO; however, the dissociation is reversible.'" The lowest oxy-
gen partial pressure before LaMnO, dissociates into multiple
phases is termed "the critical oxygen partial pressure." This
critical partial pressure depends on temperature, shifting to
higher values at higher temperatures. At 1 IOO"C, the critical
oxygen partial pressure for undoped LaMnO, is about 10 l 4 to
10 I s atm (lO-'to lo-'" For SOFC applications, sig-
nificant changes in oxygen stoichiometry of LaMnO, (espe-
cially during fabrication) must be avoided to minimize
undesired dimensional change^.'^
In addition to oxygen nonstoichiometry, LaMnO, can also
have lanthanum deficiency and excess. LaMnO, with lantha-
num excess may contain La,O, second phase, which tends to be
hydrated to La(OH),. This hydration is undesirable for SOFC
applications because it can cause disintegration of sintered
LaMnO, structure. Since it is very difficult to prepare the stoi-
chiometric material, LaMnO, with a lanthanum deficiency is
recommended for use in SOFCs.
LaMnO, has intrinsic p-type conductivity due to the forma-
tion of cation vacancies. Thus, the electrical conductivity of the
material can be enhanced by substituting a lower-valence ion on
either the A or B sites. Doping LaMnO, with various lower-
valence cations such as strontium, calcium, barium, nickel, or
magnesium has been Strontium-doped LaMnO, is
currently the preferred cathode material in SOFC because of its
high electronic conductivity in oxidizing a t m ~ s p h e r e s . ~ ~ ~ the
Strontium doping enhances the electronic conductivity of
LaMnO, by increasing the Mn4+ content by the substitution of
La'+ by Sr2+:%'
LaMnO,% La:+,S<+Mn?t,Mn:'+O, (2)
The electronic conductivity of strontium-doped LaMnO, takes
place via the small polaron conduction mechanism. Figure 10
shows the temperature dependence of the conductivity of both
undoped and strontium-doped LaMnO, ." At temperatures
below 1000°C, plots of In uT(where u is the conductivity and T
the temperature) vs l/T are linear, as predicted by the following
equation derived for the small polaron conduction:
u = (A/Oexp( - E,/k7') (3)
where A is the preexponential factor, k the Boltzmann constant,
and E, the activation energy for conduction. The E, values cal-
culated from the slopes of the plots are 18.3, 18.3, 15.4, and
8.7 kJ/mol for undoped, 5 , 10, and 20-mol%-strontiuni-doped
LaMnO,, respectively. The variation of the conductivity of
La, _,Sr,MnO, with strontium content appears to exhibit a max-
imum. However, the strontium level where the maximum con-
ductivity is observed has not been well established (e.g., 15
o LaMnOJ
5 Cornnosition
-0
50
60 90 120 150 180 210
lTr, 1 V K '
Fig. 10. In OT vs IITfor undoped and strontium-doped LaMnO,
Cerumic Fuel Cells 569
24
-f 2 2
-0
$ 20
0
$ 18
F
2 16
D
14 5
Q
3 12
-
101' I
-160 -140 -120 -100 -80 -60 -40 -20 00
LOG OXYGEN PARTIAL PRESSURE, ATM
Fig. 11. Conductivity as a function of oxygen partial pressure for
La,, >MnO,at various tcmperatures."
mol% strontium in one studyXSand 55 mol% strontium in
another study"), probably due to differences from study to
study in synthesis methods, sintering conditions, sample
microstructures, and measuring techniques. For LaMnO,
doped with less than SO mol% strontium, the conductivity
shows negative temperature dependence at temperatures above
1 OOO°C, suggesting a semiconducting-to-metallic transition.
The metallic-type conduction behavior is observed for SO- to
60-mol%-strontium-doped LaMnO, at lower temperatures
(200" to 1000°c~.87
Oxygen activity and cation deficiency significantly influence
~ ~electrical
-~~ behavior of doped LaMnO,. At 10OO"C, the con-
ductivity of strontium-doped LaMnO, shows little dependence
on oxygen partial pressure in the high oxygen partial pressure
region, and this region becomes narrower with increasing tem-
perature (Fig. 1 l)." As the oxygen partial pressure is reduced,
the conductivity decreases as a function of the fourth root of
oxygen partial pressure. At the critical oxygen partial pressure,
an abrupt decrease of the conductivity is observed due to the
decomposition of the LaMnO, phase. This critical oxygen par-
tial pressure shifts to higher values when the temperature and/or
the strontium content are increased.
Vacancies at the lanthanum site influence the phases and
electrical properties of doped LaMnO,. (La, - ,SrJI -.MnO,-,
undergoes a phase transition at about 700°C in air." The con-
ductivity behavior of the material changes at the phase-transi-
tion temperature. Below 700"C, the small polaron hopping
mechanism is applied for the conductivity. Above 700°C, the
conductivity shows little dependence on the temperat~re.'~
The thermal expansion coefficient of undoped LaMnO, is
about 11.2 x 10 -'cm/(cm.K). Doping LaMnO, with stron-
tium increases the material thermal expansion coefficient,"'.''
and the coefficient increases with increasing strontium content
(Table II)." Thus, the thermal expansion coefficient of the
strontium-doped LaMnO, cathode is higher than that of the
YSZ electrolyte. However, there are few reported problems due
to this thermal expansion difference, probably because the
material has been tailored to minimize the mismatch. Substitu-
tion of lanthanum with smaller cations, such as calcium, lowers
the thermal expansion coefficient of LaMnO,. ' .**
Table 11. Thermal Expansion Coefficientsof
hW
- ,SrNnO,*
Thermal expansion coefficient
( x 10 ' crn/icrn.K))
240
''
570 Journal of the American Ceramic Society-Minh
In the fabrication and operation of the SOFC, there are con-
cerns regarding the chemical compatibility of LaMnO, cathode
with the YSZ electrolyte. Manganese is known to be a mobile
species at high temperatures and can easily diffuse into the elec-
trolyte, changing the electrical characteristics or the structure of
both the cathode and the electrolyte. Fabrication temperature is
generally limited to below 1400°C to minimize this migration.
At lOOO"C, manganese migration is negligible,94.y5 and there is
no report on any significant manganese effects for SOFCs oper-
ated up to 10000 h. The interaction between LaMnO, and YSZ
has been studied at SOFC operating and fabrication tempera-
ture~.~""'~ No significant reactions between LaMnO, and ZrO,
have been observed at temperatures below 1200°C; above
1200"C, the manganite reacts with ZrO, to produce
La,Zr,07.94.97 Another reaction product, SrZrO,, may also form
with LaMnO, containing high strontium dopant content (x =
0.3).9h.1mThese reactions can be predicted using the chemical
potential diagrams for the La-Mn-Zr-0 system. IM The forma-
tion of La,Zr,O, in the SOFC can significantly influence the
performance of the cell because the conductivity of this phase is
about 2.5 orders of magnitude lower than that of YSZ. To mini-
mize the reaction with YSZ, LaMnO, with substantial lantha-
num deficiency is preferred. In addition to reaction with YSZ,
LaMnO, may react with doped LaCrO, when in contact with the
interconnect at high temperatures. Strontium and calcium dop-
ants in LaCrO, tend to migrate to the interface to form com-
pounds such as (Sr,La),Mn,O, and (Ca,La),Mn,0,.'"3~'04
Solid solutions or mixtures of doped LaMnO, with other
compounds have also been investigated for SOFC applications.
LaCrO,-LaMnO, solid solutions are suggested to be used as
cathode materials to provide better morphological stability and
to increase electrode resistance toward reduction. 1"5-107 LaCoO,
has been added to LaMnO, both to tailor cathode thermal
expansion and to improve cathode electrical conductiv-
ity.".lnX.'OV
Cathodes made of YSZ-LaMnO, mixtures have been
found to have better resistance to sintering."' Additions of plat-
inum to LaMnO, cathodes improve cell performance by
increasing cathode conductivity and reducing contact resistance
between cathode and current collector."'
(b) Other Cathode Materials: Doped lanthanum cobaltite
(LaCoO,) is another perovskite oxide of interest as SOFC cath-
ode material."2-"5 LaCoO, has been extensively studied as an
oxygen electrode catalyst for controlling automotive exhaust
emissions. ' I 6 LaCoO, belongs to the same class of oxide com-
pounds as LaMnO,. The material shows a large oxygen defi-
ciency at high temperatures. 117.11X Previous studies have shown
that, similar to LaMnO,, LaCoO, has intrinsic p-type conduc-
tivity, and the conductivity can be enhanced by substituting a
lower-valence ion (such as strontium or calcium) on the lantha-
num site. 1'9~120LaCoO, has a higher electrical conductivity than
LaMnO, under similar However, there are sev-
eral key differences in the characteristics of LaMnO, and
LaCoO, as SOFC cathode materials. First, LaCoO, phase is
much less stable against reduction when compared with
LaMnO,. At 1000°C, LaCoO, dissociates into other phases at
oxygen partial pressures of less than atm ( Pa),' (for
comparison, LaMnO, decomposes at oxygen partial pressure of
about lo-'' atm (lo-'' Pa)). Second, the thermal expansion
coefficient of LaCoO, is greater than that of LaMnO,. The ther-
mal expansion coefficient of La,,Sr,,CoO, is 23.7 x lo-'
cm/(cm.K),12'whereas the thermal expansion coefficient of
La,,Sr,,MnO, is only 12.8 X lo-' c~n/(cm.K).~'Third,
LaCoO, tends to react more readily with YSZ than LaMnO, at
high temperatures. '22.123 At present, doped LaCoO, is being
used mainly as cathode material in SOFC stacks of a segment-
ed-cell-in-series design (see section on stack design and
fabrication).
Early SOFCs used tin-doped indium oxide (In,O,) as the
cathode material. '24-126 This material exhibits excellent electri-
cal conductivity under fuel cell operating conditions and can be
applied as thin films by the chemical vapor deposition
method. The material performed satisfactorily for up to 5000
Vol. 76, No. 3
h without degradation. However, In,O, represents the most
costly and least thermodynamically stable component in the
SOFC. Therefore, In,O, has been replaced by doped LaMnO,.
Other materials containing In,O,, such as In,O,-Pro,-HfO,
and In,O,-PrO,-ZrO,, have also been proposed. 128-130 Doped
YMnO, compositions have recently been considered for their
possible applications as cathodes in SOFCs. '"
( C ) Interconnect: ( a ) Doped Lanthanum Chromite:
The stringent requirements for the interconnect of a SOFC elim-
inate all but a few oxide systems from consideration. Lantha-
num chromite (LaCrO,) is particularly suitable from the
standpoint of high electronic conductivity under fuel and oxi-
dant atmospheres, stability in the fuel cell environment, and
compatibility with other cell components. LaCrO, is currently
the most common material for the interconnect in the SOFC.
LaCrO, is a perovskite oxide with very refractory properties
(melting point >2400"C). The oxide is orthorhombic at room
temperature"2 and undergoes a crystallographic transformation
from orthorhombic to rhombohedral at about 240" to
2800C,I33-135The rhombohedral form of the oxide is stable up to
1000°C. A further increase in temperature results in a rhombo-
hedralxubic transition at about 1650°C.134.136-138 LaCrO, has
oxygen stoichiometry in oxidizing atmospheres but becomes
oxygen deficient under very reducing conditions. '" LaCrO, can
also have lanthanum deficiency or excess. The temperature at
which the orthohombic-rhombohedra1 transformation occurs is
dependent on the lanthanum stoichiometry and increases with
increasing lanthanudchromium ratio.y3 Similar to LaMnO,,
excess lanthanum in LaCrO, tends to precipitate as La,O,, caus-
ing hydroxide formation and subsequent disintegration of
LaCrO, structures at room temperature. 14"
LaCrO, can be substituted with a cation on either the lantha-
num or chromium sites. Examples of the substituents or dop-
ants include strontium and calcium (lanthanum ~ i t e ) ' ~ , ' ~and
'.'~'
magnesium, cobalt, zinc, copper, nickel, iron, aluminum, and
titanium (chromium site).143-149 The substitution of LaCrO, with
a lower-valence ion influences the properties of the material in
many ways, including phase transformation, conductivity, oxy-
gen stoichiometry, and thermal expansion. The orthorhombic-
rhombohedral transformation temperature of doped LaCrO, is
dependent on the dopant. Strontium substitution for lanthanum
in LaCrO, lowers the transformation temperature, stabilizing
the rhombohedral structure at room temperature. '" Nickel or
calcium substitution raises the transformation temperature.146
Magnesium substitution, on the other hand, does not affect the
orthorhombic-rhombohedra1 transformation temperat~re.~'
LaCrO, is a p-type conductor due to holes in the 3d band of
the chromium ions. Under oxidizing conditions, substitution of
a lower-valence ion on either the lanthanum or chromium sites
of LaCrO, results in a charge-compensating transition of C 8 +
to Cr4' ions, thereby enhancing the electronic conductivity of
the material. Under reducing conditions, charge compensation
occurs by the formation of oxygen vacancies; thus, no increase
in the electronic conductivity is anticipated. To have adequate
conductivity for SOFC interconnect uses, LaCrO, is often
doped with divalent ions. The most common dopants are stron-
tium, calcium, and magnesium. Figure 12 shows as an example
the conductivity (in air) of strontium-doped LaCrO, as a func-
tion of temperature. The linearity of the plots of log UT vs 1/T
for doped LaCrO, indicates thermally activated hopping of
small polarons as the conduction mechanism. 's"-'s6 The activa-
tion energy for conduction and the conductivity at 1000°C for
several doped LaCrO, are given in Table 111. The conductivity
of doped LaCrO, depends on the equilibration atmosphere.
Equilibration in a reducing atmosphere, such as hydrogen gas,
causes an appreciable decrease in the conductivity.148.152 The
conductivity of doped LaCrO, in hydrogen is 3 orders of mag-
nitude lower than that in air.Is7Since the LaCrO, interconnect in
a SOFC is subjected to a dual atmosphere (with fuel on one side
and oxidant on the other), a conductivity gradient across the
material may exist. However, the overall conductivity of the
material is still adequate for its use.158.159
For example, under
March 1993 Ceramic Fuel Cells 57 1

lo5 I
0.04
t
0
B
c
l
'- - j L z 0.03
lO3 1 x = 0.05 x = 0.10 t!
0.02

10-2
3
0
I
0.01

10 '
5
I
10
I
15
in,104K-l -11 -9 -7 -5 -3 -1 1 3
LOG OXYGEN PARTIAL PRESSURE, Pa
Fig. 12. log oT vs 1/Tfor La, _,Sr,Cr0,.i56
Fig. 14. Oxygen vacancy concentration and electrical conductivity
as a function of oxygen partial pressure and dopant content for
the fuel cell operating environment, the conductivity of magne- LaCr, -rMg,O, at 1200"C.ih2
sium-doped LaCrO, is about 2 W ' . c m - l , exceeding the con-
ductivity requirement for the interconnect. I S 9 For
polycrystalline LaCrO, exposed to an oxygen potential gradi- The thermal expansion coefficient of LaCrO, at room tem-
ent, such as the SOFC dual atmosphere, the material equili- perature is about 6.7 X lo-' cm/(cm.K). Above 240°C (the
brates quickly due to its rapid oxygen exchange ra@et'. ' orthorhombic-rhombohedra1 transformation temperature),
The conductivity of doped LaCrO, equilibrated under vari- LaCrO, has a thermal expansion coefficient of about 9.2 x
ous oxygen activities has been correlated to the material defect 10-6cm/(cm.K) The thermal expansion of LaCrO, can be
chemistry.13Y.143.161-165 The correlation shows that, at high oxy- modified by substitution of aliovalent or isovalent ions into the
gen partial pressure, electronic compensation occurs by a Cr3+ structure. The substitution of aluminum ions markedly
to Cr4+transition, whereas ionic compensation takes place at increases the thermal expansion coefficient. Magnesium ions
low oxygen partial pressure. The critical oxygen partial pres- do not affect the thermal expansion coefficient.166On the other
sure (at which the electronic conductivity of LaCrO, signifi- hand, the substitution of calcium ions'67or strontium ion^^'^''^
cantly decreases) is dependent both on dopant concentration increases the thermal expansion coefficient of LaCrO,. Table
and temperature. This critical oxygen partial pressure is lower IV summarizes thermal expansion coefficient data for undoped
at lower dopant concentrations and lower temperatures. Figures and doped LaCrO, materials.
13 and 14 show how the conductivity and oxygen vacancy con- One of the requirements for the LaCrO, interconnect in
centration of magnesium-doped LaCrO, vary with temperature, SOFCs is that it must be dense to avoid cross leakage of fuel and
oxygen activity, and dopant oxidant gases. It is well-known that LaCrO, is difficult to sinter
to high densities under high oxygen activity conditions. LaCrO,
appreciably volatilizes chromium oxides in oxidizing atmo-
spheres. 137.148.166.lb9. I70 Because of the volatilization, the predom-
Table 111. Conductivity Data for Doped LaCrO,* inant mass-transport mechanism is a gaseous process mainly
Activation energy involving the chromium oxide compounds. This leads to an
Dopant Composition Conductivity (Io0o"C) (kJ/mol)
(MO) (mol% MO) (0-'.cm ') ~ [Reference] evaporation-condensation mechanism of sintering in which the
lanthanum and chromium ions evaporate in some form from the
None 0 I 18 [150] surface of the original grains and condense out onto the points
10 3 19 [162]
YAO
CaO
10
20
14
35
12[156]
13 [165]
of irregular contact, which are the areas of maximum surface
energy. Because neck growth is accomplished without the
*Air atmosphere
transport of the material from the bulk of the grains, little densi-
fication or pore removal occurs. The sinterability behavior of
LaCrO, has been correlated to chemical potential diagrams and
vapor pressures of chromium oxides calculated for La-Cr-0
systems.171The poor sinterability of LaCrO, in air or oxidizing
0.05
6 atmospheres is ascribed to the formation of a thin layer of Cr,O,
t 0.4
0 (from CrO, gases) at the interparticle neck during the initial
6 0.04
eg stage of sintering. Because of the high volatility of chromium
0
z 0.2 oxides, to sinter LaCrO, to high densities, firing temperatures
g 0.03 9 greater than 1600°C under low oxygen partial pressures have
5; 0.0
0
v) 0.02
2
2 -0.2
Pq
Table IV. Thermal Expansionof LaCrO,*
= 0.01 0'
-0.4 -
z Composition (nominal)
Thermal expansion coefficient
( x 10 ' cm/(cm K))

-11 -9 -7 -5 -3 -1 1 3 LaCrO, 9.5

LaCro YMg" 1 0 3 9.5
LOG OXYGEN PARTIAL PRESSURE, Pa L a ,Sr0 ,CrO, 10.7
L a &a, ,Ffl, 10.8
Fig. 13. Oxygen vacancy concentration and electrical conductivity LaCr, ,Coo ,O, 13.1
as a function of oxygen partial pressure and temperature for La, RCa, 0" ,COI, 10, 11.1
LaCr,,,Mg, "References 93 and 183
512 Journul ofthe American Ceramic Society-Minh
traditionally been used. '72 Control of oxygen partial pressures
close to those specified by the chromium/Cr,O, phase bound-
aryI7' suppresses grain growth and allows maximum densifica-
tion to occur.
Several approaches have been investigated to enhance the
sinterability of LaCrO, at firing temperatures below 1600°C in
oxidizing atmospheres:
(i) Highly reactive powders: Improvements in the densi-
fication of LaCrO, can be obtained when highly reactive (high
surface area) powders are used. 171.17sUniform, high-surface-
area powders without agglomeration lower the temperature
required to densify LaCrO,. For example, a synthesis technique
called the glycineinitrate process has been developed to pro-
duce chrornite powders of high-quality, ultrafine crystalline size
(25 to 100 nm)."4 LaCrO, powders produced by this method
can be sintered to near-full density in air at 1550°C.
(ii) Nonstoichiometry: Nonstoichiometry can influence
sintering of LaCrO, in air. The sinterability of LaCrO, has been
found to vary significantly with relatively small change in the
material stoichiometry. Chromium deficiency is particularly
effective in enhancing the sintering. 1h7.176.177For strontium-
doped LaCrO,, higher sintered densities have been obtained for
samples with chromium deficiencies.'7x.'7"Chromium-defi-
cient, calcium-doped LaCrO,, La,,,Ca,,,Cr,-,O, (0 < y <
0.02), can be sintered to 94% of theoretical density in air at
1300°C,whereas no densification is observed for the stoichio-
metric compound, La,,,Ca, ,CrO, ( y = O)."" The exact sin-
tering mechanism in chromium-deficient materials is not well
understood, although vapor-, liquid-, and solid-phase mass-
transport mechanisms appear to be operative in this case.'")
(iii) Dopants: One way to enhance the fundamental sin-
terability of LaCrO, is to dope it with an ion that will increase
the concentration of vacancies present, allowing bulk or grain-
boundary mass transport to occur. Also, dopants can improve
the sinterability of LaCrO, by reducing the volatility of chro-
mium from the surface during sintering. For example, the sub-
stitution of aluminum for chromium has been found to
substantially decrease the volatilization of magnesium-doped
LaCrO,. '" Dopants can also form a transient liquid phase dur-
ing firing and enhance the densification by liquid-phase sin-
tering. The enhanced sinterability of LaCrO, doped with
strontium may be due to the formation of SrCrO, melt.174The
densification of calcium-doped LaCrO, can be contributed to
the presence of Ca-Cr-0 melts. 'xo Similarly, calciumicobalt-
doped LaCrO, can be sintered to full density at temperatures
below 1400°C in air due to the presence of a transient liquid
p h a ~ e , ' ~ ~which
. ' ~ ' composition is dependent on the amount of
cobalt and calcium substitution. The main problem with tran-
sient liquid phases is that, in cofiring LaCrO, with other SOFC
components, the liquid phase tends to diffuse into other conipo-
nents and no densification of the chromite is obtained. Ix0.1x4.'xs
(iv) Sintering aids: Introduction of a liquid-phase sin-
tering aid-a second phase with a significant lower melting
point-ncourages densifcation of LaCrO, in oxidizing envi-
ronments. The function of liquid-phase sintering aids is to pull
the particles closer together by surface tension forces and to
enhance diffusion of the solid phase to the points of particle-to-
particle contact to promote densification. Sintering aids, such
as low-melting oxide eutectics and LaF,, YF,, and MgF2up to 8
to 10 wt% have been used to densify LaCrO, in air at tempera-
tures below 1400°C.'x"'xxSimilar to transient liquid sintering,
the main difficulty involving sintering aids is that they may
migrate to other cell components, causing elemental migration
and morphological changes.
( v ) Processing techniques: In addition to the main
approaches described above. processing techniques can be
modified or tailored to enhance the densification of LaCrO,.
For example, microwave processing of LaCrO, has shown
promise to lower the sintering temperature. I*') Firing LaCrO,
between CrzO lates improves the densification of strontium-
doped LaCrO: '
Vol. 16, No. 3
(b) Other Interconnect Materiuls: As mentioned earlier,
only very few oxides can be considered for interconnect appli-
cations."' Early SOFCs used doped CoCr,O, as interconnect
material."* This compound was later replaced by LaCrO,.
Recently, YCrO, has been evaluated as an alternative material
to LaCrO,. '5h~lX'.ry3~1ys Although YCrO, is less refractory than
LaCrO,, the yttrium compound has the advantage of greater
stability (less interaction, no hydration) in the fuel cell environ-
ments. Glass composites have also been c o n ~ i d e r e d . ' ~ ~In. " ~
addition to ceramics (oxides), use of certain high-temperature
alloys as SOFC interconnect is also possible."* The primary
concerns regarding metallic interconnects are thermal expan-
sion mismatch with other cell components and long-term insta-
bility (oxidation, corrosion) under fuel cell operating
conditions. Coating with a LaCrO, film can be used to protect
metallic interconnect. lYy
(2) Gas Reactions at Solid-Oxide Fuel Cell Electrodes
The reversible voltage E" is the maximum voltage that can be
achieved by a SOFC under specified conditions of temperature
and gas composition. E" can be calculated from the Nernst
equation. The voltage of an operating cell E is always lower
than ED.As the current is drawn from the fuel cell, the cell volt-
age falls due to internal resistance and polarization losses.
Thus, the voltage of an operating cell is given as
E = E" - IR, - +
(q2$ qc) (4)
In the above equation, I R , is the internal resistance or ohmic
loss ( I is the cell current. R, the internal resistance of the cell)
and qdand qcthe anode and cathode polarization, respectively.
Ohmic losses result from the resistance of the electrolyte and
other cell components. Polarization (overpotential) losses are
associated with the electrochemical reactions taking place at the
interface between the electrodes and the electrolyte. The kinet-
ics of these reactions (the oxidation of hydrogen and CO at the
anode and the reduction of oxygen at the cathode) play a critical
role in determining polarization losses in SOFCs. Other
important reactions in SOFCs are those of fuel contaminants
(such as sulfides) and the reforming of hydrocarbon gases at the
anode.
( A ) Reactions uf Anode: The electrochemical oxidation
of hydrogen on nickel anodes in contact with YSZ electrolytes
has not received much attention in SOFC development proba-
bly because polarization losses at SOFC anodes are believed to
be small in comparison with those from the reduction of oxygen
at cathodes. The hydrogen oxidation at nickel electrodes pro-
duces water, according to the following reaction:
H2 + 0;)= H,O + V ; + 2e- (5)
It has been generally assumed that the nickel metal plays the
catalytic role in the oxidation. The influence of electrode mate-
rials on the electrochemical characteristics of the hydrogen
reaction at 1000°C has been demonstrated.'"".'"' The catalytic
effect of the electrode surface is also supported by the observa-
tion that an increase in electronic carrier concentration
enhances the reaction rate."" In this case, the reaction mecha-
nism involves the adsorption of hydrogen on nickel followed by
the electrochemical reaction
H2 + 2Ni = 2NiH (6)
2NiH + 0;)= H,O + 2Ni + y, + 2e-
(7)
Recently, however, there is evidence suggesting that the elec-
trolyte plays a major electrocatalytic role in the hydrogen reac-
t i o n , m ~ ~ xThe
) ~ supporting experimental observations include
the following: rate of oxidation of hydrogen and hydrocarbons
at a metal anode with solid electrolyte is independent of the
electrode material; activation enthalpies of the reaction are also
independent of the electrode material; and blackening of the
electrolyte by electrolysis leads to marked enhancement in the
reaction rate. Thus, it has been concluded that the major reac-
tion steps occur at active sites on the electrolyte surface. The
March 1993
electrochemical reactive sites (ERS) are hypothesized to be
oxygen vacancies (VkdRs)with electrons migrating along the
electrolyte surface to or away from these active sites. The fol-
lowing reaction mechanism has been postulated:
H2 + 2vERS = 2HERS
0; + 2H,,, = HZO + V, + 2VERs+ 2e-
At present, it appears that both the electrode and electrolyte
surface contribute to the reaction process.
At nickel and other metal electrodes, the oxidation of dry
hydrogen occurs with significant overpotential or interfacial
(In SOFCs and other solid electrolyte systems,
voltage losses besides material resistance losses are commonly
referred to as interfacial resistance losses.) A few mole percent-
age of H,O in hydrogen can dramatically reduce the electrode
interfacial resistance2I2(Fig. 15). At high H,O concentrations,
the interfacial resistance increases with increasing H,O/H,
ratio. The hydrogen electrode is thus expected to exhibit a mini-
mum interfacial resistance at a certain H,O/H, ratio. The role of
H,O in the hydrogen oxidation is not clearly understood
although H,O is believed to adsorb on the surface of the ZrO,
electrolyte and enhance the electronic conductivity around the
triple contact (electrolyte-electrode-gas) point, resulting in
increased reaction rate.202,211 In SOFCs, interfacial resistance
losses at anodes due to lack of H,O do not pose a problem since
H 2 0 is always present (at least a percentage) during fuel cell
operation.
The overpotential of the hydrogen oxidation at SOFC nick-
el/ZrO, anode obeys the Tafel e q ~ a t i o n : ~ ' ~ - ~ "
RT i (>100 ppm) can result in severe performance losses which are
q = -1n-
2F io
where -q is the overpotential, R the gas constant, T the tenipera-
ture, i the current density, and i,) the exchange current density.
The overpotential characteristics of the reaction are strongly
influenced by the formation of oxide on the electrode sur-
face,2'5-219
The electrochemical reactions at SOFC anodes can also
involve the oxidation of CO. Compared to the hydrogen reac-
tion, the oxidation of CO on nickel electrode at 1000°C is
accompanied by higher overpotential. 20922'1-221 Similar to the
hydrogen electrode, the CO oxidation at a metal electrode also
exhibits a minimum interfacial resistance as a function of
CO,/CO ratio.2'2.224,225
The role of CO, is similar to that of H,0
in H,O/H, systems. The addition of hydrogen gas to CO
2.00
1.75
N
5 1.50
z equilibrium are the operating pressure, the temperature, and the
$ 1.25
0
2
4 the feed gas). Equation (12) is favorable at low pressure, high
5 1.00
tc
W ent on the left side of Eqs. (1 1) and (12), carbon may be depos-
0.75
5
d
a
W 0.50
2 CH,
0.25
0.00
lo" 10-3 1 o-*
H20 PARTIAL PRESSURE, ATM
Fig. 15. Interfacial resistance of nickel/ZrOz cermet electrode as a
function of H,O partial pressure (balance H,) at 1000°C.2'z
Cerumic Fuel Cells 513
reduces interfiacial resistance. In gas mixtures, such as coal
gases that contain H?, H 2 0 , and CO, the favorable path for the
oxidation of CO is via the generation of hydrogen by the shift
reaction
(8) CO + H,O = CO, + HZ ( 1 1)
(9) Under fuel cell operating conditions, a nickel anode is expected
to have low overpotentials of the electrochemical reactions,
thus small interfacial resistance losses. However, it is not
always the case in practice. Because the SOFC anode consists
of nickel-metal particles dispersed on a stabilized ZrOz support,
the anode performance strongly depends on electrode prepara-
tion conditions and electrode n ~ o r p h o l o g y . " ~ . ~For
~ ~exam-
-~~"
ple, the nickelistabilized ZrO, cermet anode shows a strong
dependence of electrode performance on nickel distribution.
Lower interfacial resistances are obtained for anodes with
smaller nickel particle separation.'" Reducing the nickel parti-
cle size in the anode significantly decreases the anode interfa-
cial resistance in SOFCs.
Many applications of SOFCs will use gases other than pure
hydrogen (e.g., coal gas and natural gas) as the fuel.
Depending on the source of the gases and the cleanup process
used, varying amounts of impurities or contaminants will be
present. The impurity expected to have the greatest impact on
SOFC performance and life is sulfur, present primarily as
hydrogen sulfide (H2S). Even low levels (parts per million
(ppm)) of H,S may cause significant performance loss at the
anode. In general, if the sulfur contaminant concentration is
low, a full recovery of fuel cell Performance is possible upon
switching to clean fuel.27'' Operations at high sulfur levels
only partially The tolerance limit for H,S in the
fuel for SOFCs has not been firmly established.
Several possible mechanisms may account for the decrease in
performance of SOFCs due to the presence of H,S in the fuel:
formation of nickel sulfide on the nickel electrode can poison
the anode; hydrogen sulfide can poison the hydrogen oxidation
reaction by adsorbing on anode active sites; and adsorbed H,S
can poison the water gas shift reaction, causing a hydrogen
deficiency in the fuel cell. At present, the exact mechanism
responsible for performance loss is not clearly defined.
Because of its high operating temperature (around I OOO"C),
a SOFC can reform conventional hydrocarbon fuels internally.
Internal reforming in a SOFC is expected to simplify the overall
fuel cell system design because of elimination of the external
reformer. The feasibility of internal reforming in SOFCs has
been demonstrated,?10.211.211-233 The steam reforming of hydro-
carbon fuels involves the following reaction (written for
methane):
CH, + H 2 0 = CO -t 3H2 (12)
During the reforming reaction, the water gas shift equilibrium
(Eq. 1 1 ) is also established. Consequently, a mixture of H,,
CO, CO,, and CH, is obtained. The factors which affect the
steam ratio (the ratio of moles of steam to moles of carbon in
temperature, and high steam ratio. If insufficient steam is pres-
ited according to the following reactions:
2co = CO? +c (13)
= 2H, +c (14)
Carbon formation is undesirable in SOFCs because deposited
carbon can plug gas flow and degrade anode performance by
blocking the active sites.
lo-' In general, the reforming activity of a SOFC anode is
improved by high nickel surface area, i.e., small nickel crystdl-
line size. The acidity and water adsorption capability of the
support also influence carbon formation although preliminary
results indicate that the ZrO, support plays little role in carbon
574 Journal of the American Ceramic Society-Minh Vol. 76, No. 3

formation.234Modified supports have been used to prevent car-
bon deposition.235Anodes based on conductive CeO, have been
found to be effective in oxidation of CH, without significant
carbon formation.236
( B ) Reactions at Cathode: The overall reaction for the
oxygen reduction at a SOFC cathode can be written as
+
O2 2V; + 4e- = 20;
This reaction is made up of a series of bulk and surface pro-
cesses. One or several of these processes can be rate-determin-
ing steps. Figure 16 shows some possible controlling steps:237
gas diffusion external to the electrode or within the pores of the
electrode; adsorption and dissociation of oxygen on the elec-
trode surface or the electrolyte; diffusion of adsorbed oxygen
on the electrode, on the electrolyte to the three-phase boundary
line (between gas, electrode, and electrolyte), or into the elec-
trode/electrolyte interface; diffusion of dissolved oxygen in the
electrode or electrolyte; diffusion of electron holes in the elec-
trolyte; and charge transfer across the electrode/electrolyte
phase boundary. To understand the cathode polarization, identi-
fying the various reaction steps and determining the rate-con-
trolling step are necessary.
Most of the studies on the oxygen reaction have been con-
ducted on platinum electrodes in the temperature range of 400”
to 800°C.238Various reaction mechanisms and rate-controlling
steps have been suggested. Proposed rate-controlling steps
include diffusion of gaseous oxygen in the pores of the plati-
num e l e c t r ~ d e , adsorption
~ ~ . ~ ~ ~ of oxygen on the electrode
and the e l e c t r ~ l y t e , * ~dissociation
* ~ ~ ~ ~ - ~of
~ oxygen molecules
into a t o r n ~ , ~diffusion
~ ~ - * ~ of
~ oxygen along the electrode sur-
251-255 diffusion of oxygen atoms through the elec-
t r ~ d e , ~ ~diffusion
” ~ ~ ’ of electrons in the e l e c t r ~ l y t e , diffu-
~~~~*~~ tion of oxygen molecules although the detail of the reaction
sion of oxygen ions in the electrolyte,239~2s1~2s9-261 and charge
0 2
ELECTRODE
z trocatalytic activity of doped LaMnO, electrodes is greatly
’v)0
2 conditions, the electrode material is partly reduced, resulting in
u-
0
Ev)
0
3
z according to the following equations:
Y
LT
0
LT
a
-1
3
Y Thus, the enhanced activity of the electrode can be attributed to
-1
P electronic and ionic conduction) in the electrode material. 27a280
7 between electrode microstructures and electrochemical proper-
Fig. 16. Schematic diagram of possible steps for oxygen reduction at
an electrodelsolid electrolyte interface.*”
transfer reaction.262-*“It is well established that the rate-con-
trolling step for the oxygen reduction on platinum electrodes
varies, depending on the experimental conditions, such as oxy-
gen partial pressure, temperature range, overpotential regime,
and electrode characteristics. However, to date, there is still
considerable disagreement on the exact nature of the reaction
kinetics. One of the reasons for the disagreement is variations
(15) in the platinum electrode morphology from study to s t ~ d y . ~ ~ ’ ~ ~ ~ *
The location of the electrochemical reactive site on platinum
electrodes is also not well established although the three-phase
boundary (where the gas, electrode, and electrolyte meet) is
commonly believed to be the site where the charge transfer step
occurs .269
Compared to platinum electrodes, the oxygen reduction on
oxide electrodes has not been studied extensively. The behavior
of oxide electrodes is expected to be different from platinum
electrodes since the polarization process is markedly dependent
on the electrode materia1.27”~27’ The influence of electrode mate-
rial on the oxygen reaction kinetics has been demonstrated by
the wide variations of specific currents measured for different
metal and oxide electrodes on YSZ at 1000°C27’and lower
temperatures .*72.273
Different oxide materials show different reaction mechanism
and different catalytic activity for the oxygen reduction.274For
example, the activity of four doped perovskite oxide electrodes
studied at 800°C follows the following order: LaCoO, >
LaMnO, > LaFeO, > LaCrO,. The difference in activity
among the electrodes has been ascribed to their different cata-
lytic ability for oxygen-molecule diss~ciation.~’~ Under SOFC
conditions, the most probable rate-determining step for the oxy-
gen reduction on LaMnO, electrodes is the dissociative adsorp-
mechanism has yet to be elucidated. A similar rate-determining
step has also been proposed for other oxide
Defect chemistry plays an important role in the activity of
doped perovskite electrodes.276The concentration of oxygen
adsorption sites is directly related to the concentration of
defects in the electrode. In doped perovskites, a certain level of
oxygen vacancies is present, influencing the exchange of oxy-
gen,*” thus, the reaction rate, at the material surface. The elec-
enhanced under high cathodic p ~ l a r i z a t i o n . ~ ~Under
~ ~ ‘ ~ those
’
a marked increase of the oxygen vacancy concentration inside
the electrode. The oxygen reaction takes place not only at the
three-phase boundary but also on the electrode surface
the presence of both electrons and oxygen vacancies (mixed
Doped LaMnO, electrodes exhibit close relationships
ties.2x‘-2MThe interfacial resistance (conductance) and capaci-
tance of doped LaMnO, depends on the firing temperature. This
behavior has been explained by changes in the contact area at
the electrolyte/electrode interface and the length of the three-
phase boundary where the electrochemical reaction takes
place.2x1~282 Electrodes fired at higher temperatures have
smoother particles, and, as the result, the contact between the
electrode particles and the electrolyte increases, thus, larger
capacitance. On the other hand, because of smoother particles,
the three-phase boundary becomes shorter, resulting in higher
interfacial resistance. Thus, the electrochemical properties of
LaMnO, are expected to vary with starting material characteris-
tics and preparation conditions, especially firing conditions.
During firing, the interaction between the LaMnO, electrode
and the electrolyte must be minimized because it can cause
March 1993 Ceramic Fuel Cells
significant degradation in the cathode electrochemical
performance,'W2R5.286
An empirical equation has been developed for the oxygen
reaction rate at the LaMnO, electrode. 282.287 The reaction rate,
given as the steady-state current i , obeys the following
equation:
where io is the rate constant (exchange current), Po, the oxygen
partial pressure, and a, the oxygen activity in YSZ at the
LaMnOJYSZ interface. The value of i, has been found to be
about 2.7 mAlcm2 at 1000°C, and its activation energy is 178
kJ/mol. From the reaction rate, the electrode interfacial resis-
tance, RE, has been calculated and is given as
RT
R E B = -[exp(2qF/RT)
4F - exp( - 2qF/RT)] (19)
where S is the surface area of the LaMn0,lYSZ interface.
Equation (19) holds irrespective of the morphology of the
LaMnO, electrode layer.282
(3) Stack Design and Fabrication
At present, four common stack configurations have been pro-
posed and fabricated for SOFCs: sealless tubular design, seg-
mented-cell-in-series design, monolithic design, and flat-plate
design. The designs differ in the extent of dissipative losses
within the cells, in the manner of sealing between fuel and oxi-
dant channels, and in making cell-to-cell electrical connections
in a stack of cells. The ease of fabrication and assembly varies
among the designs, but the differences are hard to quantify at
this stage of development.
( A ) Sealless Tubular Design: The sealless tubular design
is the most advanced among the several SOFC concepts pro-
posed. In this design, the cell components are configured as
thin layers on a closed-one-end tubular support (Fig. 17).2"292
For cell operation, oxidant is introduced to the cell through an
injector tube near the closed end, where it traverses and exits
from the open annulus between the support tube and the oxidant
injector tube. Fuel flows on the outside of the support tube. At
the open end of the cell, unreacted fuel is combusted using the
oxidant stream exiting the cell.
The present support is a porous (35% porosity) 15-mol%-
CaO-stabilized ZrO, tube which has an inside diameter of 12 to
13 mm, a 1- to 1.5-mm wall thickness, and a 36-cm to 1-m
length. The tube is overlaid with a 1.4-mm porous (about 35%
porosity) strontium-doped (10 mol%) LaMnO,. A 40-pm gas-
tight Y,O,-stabilized (10 mol% Y,OJ ZrO, electrolyte layer
covers the cathode except in a strip of about 9 mm along the
active cell length. This strip of exposed cathode is covered with
a 40+m gastight magnesium-doped LaCrO, interconnect layer.
The 100-pm nickel/stabilized ZrO, cermet anode covers the
entire electrolyte surface. Work is currently going on to extend
INTERCONNECTION
AIR
OROUS SUPP
L ELECTRODE
ELECTROLYTE
Fig. 17. Sealless tubular design of solid-oxide fuel cell.*"'
515
the cell length to 2 m or morez9'and to replace the ZrO, support
tube with a cathode tube.
Individual cells are bundled in series and parallel electrical
connection to form a basic power-generating building block
(Fig. 18). The series and parallel electrical connection is
designed to protect the bundle or stack against complete failure
if an individual cell fails. Nickel felt is used to connect the
anode of one cell to the nickel plating on the interconnect of the
next cell for series connection and the anode of one cell to the
anode of the adjacent cell for parallel connection. The felt pro-
vides compliancy, thus minimizing stress placed on the cells
during operation.
One distinct feature of this design is that it has no seals;
therefore, the problems with gastight seals for ceramics at high
temperatures are eliminated. In addition, this design has the
advantage that each single cell is built as a unit structure. This
allows some freedom of thermal expansion and minimizes the
problem of cracking caused by undue thermally induced
stresses in a monolithic pack of connected cells. On the other
hand, the sealless tubular design has a relatively long current
path through the The current path is long in the plane of
the electrodes, resulting in a greater resistive loss. The support
tube is a limitation on cell performance. The thick support tube
restricts the amount of oxygen which can be transported to the
cathode/electrolyte interface. Thus, gas diffusion through the
tube can become the rate-limiting step and sets the limiting cur-
rent for the cell. Even below the limiting current, gas transport
represents a loss in cell performance. The electrochemical
vapor deposition (EVD) process used in the fabrication limits
the selection of suitable dopant materials for the electrolyte and
interconnect to a small number.
Sealless tubular SOFCs are fabricated by a manufacturing
process shown in Fig. 19 29s.296 as described below:
(i) The support tube is formed by an extrusion process.
Extrusion is the preferred low-cost method of forming large
quantities of support tubes. For practical use, the sintered sup-
port tube must possess adequate mechanical strength (low-
porosity material required) and allow high gas-diffusion rates
(porous structure required). Thus, starting material characteris-
tics and processing conditions must be tailored to obtain opti-
mal tube properties.297At present, the support tube for sealless
tubular SOFCs is fabricated by extrusion of a plastic mixture of
CaO-stabilized ZrO, powder plus cellulose and starch as pore
followed by sintering in air at about 1550°C.
(ii) The cathode is fabricated by depositing a slurry of
doped LaMnO, on the support tube and sintering in air at about
1400°C. The procedures in this fabrication step are tailored to
produce sintered cathode layers having the desired proper tie^.'^
(iii) The interconnect is made by the EVD technique. The
technique has proved to be the only reliable method of produc-
ing the thin, dense, interconnect layer for the sealless tubular
design. More details of the EVD process are discussed later.
Masking is used to limit the deposition of interconnect into a
strip along the length of the cathode. The masking material can
be easily removed in postdeposition cleaning operations.
(iv) The electrolyte is also made by EVD. The electrolyte
is deposited over the entire active area of the cell, including
overlap regions of about 0.5 mm on all sides of the intercon-
nect. Again, a masking material protects the interconnect dur-
ing the electrolyte deposition.
(v) Nickel is plated on the interconnect to provide electrical
contact.
(vi) The anode is applied by dipping the cell in a nickel
slurry. The anode covers the entire electrolyte surface, but not
in contact with the interconnect, to avoid internal cell shorting.
Suitable masking is used to cover the interconnect. The anode
is then fixed by EVD of doped ZrO, in the nickel matrix. This
ZrO, acts as a sintering inhibitor and maintains a porous, struc-
turally stable anode.
The EVD process is the key fabrication technique in the seal-
less tubular SOFC technology. The principle of the process is
576 Journal of the Americun Cerumic Society-Minh Vol. 76, No. 3

POSITIVE CURRENT COLLECTOR

IEECTROLME

POROUS SUPPORT TUBE

NEGATIVE CURRENT COLLECTOR

Fig. 18. Electrical connection in acalless tubular solid-oxide fuel cells.""'

TUBE MANUFACTURING I AREA 2

CATHODE APPLICATION I
-MASKING
*TUBE MANUFACTURING
*TUBE FINISHING *SINTERING

-+-
* EVD FIX
AREA 6
EVDANODE

* DIP PROCESS

1 *CLEANING

FINISH

CELL TESTING

Fig. 19.
I Ni PLATE-INTERCONNECT

-- Ni FLASH AND PLATE

WASHING/DRYING

Sealless tubular SOFC fabrication process.'"'

EVD-ELECTROLYTE

.DEMASKING

schematically shown in Fig. 20. The process (a modified cheni-

ical vapor deposition (CVD)) involves growing a dense oxide
layer on a porous substrate at elevated temperatures and
reduced pressures.'"' In the EVD of components for sealless
tubular SOFCs, steam and/or oxygen is fed to the interior of the
support tube while metal chloride vapor, hydrogen, and argon
are fed to the outside. Hydrogen is used to remove the chlorine Porous
formed, and argon is used as a flow-regime conditioning gas.3'" substrate
The growth of the oxide layer takes place in two stages at tem-
peratures of 1200" to 1350°C and at pressures of 53 to 267 Pa
(0.4 to 2.0 torr):
( i ) Stage 1, a CVD process, involves the formation of the PHASE I PORE CLOSURE BY CVD
oxide compound according to the following reactions:
+ H20 = MeO t 2 HCI
MeCI, + iH,O = MeO,.,, + yHCl (20)
MeCl2

2MeCI, + lo2+ yH, = 2Me0,,, + 2yHCI (21) PHASE II SCALE GROWTH BY EVD

This oxide formation closes the pores of the substrate. MeCI2 + 02- = Me0 + C12 t 2e-
(ii) Stage 2, an EVD process, involves the growth of the H20 + 2e- = H2 t 02-
oxide scale by reaction of metal chloride with oxygen ions in
the oxide (with the presence of some electronic conduction). Fig. 20. Principle of electrochemical vapor deposition.'""
March 1993
Oxygen ions are transported to the reaction sites by diffusion
across the scale.
MeCl, + f0'- = MeOIir + ;Cl2 + ye-
fHzO + ye- = i H 2 + i0'-
The scale growth rate of the EVD can be varied by temperature,
pressure, and chloride concentration and, practically, lies
between 0.5 and 2 pmimin.'"' Several aspects of the EVD pro-
cess have been studied .302-31' EVD reactors have been devel-
oped to automatically process batches of as many as 60 fuel
The sealless tubular SOFC has been fabricated in a number of
different sizes. The performance and life of single cells of this
design have been extensively e ~ a l " t e d . ' ~ " . ' ' ~ -State-of-the-
~~~
art cells have exhibited excellent and stable performance. Typi-
cal performance of sealless tubular SOFCs is about 0.68 V at
250 mA/cm2 on hydrogen fuel (89% H1,I I % H'O) with 85%
fuel Some cells have been tested for up to 30000
h. Stacks of different power output have also been constructed
and operated.'2''~''5 Tested stacks have demonstrate.d the overall
performance and reliability of the technology. For example, a
sealless tubular SOFC stack of 144 cells has been operated on
desulfurized, pipeline natural gas for more than 5000 h, pro-
ducing about 3 kW at I10 Recently, a 20-kW system con-
sisting of 576 cells of 50-cm active length has been built and
has been tested.2y2
( B ) SeRmented-Cell-in-SeriesDesign: The segmented-
cell-in-series design consists of segmented cells connected in
electrical and gas flow series. The cells are either arranged as a
thin banded structure on a porous support tube (banded cell
configuration) (Fig. 2 I ) I ? 5 . ? X X . 1 0 1 .??h-3?9 or fitted one into the other
to form a tubular self-supporting structure (bell-and-spigot con-
figuration) (Fig. 22).''"-3" The interconnect provides sealing
(and electrical contact) between the anode of one cell and the
cathode of the next cell. In this design, the fuel flows from one
cell to the next inside the tubular stack of cells and the oxidant
flows outside. In the banded cell configuration where the sup-
port tube (made either of Zr0,3"' or A1,033'X)is used, cells can
be made with component thickness on the order of 100 to 250
pin. In the bell-and-spigot Configuration, individual cells form
into short cylinders of about 1.5 cm in diameter. The cells are
about 0.3 mm thick to provide structural support.
The segmented-cell-in-series design offers the advantage of
improved efficiency. Cells in gas flow series have less power
/:I>
Lz/
ELECTROLYTE CATHODE INTERCONNECT
/ /
ANODE
FUEL
-----,
OXIDANT +
Fig. 21. Segmented-cell-in-series design of solid-oxide fucl cell
(banded cel I configuration).4
Crrurnrc Furl Crlls
ELECTROLYTE
I
(22)
(23)
INTERCONNEC?
OXIDANT
FUEL
Fig. 22. Segmented-cell-in-series design of solid-oxide fuel cell
(bell-and-spigotconfiguration).'
wasted in resistance losses because the first cell in series has a
higher output voltage. For example, four or five cells in fuel
flow series can generate about 10% more power than a single
cell of the saine total active area. The benefit of adding still
more cells diminishes rapidly above five or six cells in fuel flow
series. Like the sealless tubular design, the thick support tube
in this design restricts gas transport, thus limiting cell perfor-
mance. In the case of the bell-and-spigot configuration, the
self-supporting electrolyte reduces the losses arising from gas
transport but can significantly increase the resistive losses. Cell
internal resistance is an important consideration in this design.
The cell length is kept short to minimize the path for current in
the electrodes. Gastight seals are required for the segmented-
cell-in-series design. Fuel and oxidant must be separated by a
seal on both ends of a stack. In addition, gastight seals must be
maintained between each cell at interconnecting areas.
At present, the cell layers of the banded cell configuration are
made by a process based on plasma- and flame-spraying meth-
,3?8.1?9.3?l Plasma spraying is a process in which the desired
coating material in powder form is heated to above its melting
point while being accelerated by a carrier gas stream through an
electric arc. The molten powder is directed at the substrate, and
on impact, forms a coating on the substrate surface.
The fabrication of the components on the support tube is as
follows. Gastight A1,0, layers are first applied on the tube by
plasma spraying. The function of these thin A1,0, layers is t o
provide sealing at interconnecting areas. Thin copper tapes are
used for masking to make the required pattern on the tube. Dur-
ing spraying, the support tube rotates around its axis while the
spray gun traverses along the support tube axis. The anode
(NiO, 80 to 110 p m thick) is coated on the support tube by an
acetylene-flame-spraying process. The electrolyte (Y?O,-stabi-
lized ZrO?, 100 to 150 p m thick, 22 mm wide) is plasma-
sprayed on the anode after appropriate masking. A minimum
thickness of about 100 p m is required to achieve gastightness
without pinholes. The gastightness of the electrolyte has been
improved by applying low-pressure plasma spraying.'"'
Recently, a coating technique based on a C 0 2 laser has been
developed for making electrolyte layers. The interconnect
(NiAI, 200 to 250 p m thick) is fabricated by plasma spraying.
The interconnects at the ends of the support tube are covered
with an Al,O, coating to prevent oxidation during cell opera-
tion. The cathode (doped LaCoO,, 150 to 200 pm thick) is
578 Journal of the American Ceramic Society-Minh
deposited on the electrolyte and interconnect layers by acety-
lene flame spraying. During the spraying process, the crystal-
line structure of the cobaltite cathode can be destroyed;
however, the structure is recovered by firing at 1100°C for sev-
eral hours in air.343Gas permeabilities of electrode layers have
been
For the bell-and-spigot SOFC, self-supporting electrolytes
are fabricated by axial p r e ~ s i n g . ”Diffusion
~ welding is used to
make the interconnection seal between electrolyte cylinders.34h
The electrodes are applied by slurry coating.’l9
At present, development work on the segmented-cell-in-
series design has been focused on the banded cell configuration.
Six-, twelve-, and fifteen-cell tubes have been fabri~ated.’~’
Cell performance of 0.65 V at 200 mA/cm2 and 80% fuel utili-
zation has been achieved,34x and stacks have been tested for
more than 5000 h.34yA I-kW module (dimensions: 0.7 m in
diameter and I .6 m in height) containing 48 tubes has been con-
structed and operated. A power output of 1.3 kW at 56% fuel
utilization has been achieved.’4x
(C) Monolilhic Design: The monolithic design consists
of thin cell components formed into a compact corrugated
structure of either gas coflow or crossflow configurations (Fig.
23) ,3so.351 The fuel cell of this design is made of two types of
multilayer ceramics, each composed of three cell components:
anodelelectrolytelcathode and anodelinterconnectlcathode.
Typical layer thickness and cell-to-cell distance are 100 IJ-mand
1 to 2 mm, respectively. In the coflow version, fuel and oxidant
flow parallel in adjacent channels formed by corrugated
anode/electrolyte/cathode and flat anodelinterconnecticathode
laminates. In the crossflow version, the fuel cell consists of
alternating flat layers of anodelelectrolytelcathode laminate and
anodelinterconnectlcathode laminate, separated by corrugated
anode and cathode layers. The anode and cathode corrugations
are oriented at right angles to each other. The major differences
between the two versions are power density and gas mani-
folding. The crossflow version results in a reduction in power
density when compared with that of the coflow. On the other
hand, the crossflow offers a simpler means of ducting gases into
and out of the fuel cell ceramic structure.
The key features of the monolithic design are small cell size
and high power density. The small cell size increases the active
surface area and reduces resistive losses due to short elec-
tronlion paths. As a result of low resistance, the monolithic sol-
id-oxide fuel cell can be operated at higher current densities
than other designs while achieving the same output voltage.
COFLOW
Fig. 23. Monolithic solid-oxide fuel cell design (coflow and crossflow configurations).
Vol. 16, No. 3
The monolithic design has high power per unit mass or volume.
The high power density results from the higher active surface
area, higher current density, and lower weight. The lower
weight in the monolithic design is primarily the result of elimi-
nating inactive structural supports. The development of suitable
materials and fabrication processes is critical to the monolithic
design.’s2 The main disadvantage of the monolithic design is
the difficulty in fabricating the corrugated structure. Because of
its intricate structure, the monolithic fuel cell is made by cofir-
ing. Thus, the structural integrity of such a structure depends
upon two important factors: thermal expansion and firing
shrinkage match of the four cell components. Any significant
mismatch in the thermal expansion and shrinkage can cause
stress in the fired bodies and result in cracking during pro-
cessing and operation.’4Js3
The current approach in the fabrication of the monolithic fuel
cell is to form the fuel cell in the green state and cofire the green
body at elevated temperatures to produce the sintered structure.
Tape and tape calendering”’ have been developed for
the fabrication of thin ceramic layers and multilayers required
for building the monolithic fuel cell.
Tape casting has been developed for forming large-area, thin,
flat ceramic layers for the monolithic SOFC. The tape-casting
process starts with a slip of ceramic materials dispersed in a liq-
uid. The liquid contains dissolved organic binders and plasti-
cizers all diluted in a solvent system. The slip is spread on a flat
surface to a controlled thickness with the knife edge of a doctor
blade and the solvents are allowed to dry. This process is illus-
trated by Fig. 24(A). Multilayer tapes are fabricated by sequen-
tially casting one layer on top of another. The resulting tape
which is flexible, can be stripped from the casting surface, cut
to size, corrugated, or otherwise formed prior to firing.
The tape-calendering technique has also been used to pro-
duce thin and flexible ceramic layers required for the monolithic
SOFC. In this process, ceramic powder, binder, and plasticizer
are mixed in a high-intensity mixer. The friction resulting from
the mixing heats the batch and softens the binder to form a plas-
tic mass. The mass is rolled into a thin, flat tape using a two-roll
mill (Fig. 24 (B)). Tape thickness is controlled by the spacing
of the two rolls. To form multilayer tapes, individual tapes
are laminated in a second rolling operation, as shown in
Fig. 24(B).
Successful fabrication of the monolithic fuel cell structure by
tape casting or calendering depends upon several critical factors
in starting powder characteristics, green-state forming, and
firing:
CROSSFLOW
INTERCONNECT
v
CATHODE
March 1993 Cerurnic Fuel Cells
DOCTOR BLADES
CARRIER FILM
Fig. 24. Schematic diagrams of (A) tape casting and (B) tape calendering.
(i) Starting powder characteristics (especially surface area
and particle size) influence the fabrication of the monolithic
SOFC in many significant ways, including the amount of bind-
ers required to form the green body, sintering behavior, and the
sintered porosity/density and microstructure. The characteris-
tics of each material must be tailored to match firing shrinkage
profile and to produce cell components with the desired proper-
ties. For example, mixtures of LaMnO, powders of different
sinterability have been used to attain the desired porosity level
and to adjust the firing shrinkage profile of the cathode layer.'56
(ii) Careful control of green-state forming parameters is
essential to achieve acceptable results in the fabrication of the
monolithic fuel cell. For example, a compromise between
formability and sinterability is required when the solids loading
is determined. A high solids content facilitates densification
with less shrinkage. On the other hand, high solids loading pro-
duces less-flexible tapes, leading to difficulty in lamination and
corrugation.
(iii) The firing process is extremely important in the fabri-
cation of the monolithic SOFC. The rates of shrinkage during
both the binder burnout phase and the sintering phase of the fir-
ing operation must be reasonably well matched among the vari-
ous component^.^^^,^^^ Both the rate of heatup and the time at
temperature are important variables from the viewpoint of
allowing the various components to shrink uniformly during the
firing process.
In addition, nondestructive evaluation methods need to be
developed for the monolithic SOFC fabrication process to
ensure reliable manufacture.359
At present, a number of small, laboratory-scale coflow and
crossflow structures have been Figure 25
shows an example of sintered crossflow stacks. Low area-spe-
cific resistances and high current densities have been achieved
for the monolithic fuel ~ e 1 1 ; 3 ~monolithic
,'~~ SOFC cells have
been operated at 2.2 A/cm2with hydrogen as fuel and air as oxi-
d a n Multicell
~ ~ ~ stacks of crossflow configuration have been
tested. A stack (consisting of two cells in electrical series; each
with an active area of 9 cm2) has been operated for more
than 650 h.3MReforming and regenerating capabilities of the
monolithic SOFC have also been evaluated and demon-
~trated.~~'.~~'"
( D ) Flat-Plate Design: This design, common in other
types of fuel cells, consists of a single cell (anode/electrolyte/
cathode) and interconnect configured as thin, flat plates (Fig.
26). Individual cell thickness (mainly electrolyte thickness) is
typically thicker than 200 pm to be self-supporting. The
interconnect, having ribs on both sides, forms gas channels and
serves as a bipolar gas separator contacting the anode and cath-
ode of adjoining cells. The porous structures of the electrode
layers made with pressed powders have also been used to pro-
vide gas flow passages.367The flat-plate design permits several
519
PLASTIC-LIKE MASS
THIN TAPE
MULTIMYER TAPE
HIGH INTENSITY MIXER TWO-ROLL MILL
(B)
different ways of ducting gases in and out of the fuel cell. In
the most common flow geometry, fuel flows in one face of the
fuel cell stack and out the opposite face, as shown in Fig. 26.
Similarly, oxidant flows in one face and out the opposite face.
Other geometries include parallel floWjhXand radial or axial
floW367.369-372 with gas inlet and outlet located inside the fuel
cell stack.
The flat-plate design offers improved performance and
improved power density relative to the sealless tubular and
segmented-cell-in-series designs. Because of in-plane con-
duction, internal resistance losses of flat-plate SOFCs are inde-
pendent of cell area. Thus, cell components can be made very
thin to minimize electrical resistance. The flat-plate design also
offers simpler fabrication. The two dense components, the
electrolyte and the interconnect, can be fabricated indepen-
dently. This avoids the difficulties in cosintering LaCrO,
interconnect and provides multiple processing options. Further-
more, the fabrication of the flat-plate SOFC allows cell compo-
nents to be assessed individually, thus ensuring better quality
control.
The flat-plate SOFC requires high-temperature gas seals at
the edges of the plates. Compressive seals, cement seals, glass
seals, and glass-ceramic seals have been proposed. However,
the unforgiving nature of a compressive seal can lead to a non-
uniform stress distribution on the ceramic and cracking of the
layers. Cements and glasses tend to react with cell materials at
the 1000°C operating temperature. Further, seals may limit the
height of a cell stack. There is a higher probability for mis-
matches in tolerances (creating unacceptable stress levels) in
taller stacks. Contact resistance can be relatively high in flat-
plate SOFCs. Some configurations incorporate limited contact
area (via the interconnect) between the anode of one cell and
the cathode of another. As a result, there is a long path for cur-
rent in the plane of each electrode and the resistive losses can be
large. Stacking large, sintered ceramic layers is expected to be
difficult; this may set a limit on practical cell size for the flat-
plate design.
Fabrication and stack assembly appear to be simpler for the
flat-plate design as compared with the other designs. The elec-
trolyte is commonly made by tape ~ a s t i n g . ' Flat,~ ~ , stabilized
~~~
ZrO, electrolytes 50 to 120 pm thick have been fabricated by
tape ~ a s t i n g . ~ ~The
' , ' ~electrodes
~ are applied on the sintered
electrolyte by the slurry m e t h ~ d , ~ ~by~ ,screen
' ~ ' printing,"' by
plasma spraying,379or by other deposition technique^.^^.^^^.^^'
The electrodes have also been cofired with the electro-
lyte.372,382.3X3The LaCrO, interconnect is fabricated by tape cast-
ing'xx.384 or hot pressing. "* In addition to LaCrO, ceramics,
metals can be used for cell interconnection in flat-plate
SOFCs.53.36Y.385 Some proposed metallic materials are high-tem-
perature alloys based on iron and nickel. Alloys coated with a
thin film of perovskite oxide are also proposed.3x6Flat-plate
580 Journal of thc American Cerurnic Society-Mirth
Fig. 25. Sintered crossflow monolithic solid-oxide fuel cells
/ \ ,
INTERCONNECl
ANODE
ELECTROLVE
CATHODE
F .4Y .408.40Y Those oxides have been studied for use as fuel
Fig. 26. Flat-plate design of solid-oxide fuel
SOFC stacks are formed by stacking up layers to the desired
height. Compressive load and conductive brazing materia13e7.3X7
have been used to improve electrical contact between the layers.
The nature of the fat-plate design permits a variety of fabri-
cation options. Thus, several fabrication methods have been
investigated for making cell components:’xx spray pyrolysis,3x”
vacuum evaporation, R w ~ 3 yrfi sputtering,392w’4plasma metal
organic CVD (MOCVD),”’ EVD,3”7.”hCO 1aser evapora-
t i ~ n , ~plasma
’~ and vapor-phase electrolytic
~ . ~ ’ ’ of these techniques are capable of pro-
d e p o ~ i t i o n . ~ ’ Many
ducing micrometer-thick layers for flat-plate cells. Thin compo-
nents reduce ohmic resistances and offer the possibility of
lower-temperature operation. The benefits of lower operating
temperature include wider choice of cell and ancillary materi-
als, longer cell life, reduced thermal stress, improved reliabil-
ity, and reduced fuel cell cost.
Flat-plate SOFCs have been fabricated and operated under
various conditions. For example, a current density of 1 .9 Aicm’
has been achieved for flat-plate SOFCS.~‘”Single cells have
been operated at 0.7 V and 260 mA/cm2 for more than 5000 h
with less than 4%/ I000 h performance Multicell
stacks of the flat-plate design have been fabricated and
tested, 37X.4M 407 The operation of a I-kW-class stack (30 cells
and 225 cm2footprint area) has been demonstrated with a power
density of 0.2 W / C ~ ’ . A ~ ”40-cell
~ flat-plate stack has also been
Vol. 16, No. 3
tested for up to 1800 h, producing 45-W peak The
area-specific resistance of the stack is 1 . 1 Q.cm2.
V. Ceramic Fuel Cells Based on Proton Conductors
Only a brief discussion on ceramic fuel cells based on proton
conductors is given here. Certain oxides, especially perovskite
oxides, have been found to exhibit appreciably high proton con-
duction in hydrogen-containing atmospheres at elevated tem-
cell solid electrolytes. At present, the most common high-tem-
perature (600”to 1000°C) proton conductors are doped SrCeO,
and BaCeO,. High-temperature fuel cells based on proton con-
ductors generate steam in the oxidant electrode, thus eliminat-
ing the need of removing water in the fuel gas. To date, work on
proton-conductor SOFCs is limited to material studies, clari-
fication of conduction mechanism, and testing of small labo-
ratory-scale single cells. Several references are cited here
as an example of publications on proton-conductor fuel cell
work. 41( M I 5
References
‘W. R. Grove, “On Voltaic Series and the Combination of Gases by Plati-
num,” Philos. M u g . , 14, 127-30 (1839).
‘W. Nernst, “Uber Die Elektrolytische Leitung Fester Kiirper Bei Sehr Hohen
Tcniperaturcn,”Z. Elektrochem., 6,4143 (1899).
’E. Baur and H. Preis, “Uber Brennstoff-Kelten Mit Festleitern,” Z. Elekrro-
chrm.. 43.727-32 (1937).
‘N. 6.Minh, ’H&h:Temperature Fuel Cclls. Part 2: The Solid Oxide Cell,’’
CHEMTECH, 21, 120-26 (1991).
’Advances in Ceramics, Vol. 3 , Sciencr und Tc.chno/o~yofzirconid. Edited
by A. H. Heuer and L. W. Hobhs. American Ceramic Society, Columbus, OH,
1981.
‘Advances in Ceramics, Vol. 12. S m w e unrl E~chnolngyf. Zinoniu 11.
Edited by N. Claussen, M. Riihle, and A. H. Heuer. American Ceraiiiic Society,
Columbus, OH, 19x4.
’Advances in Ceramics, Vol. 24, Science und Te1.hnology of Zirconru 111.
Edited by S. SEmiya. N . Yamamoto, and H. Yanagida. American Ceramic Soci-
ety, Westerville. OH, 1988.
‘U. Stevens. An Introduc~ion r1) Zirconin. Magnesium Elektron, London,
U.K., 19x6.
“T. H. Etsell and S . N. Flengas, “The Electrical Properties of Solid Oxide
Eleclrolytcs,” Chem. Rev., 70, 339-76 (1970)
“‘E. C Suhharao and H. S . Maiti, “Solid Electrolytes with Oxygen Ion Con-
duction,”So/ir/Stutp Innics, I I , 3 17-38 (1984).
March 1993 Ceramic Fuel Cells
“J. W. Patterson, E. C. Borgen, and R. A. Rapp, “Mixed Conduction in
zr,,xA&qi ,,O, xi and Th,,,,Y,, <<O, Solid Electrolytes,” J. Eleelrochem. Soc.,
114,752-58 (1967).
”J. F. Baumard and P.Abelard, “Defect Structure and Transport Properties of
ZrO,-Based Solid Electrolytes”; see Ref. 6 , pp. 555-7 1.
”C. B. Choudhary, H. S . Maiti, and E. C. Subbarao. “Defect Structure and
Transport Properties”; pp. 1-80 in Solid Elerfro/.ytes und Their Applicutions.
Edited by E. C. Subbarao. Plenum Press, New York, 1980.
I4S. I? S . Badwal and A. E. Hughes, “Modification of Cell Characteristics by
Segregated Impurities”; pp. 445-54 in Proceedings of the Second lntrrnarionul
Symposium on Solid Oxide Furl Cells. Edited by F. Gross, P Zegers, S . C. Sin-
ghal, and 0 Yamanioto. Commission of The European Communities, Luxeni-
bourg, 1991.
”J. E. Bauerle, “Study of Solid Electrolyte Polarization by a Complex Admit-
tance Method,” J . Phys. Chem. Solid.s, 30, 2657-70 (1969).
‘“M. Kleitz, H. Bernard, E. Fernandez, and E. Schouler. “Impedance Spec-
troscopy and Electrical Resistance Measurements on Stabilized Zirconia”; see
Ref. 5 , pp. 310-36.
”M. J. Verkerk. B. J. Middelhuis, and A. J . Burggraaf, “Effect of Grain
Boundaries on the Conductivity of High-Purity ZrOz-Y,O, Ceramics,” Solid
Stute lonics, 6, 159-70 (1982).
‘“E. l? Butler, R. K. Slotwinski, N. Bonanos, J . Drennan, and B. C. H.
Steele. “Microstructural-Electrical Property Relationships in High-Conductiv-
ity Zirconias”; see Ref. 6, pp. 572-84.
“W. Baukal, “Solid Oxide Electrolyte with Time-Dependent Conductivity”;
pp. 247-54 in From Elrcrroc.urulysist o Fuel Cells. Edited by G. Sandstede. Uni-
versity of Washington Press, Seattle, WA, 1972
>“Y.Suzuki, A. Shiniada, and S . Senda. “Time-Dependent Change in Electri-
cal Resistivity of Polycrystalline YSZ and CSZ,” Solid Stute lonics, 42, I2 1-25
( 1990).
2’S.I? S . Badwal and J. Drennan, “Yttria-Zirconia: Effect of Microstructure
on Conductivity,” J . Moler. Sci., 22, 3231-39 (1987).
22M.Ciftcioglu and M. J. Mayo, “Processing of Nanocrystalline Ceramics”;
presented at the Spring Meeting of the Materials Research Society, San Fran-
cisco, CA, April 16-21, 1990. Rept. No. DE90-015700, SAND-YO-I639C,
CONF-900466-78, National Technical Information Service, Alexandria, VA,
1990.
”C. E. Scott and J. S . Reed, “Analysis of CI Ions Laundered from Submi-
cron Zirconia Powders,” Am. Cerum. Soc. Bull. , 57, 7 4 1 4 3 (1978).
‘T.E. Scott and J . S. Reed, “Effect of Laundering and Milling on the Sin-
tcring Behavior of Stabili7ed ZrOL Powders,” Am. Ceram. Soc. Bull.. 58,587-
90 (1979).
”A. G. Evans, “The New High-Toughness Ceramics”; pp. 267-91 in Frac-
ture Mechunics: Perspec.tive und Directions (Twentieth Symposium), ASTM
STP 1020. Edited by R. P.Wei and R . P. Gangloff. American Society for Testing
and Materials, Philadelphia. PA, 1989.
2‘1J. P. Singh, A. L. Bosak. D. W. Decs, and C. C. McPheeters, “Improved
Fracture Toughness of ZrO, Electrolyte for Solid Oxide Fuel Cell”; pp. 1 4 5 4 8
in I988 Fuel Cell Seminur Abs/ruc.ts (Long Beach, CA, Oct. 23-26, 1988).
Courtesy Associates, Washington, DC, 1988.
”F. Ishizaki, T. Yoshida, and S. Sakurada. “Effect of Alumina Addition on
the Electrical Properties of Yttria-Doped Zirconia”; pp. 3-14 in Proceedings of
the First International Symposium on Solid Oxide Fuel Cells. Edited by S . C.
Singhal. The Electrochemical Society, Pennington, NJ, 1989.
2XM.T. Hernandez, J . R. Jurado, and P Duran, “Effect ofAl,O, Additions on
the Electrical Properties of ZToz-YiOi and Zr0,-Y,O,-CeO, Electrolytes”; see
Ref. 14, pp. 421-28.
’“0.Yarnamoto, Y. Takeda, N. Imanishi, T. Kawahara, G . Q. Shen, M. Mori,
and T. Abe, “Electrical and Mechanical Properties of Zirconia-Alumina Com-
posite Electrolyte”; see Ref. 14, pp. 4 3 7 4 .
“‘P. Duran, J . R. Jurado, C. Moure, M. T. Hernandez, and F. Capel.
“Improvement of the Mechanical Properties of Yttria-Stabilized Zirconia Elec-
trolyte”; see Ref. 14, pp. 401407.
“W. Weppner, “Tetragonal Zirconia for Solid Oxide Fuel Cells”; pp. 83-89 in
Proceedings of the lnternutional Symposium on Solid Oxide Fuel Cells. Edited
by 0. Yamamoto, M. Dokiya, and H. Tagawa. Science House, Tokyo, Japan,
1990.
”T. Yoshida, T. Hoshina, I. Mukaizawa, and S . sdkurada, “Properties of Par-
tially Stabilized Zirconia Fuel Cell,” J. Electrochem. Soc., 136, 2604406
(1989).
”0.Yamamoto, Y. Takeda, R. Kanno, and K. Kohno, “Electrical Conductiv-
ity of Tetragonal Stabilized Zirconia,” J . Muter. Sci., 25, 2805-808 (1990).
’“T. Sato and M. Shimada, “Crystalline Phase Changes in Yttria-Partially-
Stabilized Zirconia by Low-Temperature Annealing,” J . Am. Ceram. Soc., 67
[lo] C-2 12-C-2 I3 ( 1984).
15E.C. Subbarao and H. S. Maiti, “Oxygen Sensors and Pumps”; see Ref. 7,
pp. 73 1 4 7 .
“‘A. N. Vlasov and M. V. Perfiliev, “Ageing of Zr02-Based Solid Electro-
lytes,”SolidStute lonics, 25,245-53 (1987).
58 1
”T. Takahashi, H. Iwahara, and Y. Nagai. “High Oxide Conduction i n Sin-
tered Bi,O, Containing SrO, CaO, or La,Olr” J. Appl. Elecvochrm., 2,97-104
(1972).
“M. Miyayanm. T. Nishi, and H. Yanagida, “Oxygcn ionic Conductton in
Y,O,-Stabilized Bi,O, and 210, Compositcs,” .J. Muter. Si.. 22, 2624-28
(1987).
‘”M. J. Verkerk, K. Keizer, and A. J. Burggraaf, “High Oxygen I o n Conduc-
tion in Sintercd Oxides of Bi,O,-Er,O, System,” J. Appl. E/e<~truc~hem., 10, 8 I-
90 (1980).
‘“T. Takahashi, T. Esaka, and H. Iwahara, “Conduction of Bi,O,-Based Oxide
Ion Conductor Under Low Oxygen Pressure. [I.Determination of the Partial
Electronic Conductivity,” J . Appl. Elec.troc.hem.,7, 303-308 (I977).
“ R . N. Bluinenthal. F. S . Brugner, and J . E. Garnier, “The Electrical Conduc-
tivity of CdO-Doped Nonstoichiometric Cerium Oxide from 7M)” to I 500°C;’
J . Electroc.hem. Soc., 120, 1230-37 (1973).
”H. L. Tuller and A. S. Nouick, “Doped Ceri Solid Oxide Electrolyte,”
J. Electrochem. Soc., 122,255-59 (1975).
“T. E. Swarr, S. Karavolis. and D L Maricle, ”Enhanced Ceria-A 1 . o ~ -
Temperature SOFC Electrolyte”; pp. 256-6 I in Proweding.v ofthe 25th /nter.<o-
ciety Energy Conversion Engineering Confi.rcm e , Vol. 3. American Institutc 0 1
Chemical Engineers, New York. 1990.
“H. Yahiro, Y. Baba, K. Eguchi, and H. Arai, “High-Temperature Fuel Cell
with Ceria-Yttria Solid Electrolytc,” J. Elemvdwm. SOC., 135, 2077-80
(1988).
“T. h u e . T. Setoguchi, K . Eguchi, and H. Arai. “Study of a Solid Oxide
Fuel Cell with a Ceria-Based Solid Electrolyte,” Solid Strm lonics, 35, 285-9 1
( I 989).
“A. V. Virkar, “Theoretical Analysis of Solid Oxide Fuel Cells with Two-
Layer Composite Electrolytc: Electrolyte Stahility,” J. Electroc.hem. Sue., 138,
1481-87 (199 I ) .
47T. Takahashi and H. Iwahara, “Ionic Conduction in Pcrovskite-Type Oxide
Solid Solution and Its Application tt> Solid Electrolyte Fuel Cell.” Encrgv Con-
vers., 11, 105-11 (1971).
“J. A. Kilncr, P Barrow, R. J. Brook, and M. J . Norgett, “Electrolytes for thc
High-Temperature Fuel Cell: Experimental and Theoretical Studies of the Pcrov-
skite LaAIO,,”J. Power Sources, 3 , 67-80 ( 1978)
‘“R. L. Cook, R C. MacDuff, and A . F. Sammells, “Perovakite Solid Elcctro-
lytcs for Intermediate-Temperature Solid Oxide Fuel Cells,” J. Elecrroc.hem.
Soc., 137, 3309-10 (1990).
”‘A. F. Sammells, R. L. Cook, and W. L. Worrell, “Methane Conversion by
Solid Electrolyte Membranes,” Rept. No. GRI-YO/OI 36. Gas Rescarch Institute,
Chicago, IL, 1990.
”S. Murakami, Y. Miyakc, Y. Akiyama, N. Ishida. T. Saito, and N. Furu-
kawa, “A Study on Composite Anode of Solid Oxide Fuel Cells”; see Rcf. 3 I ,
pp. 187-90.
”D. W. Dees, T. D. Claar, T. E. Easier, D. C. Fee, and E C. Mrazek, “Con-
ductivity of Porous Ni/Zr0,Y20, Ccrmets,” ./. Electrochcm. .5”x.. 134, 2141-
46 (1987).
”E. Ivers-Tiffce, W. Wersing, M. SchieRI, and H . Greiner, “Ceramic and
Metallic Components for a Planar SOFC,” Ber. Bun.\en-Gcs. Phgs. Chem., 94,
978-81 (1990).
54S.Majumdar, T. Claar, and B. Flandermeyer, “Stress and Fracture Behavior
of Monolithic Fuel CellTapes,” J . Am. Crrum. Soc., 69,628-33 (1986).
”T. Easler, B . K. Flandermeyer, T. D. Claar, D. E. Busch, R . J . Fousek, J . J .
Picciolo. and R. B. Poeppel, “Electrode Development for Monolithic Fuel
Cells”; pp. 72-75 in 1986 Fuel Crll Seminar Alxtructs (Tucson, AZ, Oct. 2 6
29, 1986). Courtesy Associates, Washington, DC, 1986.
ibT. L. Markin, R. J . Bones, and R. M. Dell, “High-Temperature Solid-Elec-
trolyte Fuel Cclls”: pp. 15-35 in Confi.runcu on Supv-ionic Conducrors. Edited
by G. D. Mahan and W. L. Roth. Plenum Press, New York, 1976.
’?M. Suzuki, H. Sasaki, S . Otoshi, and M. Ippommatsu, “Devclopment of
RuiLrO, SOFC Anode”; see Ref. 14, pp. 585-9 I .
”T. Takahashi, H. Iwahara, and Y. Suzuki, “Electrode Materials for High-
Temperature Solid Electrolyte Fuel Cells”; pp. I 13-1 9 in Proceedfng.! of the
Third lnternutionul Symposium on Fuel Cells. Presses AcadCmiqucc EuropCen-
nes, Brussels, Belgium, 1969.
”B. C. H. Steele, P. H. Middleton, and R. A. Rudkin, “Material Science
Aspects of SOFC Technology with Special Reference to Anode Dcvelopmcnt.”
Solid Stute lonics, 40/41, 388-93 (1990).
““M. Mogensen, “Properties of CeO,-Based SOFC Anode Materials”: see
Ref. 14, pp. 577-84.
“K. E. Swider and W. L. Worrell, ‘Synthesis and Characteridon of Yttria-
Stabilized Zirconia-Titania Thin-Film Electrodes”; see Ref. 14, pp. 593-601.
S . Liou and W. L. Worrell, “Mixed-Conducting Oxide Electrodes for
Solid Oxide Fuel Cells”; see Ref. 27, pp. 81-89.
“3. S . Liou and W. L. Worrell, “Electrical Properties of Novel Mixed-Con-
ducting Oxides,”Appl. P h y . A , 49, 25-3 I (1989).
“C. S. Tedmon. Jr., H. S . Spacil, and S . P Mitoff, “Cathode Materials and
Performance in High-Temperature Zirconia Electrolyte Fuel Cells.” J. Electro-
chrm. SOC., 116, 1170-75 (1969).
582 Journal of the American Ceramic Society-Minh
65B.C. Tofield and W. R. Scott, “Oxidative Nonstoichiometry in Perovskites,
an Experimental Survey: The Defect Structure of an Oxidized Lanthanum Man-
ganite by Powder Neutron Diffraction,” J . Solid State Chem., 10, 183-94
(1974).
Y. H. Kuo, H. U. Anderson, and D. M. Sparlin, “Oxidation-Reduction
Behavior of Undoped and Sr-Doped LaMnO,: Defect Structure, Electrical Con-
ductivity, and Thermoelectric Power,” J . Solid State Chem., 87, 5 5 4 3 (1990).
“%. V. Subba Rao, B. M. Wanklyn, and C. N. R. Rao, “Electrical Transport
in Rare-Earth Ortho-Chromites, -Manganites, and -Ferrites,” J . Phys. Chem.
Solids, 32,345-58 (I97 I ).
LXK.Kamata, T. Nakajima, T. Hayashi, and T. Nakamura, “Nonstoichiornet-
ric Behavior and Phase Stability of Rare-Earth Manganites at 1200°C: ( I ) .
LaMnO,,”Mutrr. Rrs. Bull., 13,49-54 (1978).
h”J. Mizusaki, H. Tagawa, K. Naraya, and T. Sasamoto, “Nonstoichiometry
and Thermochemical Stability of the Perovskite-Type La, ,Sr,MnO, *.” Solid
Srutelonics,49, 111-18(1991).
’“J. H. Kuo, H. U. Anderson, and D. M. Sparlin, “Oxidation-Reduction
Behavior of Undoped and Sr-Doped LaMnO, Nonstoichiometry and Defect
Structure,” J . SoiidStute Chem., 83,52-60 (1989).
”T. Nakamura, G. Petzow, and L. J . Gauckler, “Stability of the Perovskite
Phase LaBO, (B = V, Cr, Mn, Fe, Co, Ni) in Reducing Atmospheres I . Experi-
mental Results,” Mafer-.Res. Bull., 14,649-59 (1979).
720. M. Sreedharan, R. Pankajavalli, and J. B. Gnanamoorthy, “Standard
Gibbs’ Energy of Formation of LaMnO, from EMF Measurements,” High Temp.
Sci., 16, 251-56 (1983).
’IN. Kamegashira, Y. Miyazaki, and Y. Hiyoshi, “Limiting Oxygen Partial
Pressure of LaMnO, Phase,” Muter. Lett., 2, 194-95 (1984).
’‘0. M. Sreedharan and M. S . Chandrasekharaiah, “Standard Gibbs’ Energy
of Formation of LaFeO, and Comparison of Stability of LaMO, (M = Mn, Fe,
Co, Ni) Compounds,” J . Muter. Sci., 21, 2581-84 (1986).
75R. Ruka, “Some Non-Electrochemical Requirements for Air Electrode
Materials of High-Temperature Solid Electrolyte Fuel Cells”; pp. 295-302 in
Proceedings of the Conference on High-Temperature Sulid Oxide Electrolytes,
Vol. I-Anion Conductors (Brookhaven National Laboratory, Upton, NY, Aug.
16-17, 1983). Rept. No. BNL 51728-Vol. 1, Brookhaven National Laboratory,
Upton, NY, 1983.
“G. H. Jonker, “Semiconducting Properties of Mixed Crystals with Perov-
skite Structure,” Physica (Amsterdam), 20, 1 1 18-22 (1954).
’7J. Tanaka. K. Takahashi, K. Yukino, and S. Horiuchi, “Electrical Conduc-
tion of (La, ,Ca,, ,)MnO, with Homogeneous Ionic Distribution,” Phys. Sfutus
Solidi, 80,621-30 (1983).
”M. Fandel. J. Hoschele, W. Schafer, and R. Schmidberger, “Properties of
Ca-Doped LaMnO,”; pp. 2.236-2.240 in Euro-ceramics, Vol. 2, Properties of
Ceramics. Edited by G. de With, R. A. Lerpstra, and R. Metselaar. Elsevier
Applied Science, London, U.K., 1989.
’“V. I. Pavlov, A. K . Bogush, and G. L. Bychkov, “Influence of Impurity Cen-
ters on the Electrical Conductivity of Manganites with a Perovskite Structure,”
lnorg. Muter. (En,@.Transl.), 20,752-54 (1984).
“”A. Wold, R. J . Arnott, and 1. B . Goodenough, “Some Magnetic and Crys-
tallographic Properties of the System LaMn, ,Ni,O,,,” J . Appl. Phys., 29, 387-
89 (1958).
“‘I. Ya. Lyubkina and I. F. Kononyuk, “Preparation and Electric Properties of
LaMn, ,Ni,O, (0 < x < 0.7),”Innrg.Muter. (Engl. Transl.),22,861-65 (1986).
”A. Mackor, T. P. M. Koster, J . G. Kraaijkamp, J. Gerretsen, and J. P. G. M.
van Eijk, “Influence of La-Substitution and -Substoichiometry on Conductivity,
Thermal Expansion, and Chemical Stability of Ca- or Sr-Doped Lanthanum
Manganites as SOFC Cathodes”; see Ref. 14, pp. 463-71.
*’M. Kertesz, 1. Riess, D. S . Tannhauser, R. Langpape, and F. J . Rohr,
“Structural and Electrical Conductivity of La x4Srn,,MnO,,” J . Solid Srute
Chem., 42, 125-29 (1982).
R4T.Hashimoto, N. Ishizawa, N. Mizutani, and M. Kato, “Electrical Resisti-
vity and Seebeck Coefficient of La,.,M,MnO, (M = Ca, Sr) Single Crystals,”
J . Muter. Sci., 23, 1102-105 (1988).
”K. Katayama, T. Ishihard, H. Ohta. S . Takeuchi, Y. Esaki, and E. Inukai,
“Sintering and Electrical Conductivity of La, ,Sr,MnO,.” J . Ceram. Soc. Jpn.
(Nippon Seramikkusu Kyokai Gakujutsu Ronbunshi), 97, 1324-30 (1989).
R6L.G. J. de Haart, R. A. Kuipers, K. J. de Vries, and A. J . BUrggraaf,
“Deposition and Electrical Properties of Thin Porous Ceramic Electrode Lay-
ers”; see Ref. 27, pp. 197-203.
”H. Lauret, E. Caignol, and A . Hammou, “Electrical Properties of
La, ,Sr,MnO, forx 2 0.5”: see Ref. 14,pp. 479-86.
‘*J. A. M. van Roosmalen, J. P. P. Huijsmans, and E. H. P. Cordfunke, “Sinter
Behavior and Electrical Conductivity of (La,Sr)MnO, as a Function of Sr Con-
tent”; see Ref. 14, pp. 507-16.
”A. Hammouche, E. L. Schouler, and M. Henault, “Electrical and Thermal
Properties of Sr-Doped LaMnO,,” Solid Stute lonics, 28-30, 1205-207 ( I 988).
‘9.B. Goodenough, “Theory of the Role of Covalence in the Perovskite-Type
Manganites [La,M(II)]MnO,,” Phys. Rev., 100, 564-73 (1955).
“IS. Otoshi, H. Sasaki, H. Ohnishi, M. Hase, K. Ishimaru, M. Ippommatsu,
T. Higuchi, M. Miyayama, and H. Yanagida, “Changes in the Phases and Elec-
trical Properties of (La, ,Sr,),~,MnO,~,,”J . Electrochem. Soc., 138, 1519-23
(1 991 ).
Vol. 76, No. 3
’ZA. Hammouche, E. Siebert, and A. Hammou, “Crystallographic, Thermal,
and Electrochemical Properties of the System La,.,Sr,MnO, for High-Tempera-
ture Solid Electrolyte Fuel Cells,” Mnter. Res. Bull., 24, 367-80 (1989).
”’S. Srilomsak, D. P. Schilling, and H. U. Anderson, ‘‘Thermal Expansion
Studies on Cathode and Interconnect Oxides”; see Ref. 27, pp. 129-40.
“Westinghouse Electric Corp., “High-Temperature Solid Oxide Electrolyte
Fuel Cell Power Generation System, Quarterly Technical Progress Summary
Report, January I , 1984-March 31, 1984,” Rept. No. DOEIETII7089-2217.
U.S. Dept. of Energy, Washington, DC, 1984.
3.K. Lau and S. C. Singhal, “High-Temperature Interactions at Solid Oxide
Fuel Cell Interfaces”; pp. 107-10 in 19x5 Fuel Cell Seminar Abstracts (Tucson,
AZ, May 19-22, 1985). Courtesy Associates, Washington, DC, 1985.
‘“0.Yamamoto, Y. Takeda, R. Kanno, and M. Noda, “Perovskite-Type
Oxides as Oxygen Electrodes for High-Temperature Oxide Fuel Cells,” Solid
State lonics, 22,24146 (1987).
‘”0.Yamamoto, Y. Takeda, R. Kanno, and T. Kojima, “Stability of Perov-
skite Oxide Electrode with Stabilized Zirconia”; see Ref. 27, pp. 242-53.
URH.Yokokawa, N. Sakai, T. Kawada, and M. Dokiya, “Chemical Potential
Diagrams for La-M-Zr-0 (M = V, Cr, Mn. Fe, Co, Ni) Systems: Reactivity of
Perovskites with Zirconia as a Function of Oxygen Potential,” Denki Kagaku,
58,489-97 (1990).
“0. Yamamoto, Y. Takeda, and T. Kojima, “Reactivity of Yttria-Stabilized
Zirconia with (La, ,A,),~,MnO,+l (A = Ca, Sr)”; see Ref. 31, pp. 148-61.
““‘H. Yokokawa, N. Sakai, T. Kawada, and M . Dokiya. “Thermodynamic
Analysis on Interface between Perovskite Electrode and YSZ Electrolyte,” Solid
State lonics, 40/41, 398401 (1990).
‘“’H.Tagawa, J. Mizusaki, M. Katou, K. Hirano, A. Sawata, and K. Tsune-
yoshi, “On the Solid State Reaction Between Stabilized Zirconia and Some Per-
ovskite-Type Oxides”; see Ref. 14, pp. 681-88.
“12H.Taimatsu, K. Wada, and H. Kaneko, “Mechanism of Reaction between
Lanthanum Manganite and Yttria-Stabilized Zirconia,” J . Am. Ceram. Soc., 7 5 ,
401405 (1992).
“”H. Yokokawa, N. Sakai, T. Kawada, and M. Dokiya, “Chemical Thermo-
dynamic Compatibility of Solid Oxyide Fuel Cell Materials.’; see Ref. 14, pp.
663-70.
““C. Milliken, S.Elangovan, and A. Khandkar, “Interface Reactions and Sin-
tering of Doped LaCIO, Materials”: see Ref. 31, pp. 50-57.
“”R. Koc, H. U. Anderson, and S . A. Howard, “Structural, Sintering, and
Electrical Properties of the Perovskite-Type (La,Sr)(Cr,Mn)O,”; see Ref. 27, pp.
220-41.
“*M. Mori, N. Sakai, T. Kawada, H. Yokokawa, and M. Dokiya, “A New
Cathode Material (La,Sr), ,(Mn, ,Cr,)O, (0 5 y 5 0.2) for SOFC,” Denki
Kugaku, 58,528-32 (1990).
“”J. Palma and C. Pascual, “Perovskite-Type (La,Sr)(Mn.Cr)O, Compounds
as Candidates for SOFC Cathodes”; see Ref. 14, pp. 5 3 7 4 4 .
“’*A.Iberl, H. von Philipsborn, M. SchieBI, E. Ivers-Tiffke, W. Wersing, and
G. Zorn. “High-Temperature X-ray Diffraction Measurements of Phase Transi-
tions and Thermal Expansion in (L.a,Sr)(Mn,Co)O, Cathode Materials”; see Ref.
14, pp. 527-35.
‘“A. Mackor, C. 1. M. A. Spee, E. A. van der Zouwen-Assink, J. L. Bap-
tista, and .I.Schoonman, “Mixed Conductivity in Perovskite SOFC Materials
La, ,M,Mn, ,Co,O, (M = Ca or Sr)”: see Ref. 43, pp. 251-55.
“”J. Mizusaki, H. Tagawa, K. Tsuneyoshi, A. Sawata, M. Katou, and K.
Hirano, “The La, ,Ca, ,MnO,-YSZ Composite as an SOFC Air Electrode,”
Denki Kagaku, 58,520-27 (1990).
“‘A. Tsunoda, T.Yoshida, and S . Sakurada, “Effect of Pt Additions on the
Resistance of Lq,,Sr, ,MnO, Cathode”;,see Ref. 27, pp. 204-13.
“‘Y. Ohno, S. Nagata, K. Shini. and H. Sato, “Research on Cathode Materi-
als for High-Temperature Solid Electrolyte Fuel Cells,”Bull. Electrorech. Lab.,
4 4 , 4 0 4 8 (1980).
“’Y. Ohno, S. Nagata, and H. Sato, “Effect of Electrode Materials on the
Properties of High-Temperature Solid Electrolyte Fuel Cells,” SolidStafelonics,
3/4,43942 (1981).
‘I4T. J. Gray, “Strontium Ceramics for Chemical Applications,” J . Power
Sources, 6 , 1 2 1 4 2 (1981).
‘I5H.Tagawa, J. Mizusaki, Y. Arai, Y. Kuwayama, S . Tsuchiya, T. Takeda,
and S . Sekido, “Sinterability and Electrical Conductivity of Variously Prepared
Perovskite-Type Oxide, La, $r0 ,Coo,,” Denki Kagaku, 58, 512-19 (1990).
”%. C. Sorenson, J. A. Wronkiewicz, L. B. Sis, and G. P. Wirtz, “Properties
of LaCoO, as a Catalyst in Engine Exhaust Gases,’’Am. Ceram. Soc. Bull., 53,
4 4 6 4 9 ( 1 974).
”’5. Mizusaki, Y. Mima, S . Yamauchi, K. Fueki. and H. Tagawa, “Nonstoi-
chiometry of the Perovskite-Type Oxides La, .Sr,CoO,,,” J . Solid State Chem.,
80, 102-1 I (1989).
”‘A. N. Petrov, V. A. Cherepanov, 0. F. Konochuk, and L. Ya. Gavrilova,
“Oxygen Nonstoichiometry of La,.,Sr,CoO,, (0 < x 5 0.6),” J . Solid Stute
Chem., 87,69-76 (1990).
“”J. Mizusaki, J. Tabuchi, T. Matsuura, S. Yamauchi, andK. Fueki, “Electri-
cal Conductivity and Seebeck Coefficient of Nonstoichiometric La,.,Sr,CoO,,,”
J . Electrochem. Soc., 136,2082-88 ( 1989).
March 1993 Cerumic Fuel Cells
‘2”1.F. Kononyuk, S . P. Tolochko, V. A. Lutsko, and V. M. Anishchik, “Prcp-
aration and Properties of La, ,Ca,CoO, (0.2 5 x 5 0.6),”J. SolidState Chem.,
48,209-14 (1983).
I2‘Y. Ohno, S. Nagata, and H. Sato, “Properties of Oxides for High-Tempera-
ture Solid Electrolyte Fuel Cell,” SolidState Ionics, 9/10, 1001-1008 (1983).
‘”H. Yokokawa, N. Sakai, T. Kawada, and M. Dokiya, “Stability and Reac-
tion of Perovskite Materials in SOFCs”; see Ref. 31, pp. I 18-34,
‘23J. Echigoya, S . Hiratsuka, and H. Suto, “Solid State Reaction of La-
(Co,.,Ni,)O, with 10 mol% Y,O,-ZrO,,”Mater. Trans. J I M , 30,789-99 (1989).
‘“N. J. Maskalick and C. C. Sun, “Sintered Zirconia Electrolyte Films in
High-Temperature Fuel CeIIs,”J. Electrochem. Soc., 118, 1386-91 (1971).
”’E. E Sverdrup, C. 1. Warde, and A. D. Glasser, “A Fuel Cell Power System
for Central-Station Power Generation Using Coal as a Fuel”; see Ref. 19, pp.
255-77.
l2‘E. F. Sverdrup, D. H. Archer, and A. D. Glasser, “Stannic Oxide and
Indium Oxide Films as Air Electrodes for High-Temperature Coal Reacting Fuel
Cells”; pp. 301-14 in Fue/ Cell Systems-11. Edited by B. S . Baker. American
Chemical Society, Washington, DC, 1969.
127L.N. Yannopoulos, “A Method for the Uniform Chemical Vapor Deposi-
tion of Tin-Doped Indium Sesquioxide Films on Cylindrical SubStrates,”
J . Less-CommonMet., 63, 1 1 1-21 (1979).
12”D.D. Marchant and J. L. Bates, “Preparation and Properties of Electrically
Conducting Ceramics Based on Indium Oxide-Rare-Earth Oxides-Hafnium
Oxide”; see Ref. 75, pp, 2 5 9 4 7 .
‘“J. L. Bates and C. W. Griffin, “Oxide Electrodes for Solid Oxide Fuel
Cells”; see Ref. 5.5, pp. 48-5 I .
”“J. L. Bates, W. J. Weber, and C. W. Griffin, “Solid Oxide Fuel Cell Elec-
trodes Based on In,O,-PrO, ,,-Z&,”; see Ref. 27, pp. 141-56.
‘”M. M. Nasrallah, H. U. Anderson, and J. W. Stevenson, “Defect Chemis-
try and Properties of Y,.,Ca,MnO,”; see Ref. 14, pp. 545-52.
”’S. Geller, “Crystallographic Studies of Perovskite-Like Compounds. IV.
Rare-Earth Scandates, Vanadites, Galliates, Orthochromites,” Acta Crys-
tullogr., 10, 2 4 3 4 3 (1957).
‘”J. S. Ruiz, A. M. Anthony, and M. F&x, “Sur les PropriCtCs Semi-con-
ductrices du Chromite de Lanthane,” C. R . Acad. Sci., Paris, 264B, 1271-74
(1967).
“‘S. Geller and P. M. Raccah, “Phase Transitions in Perovskite-like Com-
pounds of the Rare Earths,”Phys. Rev. B , 2, 1167-72 (1970).
”’C. P. Khattak and D. E. Cox, “Structural Studies of the (La,Sr)CrO, Sys-
tem,”Mater. Res. Bull., 12,463-72 (1977).
”‘J. P. Traverse and R. Berjoan, “Etude Radiocristallographique a Haute Tem-
Nrature du Chromite de Lanthane,” C. R . Acad. Sci., furis, 276C, 1167-69
( I 973).
137A.M. Anthony, G. Benezech, E Cabannes, M. Faucher, M. Foex, V. Loc,
and D. Yerouchalmi, “Lanthanum Chromite: New Properties”; pp. 215-33 in
Proceedings of the Third International Symposium on High-Temperature Tech-
nology. Butterworths, London, U.K., 1967.
”*R. Berjoan, A. Moibe, M. Rivot, and J . P. Traverse, “Le Chromite de Lan-
thane Dope, Nouveau Materiau pour le Chauffage a Haute Temperature sous
Atmosphere Oxydante”; pp. 343-57 in Science of Ceramics, Vol. 7. Societe
Francaise de Ceramique, Juan-les-Pins, Paris, France, 1973.
‘39J.Mizusaki, S . Yamauchi, K. Fueki, and A . Ashikawa, “Nonstoichiometry
of the Perovskite-Type Oxide La,.,SrrCrO, &,” Sotid State lonics, 12, I 19-24
(1984).
I4D. B . Meadowcroft, “Electronically-Conducting, Refractory Ceramic Elec-
trodes for Open Cycle MHD Power Generation,” Energy Cowers., 8, 185-90
( 1968).
14’R.Berjoan, “Contribution a I’ Etude des RBactions de l’Oxygtne avec les
MClanges d’Oxyde de Lanthane et d’Oxyde de Chrome 111 ou de Chromite de
Lanthane,”Rev. Int. Hautes Temp. Refract.. 13, 119-35 (1976)
142R. Berjoan, C. Romand, and J . P. Coutures, “Oxygen Reactivity of La@-
Cr,O,-CaO MHD-Related Materials,”High Temp. Sci., 13, 173-88 (1980).
I4’B. K. Flandermeyer, M. M. Nasrallah, A. K. Agarwal, and H. U. Ander-
son, “Defect Structure of Mg-Doped LaCrO, Model and Thermogravimetric
Measurements,” J Am. Ceram. Soc., 67, 195-98 (1984).
P. Tolochko, I . E Kononyuk, Yu. G. Zonov, and L. S. Ivashkevich,
“Structure and Properties of Solid Solutions LaCo,.,Cr,O,,” lnurg. Mater. (Engl.
Trans[.), 23, 7 4 3 4 7 (1987).
145S. Hayashi, K. Fukaya. and H. Saito, “Sintering of Lanthanum Chromite
Doped with Zinc or Copper,” J . Mater. Sci. Lett., 7,457-58 (1988).
IMS. P. Tolochko, 1. E Kononyuk, V. A. Lyutsko, and Yu. G. Zonov, “Phase
Transitions in Solid Solutions Based on Lanthanum Chromite,” Inorg. Mazer.
(Engl. Trans/.), 23, 1342-45 (1987).
I4’P. P. Zhuk, A. A. Vecher, V. V. Samokhval, E. N. Naumovich, and A. I?
Viskup, “Properties of Iron-Doped Lanthanum Chromite,” Inorg. Mater.,
(Engl. Trans/.), 24,88-91 (1988).
14’H. U. Anderson, “Fabrication and Property Control of LaCrO,-Based
Oxides”; pp. 469-77 in Processing of Crysta/line Ceramics. Edited by H. Pal-
mour Ill, R. F, Davis, and T. M. Hare. Plenum Press, New York, 1978.
583
““K. l? Bansal, S . Kumari. B. K. Das, and G. C. Jain, “Electrical Propertie\
of Ceramic Lanthanum Chromite Doped with TiO,,” Ph-ys. Srutus Solidi A , 64,
K125-K I27 (1981).
”“D. P. Karim and A . T. Aldred, “Locah7.ed Level Hopping Transport in
La(Sr)CrO,,” Phys. Rev. B: Condens. Mutter, 20, 2255-63 ( 1979).
“’J. B. Webb. M. Sayer, and A. Mansingh, “Polaronic Conduction in Lantha-
num Strontium Chromite,” Cun. J . Phys., 55, 1725-31 (1977).
‘‘2D. B. Meadowcroft, “Some Properties of Strontium-Doped Lanthanum
Chromite,” Br. J . Appl. Phys., 2, 1225-33 (1969).
”’K. P. Bansal, S . Kumari. B. K . Das. and G. C. Jain, “On Some Transport
Properties of Strontium-Doped Lanthanum Chromite Ccramics,”J. Mater. Sci.,
18,2095-100 (1983).
’%. T. Song, H. Y. Pan, Z. Wang. and B. Yang, “Synthesis, Properties, and
Application of High-Conductive Lac&,-Based Ceramic Materials,” Cerum.
Int.. 10, 1 4 3 4 6 (1984).
“‘Westinghouse Electric Corp., “Interconnection Materials Development for
Solid Oxide Fucl Cells,” Rept. No. DOEIMCI2IIX4-198.5. U S . Dept. of
Energy, Washington, DC. 1985.
IshW.J . Weber, C. W. Griffin, and J. B. Bates, “Effects of Cation Substitution
on Electrical and Thennal Transport Properties of YC&, and LaCrO,,” J . Am.
Ceram. Soc., 70,265-70 (1987).
I5’V. H. Schmidt, “Electrical Propertiea of Lanthanum Chromite Based
Ceramics in Hydrogen and Oxidizing Atmospheres at High Temperatures,”
Rept. No. DOEIETI I54 IS- I , U .S . Dept. of Energy, Washington, DC, I98 I .
”‘D. W. Dees and F. C. Mrazek, “Characterization of Monolithic Fucl Cell
Components”; see Ref. 5 5 , pp. 56-59.
“YN . Q- Minh, C. R. Home. F. S . Liu, D. M. Moffatt, P. R. Staszak, T. L.
Stillwagon, and J . J . Van Ackeren, “Fabrication and Characterization of Mono-
lithic Solid Oxide Fuel Cells”; see Ref. 43, pp. 256-61.
‘H’C.J . Yu, D.M. Sparlin, and H. U . Anderson, “Oxidation Kinetics of Poly-
crystalline LaCrO,,” J . Am. Ceram. Soc., 70, C-189-(2-192 (1987).
‘“H. U. Anderson, M. M. Nasrallah, B. K . Flandermeyer, and A. K. Agar-
wal, “High-Temperature Redox Behavior of Doped SrTiO, and LaCrO,,”
J . SolidState Chem., 56,325-34 (1985).
‘(”B.F. Flandermeyer, M. M. Nasrallah, D. M. Sparlin, and H. U. Anderson,
“High-Temperature Stability of Magnesium-Doped Lanthanum Chromite,”
High Temp. Sci., 20,259-69 (1985).
““B. K. Flandermeyer, M. M. Nasrallah, D. M. Sparlin, and H. U. Andcr-
son, “Thermogravimetric and Electrical Conductivity Studies of Mg-Doped
LaCrO, and La-Doped SrTiO,”; pp. 17-30 in Trunsport in Nonstoichiometrii.
Compounds. Edited by G. Simkovich and V. S . Stubican. Plenum Press, New
York, 1985.
IMH.U . Anderson, J. H. Kuo, and D. M. Sparlin, “Review of Defect Chemis-
try of LaMnO, and LaCrO,”; see Ref. 27, pp. I 1 1-28.
‘“1. ydsuda and T. Hikita, “Electrical Conductivity and Oxygen Chemical
Diffusion Coefficient of Calcium-Doped Lanthanum Chromites”; see Ref. 14,
pp. 645-52.
IhhH.U. Anderson, R. Murphy, K. Humphrey, B. Rossing, A . Aldred, W. L.
Procarione, and R. J . Ackermann, “Influence of Composition and Cation Stoi-
chiometry on the Volatility, Electrical Conductivity, and Thermal Expansion of
Lac&,-Based Oxides”; pp. 55-61 in The Rure Earths in Mudew Science and
Technology. Edited by G. J . McCarthy and J . J . Rhyne. Plenum Press, New
York. 1978.
‘”N. Sakai, T. Kawada, H. Yokokawa, M. Dokiya, and T. Iwata, “Thermal
Expansion of Some Chromium-Deficient Lanthanum Chromites,” Solid Stute
lonics, 40141, 394-97 (1990).
‘“E J . Brodmann and F? E. D. Morgan, “Advances in Lanthanum Chromite
MHD Electrode Development”; pp. 135-4 I in Conferenre on High-Temperature
Sciences Related to Open-Cycle, Coal-Fired MUD Systems (Argonne National
Laboratory, Argonne, IL, April 4-6, 1977). Rept. No. ANL-77-21, Argonne
National Laboratory, Argonne, IL, 1977.
IWD. B. Meadowcroft and J. M. Wimmer, “Oxidation and Vaporization Pro-
cesses in Lanthanum Chromite.” Am. Ceram. Soc. Bull., 58, 610-12, 615
(1979).
I7“T. Sasamoto and T. Sata, ‘Vaporization of Lanthanum Chromite at High
Temperatures in Vacuum,” Yogyo Kyokaishi, 74, 408-18 (1971)
I7’H.Yokokawa, N. Sakai, T. Kawada. and M. Dokiya, ‘Chemical Thermo-
dynamic Considerations in Sintering of LaCrO,-Based Perovskites,” J . Electro-
chem. Soc., 138, 1018-27 (1991).
172L.Groupp and H. U. Anderson, “Densification of La, ,Sr,CrO,,” J . Am.
Ceram. Sor., 59, 449-50 (1976).
173J.W. Halloran and H. U. Anderson, “Influence of 0, Partial Pressures on
Initial Sintering of AlphaCr,O,,”J. Am. Ceram. Soc., 57, 150 (1974).
174L.A. Chick, J . L. Bates, L. R. Pederson, and H. E. Kissinger, “Synthesis
of Aidinterable Lanthanum Chromite Powders”; see Ref. 27, pp. I7Lk87.
”’H. U. Anderson, C. C. Chen, J . C. Wang, and M. J . Pennell, “Synthesis of
Conducting Oxide Films and Powders from Polymeric Precursors”; pp. 749-55
in Ceramic Transactions, Vol. 12, Ceramic Powder ScienceIII. Edited by G. L.
Messing, S . I . Hirano, and H. Hausner. American Ceramic Society, Westerville,
OH, 1990.
584 Jourrral o j the American Ceramic. Society-Minh
”“M. Dokiya. N. Sakai, T. Kawada, H. Yokohawa, T. Iwata, and M. Mori,
“Overview of Planar SOFC Devclopinent at NCLI”: see Ref. 27, pp. 325-36.
”’N. Sakai, T. Kawada, H . Yokohawa, M . Dokiya. and T. Iwata, “ S i n t e r d i -
ity and Electrical Conductivity of Calcium-Doped Lanthanum Chromiter,”
J. Muter, Set., 25, 4531-74 (1990).
””J. L. Bates, “SOFC Materials Development: Chroniitc Interconnect”: pp.
I59-70 in Prorwdings of rhe Sc,cond A ~ i i i i ~Fuc4
d Cell.\ Confrai~rorsK
Meeting. Edited hy W. I Huber. Kept. No. DOE/METC-Y0/6I 12. U.S. Dept. o f
Energy, Washington, DC, 1990.
”‘I.. A. Chick, J . I,. Bates, and G. I).Maupin, “Air-Sintering Mechanisms of
Chromites”; see Rel. 14, pp. 621-28.
‘“‘N. Sakai, T Kawada, H . Yokokawa, and M . Dokiya, “Low-‘lernperat~ire
Sintering Characteristics of. Calcium-Dopcd 1,anth;inum Cliromites”: see Ref.
14, pp. 629-36.
IX’H.U. Anderson, R Murphy, A. K . Fox, B. Ros\ing, and A . Aldrtd,
”Compositional Dependence of Thermal Expatision, Lattice Parameters, Volaril-
imtion Rate, and Electrical Conductivity of LaCrO,-Based Oxides”; pp. 4 1-53
in Pror.c.ei/ing.s o/ rhe Work.shop o n High-~,Jn/~i,rutuJ-(,
Solid Oxirk, Fiid Ce//.\.
Edited by H. S. lsaacs, S . Srinivasan. and 1. L. Harry. Kept. No. B N L 50756.
Brookhaven National Lahoratory, Upton, NY, I978
Ih2R. Koc and H . U . Anderson, “Low-Temperature Sintering of LaC‘r0;-
Based Ceramics”; see Kef. 175, pp. 749-55.
“’M. M Na\rallah, J . I).Carter. H . U . Anderson, and K . Koc, “Low-Tern-
perature Air-Sinterahlc LaC‘rO, and YCrO,”: see Ref. 14. pp. 6 3 7 4 4 .
‘“N. Q. Minh, “Monolithic Solid Oxide Fuel Cell Materials”: see Ref. 17X,
pp. IX&90.
‘8”
0.Minh. T R . Armstrong, J. R . Esopa. J. V Guiheen, C. R. Hornc.
F. S. Liu, T. L . Stillwagon, and J. J . Van Ackercn, “Fahrication Methoddogie\
lor Monolithic Solid Oxide Fuel Cells”: see Ref. 14. pp. 93-98.
““B. K . Flandcrrneyer, J . T. Dusck, P E. Blackburn. D. W Dees, C. C.
n Dcvelnpment for Monolithic
Dusek, and H . U. Andcrson.
“Sintering Aid for Lanthanum Chroniite Refractories,” U . S. Pat. No.
474Y 632, June 7, I Y X X .
”‘C. Milliken and A . Khandkar, “Fabrication o f Integral Flow-Ficldilntercon-
nect for Planar SOFC Stacka“: see Ref. 27, pp. 361-76.
lX’’M. A. Janney and H . D. Kinirey, “Microwave Sintcring of Fuel Cell M m -
rials”; presented at Conference on Fossil Energy Materials, May 15-17, 1990
Kept. No. DEOO-01 1643, CONF-900546-5 National Technical Infnrniation
Service. Alexandria, VA, 1990.
““’L. W. Tai and P A. Lessing, “Tape Casting and Sintering of Strontiuin-
Doped Lanthanum Chrnmite for a Planar Solid Oxide Fuel Cell Bipolar Plate.”
J . Am. Crrcim. Six. ,74, 155-60 (1991).
“‘W. Baukal and W. Kuhn. “ l h s Elektrodenverbindungsmaterial, Ein %en-
trales Bauclenient in Hochtcmpcratur-Brcnnstoffzcllen. Teil 1: Auswahl Von
Materialien-Ein ijherblick,” J . Fowcv Sourcrs. I , 91-97 (l976ilY77).
““C. C. Sun, E. W. Hawk, and E. F. Svcrdrup, “Electrical Evaluation of
Doped and Undoped Cobalt Chromite as the Intcrconnec‘t Material for High-
’lemperaturc, Zirconia-Electrolytc, FuelLCell Batteries,” ./. Elct.rroi.hc.m.Soi. ,
119, 1433-38 (1972).
‘”T. Negas, W. R. Hoslcr, and 1.. P Domingucs. “Preparation and Properties
of Yttrium Chroniitc Ceramics”; pp. 993-1000 in Procecdinp of rhr Fortrth
/nternurwnul Mecting on Modrrn Cerumr.i Tcchnologirs Edited by P Vincen-
i n i . ElsevicriNorth-Holland, Ncw Ynrk, 19x0.
““W. J . Wcher, J . 1,. Bates, C. W. Griflin, and L. C. Olscn, “Electrical Con-
ductivity and Secbcch Coefficient of l)ivalent-Mctal-Doped YCrO,”: pp. 235-
42 in L)c./cc.f Propc~rrirscmd P rocos\ing of Hih.h-Ti’i.lino/ogvNonmetcillic. Motcrr-
crls. Edited hy Y. Chen, W. D. Kingery. and R . J . Stokes. Materials Rcscarch
Society. Pittshurgh, PA, 1986.
““G. F. Carini II, H. U . Anderson. D . M. Sparlin. and M . M . Nasrallah,
“Electrical Contluctivily, Seeheck Cocfticient, and Defect Chemistry of
Ca-Doped YCIO,,”Solic/Stotr /onic\, 49, 2 3 3 4 1 (1991 1.
““P G. Kussell, H. S. lsaacs, A . C. C. Tseung. and S. Srinivasan, “Studics o f
Glass Composites and Doped Rulile as Interconnection Materials”; scc Ref. 1 X I .
pp. 96-102.
“”P G . Russell, H. S. lsaacs, A . C. C. Tseung, and S.Srinivasan, “Evalua-
tion ofTiO,-Glass Composites ;is Interconnector Material for Solid Oxide Elcc-
trolyte Fuel Cells.” J . Appl. Eluc.rroc.hem., 11, 197-203 (1981).
““W. Wcrsing, E. Ivers-Tiffee, M . SchieBI, and H. Greincr, “New Planar
Solid Oxide Fuel Cell with Metallic Bipolar Plate”: see Kct 3 I, pp. 3 3 9 2 .
‘“H. Tenmei. H . Michihata, T. Namikawa, and Y. Yamazaki. “Preparation ol
Metal Interconnector Cmated with LaCrO, by Vacuum Evaporation,’’ D c ~ k i
Kagukir. 58, 1072-73 (1990)
J . L . Schouler and H. S. 1. , “The Reaction Kinetics of Electrodes on
Zirconia in H,/H,O Gases,”SolidSinrr~lonic.r.5, 55.5-58 (1981).
”“K. Eguchi, T. Setoguchi, M . Sawano, S. Tamura, and H . Arai, “A Study o n
Anode and Interconnector Materials lor Solid Oxide Fuel Cells”; see Rcf. 14,
pp. 607-10.
Vol. 76, No. 3
‘‘I% I.1, Schouler and M. Klcitz. “Electrocatalysis and Inductive Effects at
the Gas. Pt/Stahilized Zirconia Enterfacc,” J . EFm,rrochcw. %So(.. 134, 1045-50
( 1987).
of Coal Gas Compounds o n
””C. J . Wen and D. M. M a w n , “Electr(,catalysis on Solid Oxide Electro-
lytc\.” J . A p p / . E l c c w o d w n . , 8, X 1-85 ( 1978).
””K. A . Gofte and 11. M . Mason, “Electrocatalytic Oxidation o f Hydrocar-
bons on a Stahilir.cd-Zirconia Electrolyte Employing Gold or Platinum Elec-
trodcs.”J. App/. Eliurorhcm., 11, 447-52 (IYXI).
”“‘8 G. Ong. C. C. Chiang, and 1) M . Mason, “Electrncatalytic Role of Sta-
hiliied Zirconia on the Anodic Current Overpotential Behavior in Hydrocarhon
Fucl Cells,” Solid Stmr lonic ,\, 3/4. 447-52 ( l9X I)
””B. C. Nguycn and 11. M . Mason, “Mechanisms of Catalytic Oxidation o f
Hydrocarhons in a Solid Electrolyte Fuel Cell”: see Kcf. 181. pp. 331-47.
” ” B . C. Nguyen. T. A . Lin. and I).M. Mason. “Elcctroc;it;ilytic Reactivrty of
Hydrocarhons o n ii Zirconia Electrolyte Surface.” J . EIwtrochrm. Soc.., 133,
1x07-I5 (1986).
‘ I T H . Etsell and S. N. Flc “Overpotential Behavior of Stahilued Zirco-
nia Solid Electrolyte Fuel Cel Elrcrridwm. So(.., 118, 1x90-900 (1971)
” “ I . Weis\bart and R. R u h a Solid Electrolyte Fuel Cell,” J . Elecrrodwm.
So<, , 109, 723-26 (IY62).
“ ‘ J . Weisshart and R . Ruka, “Solid Oxide Electrolyte Fuel Cells”: pp. 3 7 4 9
iii F u d C r l k . Vol. II. Edited hy G . J Young. Reinhold, New Ynrk, 1963.
Dees, IJ Balachandran. S. f: Dorri\, J J . Hciberger. C. C.
. and J . J . Picciolo, “Electrode Development in Monolithic Solid
Cclls”: pp. I 30-36 in Proweclinfi.\ of hi,S~nipo.siimmon Furl Cd/.\
Edited by R E. White and A . J . Appleby. Thc Electrochemical Society. Pen-
ninpton, NJ, I Y X 9 .
‘“V. N Chehotin. M. V. Gloriiov. A D. Neuimin, and S . E Pal‘guev, ”Polar-
ization of a Hydrogen Electrode (rn a Solid Oxide Electrolyte,” Sov. E k r r o -
d7rm., 7,55-60(1971).
”’T Kawada. N Sahai, H. Yokokawa. M . Dokiya, M. Mori, and T Iwata.
“Ch;iractcriatics of Slurry-Coated Nichcl Zirconia Cermet Anodes for Solid
So[.., 137, 3 0 4 2 4 7 (1990).
Oxide Fuel Cells.” J . E/ectro~.hcni.
ydrogcn Oxitlation at the Nickel/
Elcctrocheinistry 01 Porous NickeliZirconia C e
”’M E. Seienten and P H . Middleton, “Re
Nichcl Anodeh”: scc Ref. 14. pp. 569-76.
“’M. V. Glumov, A . I). Neuimin, and S. F. Pal‘gucv, “PolariLation of a
Niche1 Anode i n a Solid O.YZrOl-O IY,O, Electrolyte.” Sov. Elcr.troc.hern.. 4,
I 114-16 (I96X)
””M. V. Glumov, V. N. Chehotin, S. F. Pal‘gucv. and A. D. Neuimin, “Oxi-
dation of a Nickel Electrode in Contact with a Solid Oxide Electrolyte During
Anodic Poliirimtion.” Soy. Elacrrodicvn. 6, 386-88 ( 1970).
‘”ID. ti. Archer, L,. Elikan, and R . L Zahradnih, “Pcrforniance o f Solid Elec-
trolyte Cells and Batteries on (’0-H, Mixtures; a 100-Watt Solid Elcctrolyte
Power Supply“: pp. 5 1-75 i n ffydroc.trrhorr Fur/ C‘d/ R c h r d o g y . Edited by
tl. S . Baher Academic Press, New Yorh, 1065
‘”R. 1.. Zahradnih. “Mechanism of CO Polariration at High-Temperature
Solid Electrolyte Fucl Cell Anode\”; pp. 125-30 in Troi,\ihe,j JoirrJ1c;p.v Inter-
f i i U r o n d i ~ . d’krude
s d r s Pi/c.v i Comhu.srih/r, Presses AcadCmiqucs Europeen-
I.. Zahradnik, “l)iffu.;ional Procecses in Solid Electrolyte Fuel Cell Elec-
V. Karpachov, A . T. Filyayev. arid S. E Pal’guev, “Pnlarization ol Car-
irconiu-Lime Electrolyte.“
E/rc,froc.him.Acfci, 9, 1681-85 (1964).
”’S. V. Karpachcv, A . E. Zupnik, and M. V. Perfil’ev. “Polarization for
Reduction of Carbon Dioxide at a Platinum Electrode in a Solid Electmlyte.”
Sor Eler~troi~hern. . 6 , 564-66 ( 1970)
”-V. N. Chehoshin. M. V. Glun~ov,S. F. Pal’guev, and A . D. Neuimin.
“Polarization o f a Carbon Monoxide Electrode on a Solid Oxide Electrolyte,“
So\.. Ele(.frochem..7, 179-84 ( I 9 7 I)
”“D W. Dees, IJ. Balachandran, S. E. Uorris. J . J . Heiherger, C. C
McPhcctcrs, and J . J . Picciolo, “Interfacial EI.fect\ in Monolithic Solid Oxide
Fuel Cells”: see Ref. 27, pp. 317--2 I .
”’T. Kawada. N. Sahai, H . awa, M . Dokiya, M . Mori. and T. Iwata,
“Structurc and Polariiation Ch istics of Solid Oxide Fuel Cell Anodes,“
Solid Stotr l o n i c s , 40/41, 4 0 2 4 0 6 ( 1090).
’”S. Murukami. Y. Akiyama, N . Ishida, T Yasuo, T. Saito, and N . Furu-
kawa, “Development of :I Solid Oxide Fuel Cell with Composite Anodes”: see
Ref. 14. pp. 561-68.
’”’ti. Mnggio, I.lelo, V. Antonucci. and N. Giordano, “Morphological Opti-
mimtion of a SOFC Anode Based on Theoretical Consideration\: A Preliminary
Appi-oach”: SCC Ref. 14, pp. 61 1-20
””S. C. Singhal, R. J. Ruka, J. E. Bauerle, and C. J. Spengler. “Anodc
Development for Solid Oxide Fucl Cells,” R e p . No. DOEiMCi22046-237 I.
U.S. I k p t of Eneigy. Washington. l)C, IOXO.
March 1993 Crrurnic Fuel Ce1l.c.
”‘H. Binder. A. Kiihling, H. Krupp. K . Richter, and G. Sandstcde, “Elektro-
chemische Oxydation von Kohlen-Wasserstoffen in einer Festelcktrolyt-Brenn-
stoffxlle bei Temperaturen von 900°-1 O O O T , ” ,rrtdiim. A<ya, 8 , 78 1-03
(1963).
‘”I? Singh, R . J. Ruka, and R . A. George, “Direct U t i l i d o n o f Hydrocar-
bons Fuels in High-Tcnipcrature Solid-Oxide Electrolyte Fuel Cells”; pp. 1553-
63 in P r o w e d i n p ofthe 24th Inr~rr.sor.ietyEner-gy Conversion En,yirirrring Con-
fermce, Vol. 3 . Institute of Electrical and Electronics Engineers, New York,
1989.
”’L. A. Shockling and J . M . Makiel, “Natural-Gas-Fueled 3-kWe SOFC
Generator Test Results”; see Ref. 43,pp. 224-29.
’“A. 1.. Lee, “Internal Reforming Developinent for Solid Oxide Fuel Cells,”
Rept. No. DOEIMCi2204.5-2364,U.S. Dcpt. of Energy. Washington, DC.
1987.
”’I? Singh, J. Ruka, and R. A. George, “Electrochemical Generator Appara-
tus Containing Modilied Fuel Electrodes for Use with Hydrocarbon Fuels,” U.S.
Pat. No. 4894297,Jan. 16, 1990.
”“M.Mogensen, R . Kindl, and B. Malmgreii-Hansen. “On the Prospects o f
Operating an SOFC on Dry Natural Gas”; pp. 195-98 in 19YOFurl C d l Seminur
Abstracts (Phoenix, AZ, Nov. 25-28, 1990). Courtesy Associates. Washington,
DC, 1990.
”’S. Pinini, “General Aspects of Kinetics d lon-Tranorer across Interfaces”;
pp. 46 1-76 in F m t /on 7runsport in Solids, Solid-Srute Barfrrirs, and Devicrs.
Edited by W. Van Gool. North-Holland, Amsterdam, Netherlands, 1973.
‘“D. 0. Raleigh, “Electrode Processes in Solid-Electrolyte Systems”; pp 87-
186 in Elcctroonalyticul Chemi.\try, A Series of Advances, VI. Edited by A. J
Bard. Marcel Dekker, New Ynrk, 1973.
29qT.M .Giir. I. D. Raistrick, and R. A. Huggins, “Solid ElcctrolyteiPorous
Electrode Kinetics”; pp. 113-16 in Fast Ion Trunsport in So1id.s. Edited by
I? Vashishta, J. N . Mundy, and G . K . Shenoy. ElsevieriNorth Holland, New
York, 1979.
Y?Fabry and M. Kleitz, “lnlluence of the Metal and the Electrolyte Compo-
sition on the Characteristics o f the Oxygen Electrode Reaction on Solid Oxide
Electrolyte,” J . Electrouriul. Cham. Interfuciul Elet.troc.hem., 57, 165-77
(1974).
‘‘‘E. Schouler, M. Kleitz, and C. Deportes, ”Applications Selon Bauerle du
Trace des Diagranwes d’ Adinittance Complexe en Electrnchiniie des Solides. I .
de Quelques RBactions d’Electrode sur (ZrO
Phy.i.Chim. R i d . . 70,923-35 (1973).
H . S . lsaacs and L. J . Olmer, “Correlation o f the AC and DC Polarization
ances of a Platinum ElectrodeiZirconia Solid Oxide Electrolyte Interface,”
J . Electround. Chem. lriterfui~iulElectrochem., 132,59-65 ( 1 982).
“’D. Y. Wang. “Low-Temperature Diffusioned-Conti.olled PolariLation of Pt
Electrodes with Yttria-StabiliLed Zirconia Electrolyte,” J . Electrocham. Soc.,
137,366046 (1990).
IUM. Klcitz. I? Fabry, and b;. Schouler, “Electrode Polarization and Electronic
Conductivity Determination in Solid Electrolytes”: sce Ref. 237,pp. 439-5 I
Ia5J. Sasaki, J . Mizusaki, S. Yamauchi, and K . Fueki, “Studies o n Electrode
Processes of Stabilized Zirconia Cells by the Complex Impedance Method,”
Solid Sruw / 0 1 7 i C . S , 3/4,53 1-35 (I981 ).
”‘“J. Mifusaki, K . Amino, S. Yamauchi, and K . Fueki. “Electrode Reaction
at P~,O,,,,iStabilizcd Zirconia Interfaces. Part 1: Theoretical consideration of
Reaction Model ,” Solid Stirre lonic.5, 22, 3 13-22 ( 1987).
’*’J. Miiusaki, K . Amano, S . Yamauchi, and K . Fueki, “Electrode Reaction
at Pt,O,,,,iStabilizcd Zirconia Interfaces. Part 11: Electrochemical Measurements
Solid SmrP lonics, 22, 323-30 (1987).
24xJ. Sasaki, J. Mizusaki, S. Yamauchi, and K . Fueki, ”Studies on Electrode
Processes of Stabilized Zirconia Cell System by Complex Impedance Method,”
Bull. Chem. Soc. Jpn., 54, 1688-92 ( I98 I 1.
‘+’T. Kenjo, Y. Horiuchi, and S. Osawa, “Determination of the Rate Constants
ol Oxygen Reduction in High-Temperature Air Electrodes on Solid Oxide Elec-
trolytes,” J . Electrocham. S m . . 137,2423-31 (1990).
”“T.Kcnjo. S . Osawa, and H . Murahashi, “Influence of Electrolytes and
Some Oxide Additives on High-Temperature Platinum Cathodes.” Dmki
K o g o k u , 58,53341 (1990).
“‘D. Y. Wang and A . S . Nowick, “Uiffusion-Controlled Polarization o f Pt.
Ag, Au Electrodes with Doped Ceria Electrolyte.” J. E/ectroi.hem. So<.., 128,
5 5 4 3 (1981).
252’r.M. Cur, I.D. Raistrick, and R. A . Huggins. “AC Admittance Measure-
ments on Stabilized Zirconia with Porous Platinum Electrodes,” Solid Stcite / o n -
ics, 1, 251-71 (1980).
‘”B. L. Kuzin and M. A. Komarov, “Adsorption of 0, at Pt and Kinetics of
the Oxygen Reaction at a Porous PI Electrode in Contact with a Solid Oxide
Electrolyte,” Solid State lonics. 39, 163-72 (1990).
’“T. M. Giir, I.D. Raistrick, and R. A . Huggins, “Steady-State DC Polariza-
tion characteristics o f the O,, PtIStahilized Zirconia Interface,” J . Electroc,hem.
Soc..127,2620-28 (1980).
’”M. J. Vcrkerk, M . W. J. Hammink, and A. J. Burggraaf, “Oxygen Transfer
on Substituted ZrO,, BizO,, and C e 0 2Electrolytes with Platinuni Electrodes. I
585
Electrode Resi5tance by DC Polarization.” J . Elcctrodrcvn. So(.., 130, 70-7X
(I983).
‘“‘R. J. Brook and T. L. Markin, “Elcctrodes for Solid Electrolyte Systems”:
see Ref. 237,pp. 53341.
‘”R. J. Brook. W. L. Pelzmann. and F. A Krligcr. “Platinuni Electrodes and
Calcia-Stabilized Zirconia. The Relation between Electrode Processes and Elcc-
trode Structure.” J . Elrtrroc.hrrn. So(.., 118, 185-92 (1971).
”‘H. Yanagida, R. J . Brook. and F. A. Kroger. “Direct Current-Voltage Char-
acteristics o f Calctn-Stabilized Zirconia with Porous Platinum Electrode\.”
J . Elwtrochem. Soc.., 117,593-602 (1970).
””M. V. Glumov, “The Polarization of Porous Platinum Electrodes in a Solid-
Electrolyte Cell in Oxygen Atmospheres,” Sov. E l e m o ~ ~ h e.m22, 207-1 I
( 1984).
‘“‘A. 1. Gruzdev, “Electrode Kinetics in Systems Consisting of Thin-Film
Metal Electrodes and Stnbili7ed Zirconiurn Dioxide,” So\, E l r t w u d w n i . . 26,
530-37 (1990).
”“D. Braunshtein. I>. S Tannhauser, and I. , “Diffusion~LinlitedCharge
Transport at Platinum Elcctrodes on Doped C J . E / r c r r d i e f n . .To<,. , IZX,
82-89(1981).
Ih2R. E. W Cawelton, “Blackening in Yttria-Stabilized Zirconia due to
Cathodic Processes at Solid Platinum Electrodes.”./ Appl. Elccrruchem., 4, 25-
48 (1974).
2“iD.Y. Wang and A. S . Nowick. “Cathodic and Anodic Polarization Phc-
nomena at Platinum Electrodes with Doped CeOl as Electrolyte, I. Steady-State
Overpotential.” J . E/wtrochmi. Soc.. 126, I 155-65 (1970).
‘“9. Y. Wang and A . S. Nowick, “Cathodic and Anodic Polarization Phe-
nomena at Platinum Electrode\ with Doped CeO, as Electrolyte, 11. Transient
Overpotential and AC Inipedance,”J. Elc~crrochum.Soc., 126, I 166-72 (1979).
””A. J. A. Winnubst, A . H . A . Scharenborg, and A. J. Burggraaf. “The Elec-
trode Resistance of ZrO,-Y,O,(-BizO,) Solid Elcctrolytes with PI Electrodes.”
SolidSrureloni(..,, 14, 319-27 (1984)
”“‘A. T. Filayev, S. V Karpachev, and S. F Pal’guev, “A Study of Oxygen
Electrode PolariLation in a Solid Electrolyte”; pp. 161-65 in Elc.[,rrochemr.\tr~of
Molren rind Solid Elc~crrol.vte.s.Vol. 4. Edited by A N . Barabothkin and S. F.
Pal’guev. Consultants Bureau, New York, 1967.
2h7S.Pizzini, M. Bianchi, I? Colombo, and S. Torchio, “On the Influence of
the Annealing Temperature and Heavy Current oil the Porous Structure o f Plati-
num Electrodes and on the Kinetics of the Oxygen Reaction at High Teinpera-
tures,”J. Appl. Elecrroehiw~.,3, 153-59 (1973).
‘“’T. M . Giir and R. A . Huggins, “Importance of ElectrodciZirconia Interface
Morphology in High-Temperature Solid Electrolyte Cells,” J. A p p / . E / i w r < f -
i.hem., 17, 800-806 (1987).
‘“‘’N. L . Riibertson and J. N.Michaelc. “Oxygen Exchange on PI
trodes in Zirconia Cells: Location of Electrochemical Reaction Sit
L . Schouler, and C. Y. Yang, “Electrode
Solid Stare lonics. 3/4,503-507 ( 198 I ).
;’
‘”H. S. lsaacs and L . J. Olmcr, “Cumparison of Matei-ials as Oxygen Cata-
lytic Electrodes on Zirconia Electrolyte,” J . Electrochem. Sn(,.,129, 430-43
(1982).
”>T. Inoue, N . Scki. K . Eguchi, and H . Arai, “Low-Temperature Operation of
Solid Electrolyte Oxygen Sensors Using Pel-ovskite-TypeOxide Electrodes and
Cathodic Reaction Kinetics,” J . Electrochcvn. Soc., 137, 2523-27 ( 1990).
’”T. Inouc. K. Eguchi. T. Setnguchi, and H . Arai. “Cathode and Anode
Materials and the Reaction Kinetics for the Solid Oxide Fuel Cell,” Solirl Stutc
lonirs. 40141,407-10 (1990).
27JY.Takeda, R. Kanno. M. Noda, Y. Tomida. and 0. Yamaninto, “Cathodic
Polarization Phenomena o f Perovskite Oxide Electrodes with Stabilized Zirco-
nia,” J. E/<~rrochrw?. Soc., 134, 26.56-61 (1987).
’”S. P S. Badwal, D. J . M . Bevan. and J. O’M. Bockris, “The Electrode
Kinetics of the Evolution and Dissolulion of Oxygen at the Urania-Zirconla
Interfaces,” Electrochin7. Actu, 25, I 115-25 (1980)
2”7G. F? Wirtz and H. S. lsaacs, “Defect Electrochemi\try of Oxide Elcc-
trodcs”; 5ec Ref. 75,pp 303-22.
?”K. Eguchi, T, h u e , M . Ueda, J . Kainimae, and H . Arai, “The Activation
and Transfer of Oxygen at ElectrolyteiCathodc Interface for SOFCa”; see Kef.
14, pp. 697-704.
“‘A. Hammouche, E. Siebert. M . Kleitz, and A . Hammou, “Oxygen Reduc-
tion at the La,+,Sr,MnO,iZirconia Electrode”: see Ref. 27, pp. 265-76.
27”A.Hammouche, E. Siebert, A . Hammou, and M. Kleitz, “Electrocatalytic
Properties and Nonstoichiometry of the High-Temperature Air Electrode
La, ,Sr,MnO,,”J. Electrochem. Soc.., 138, 1212-16 (1991).
””T. Jacobsen, B. Zachau-Christian. K . West, and S. Skaarup. “Linear
Sweep Voltammetry on La,)Jr,, ,,MnO ee Ref. 14,pp. 795-802.
2x’J. Mizusaki, H. Tagawa, K . Tsuneyoshi. and A . Sawata. “Reaction Kinet-
ics and Microstructure of L4),,Ca,,,MnO,lYSZ Air Electrode”; see Ref. 27,pp.
254-64.
1x2J. Mizusaki. H.Tagawa, K . Tsuneyoshi, and A. Swata, “Reaction Kinetics
and Microstructure o f the Solid Oxide Fuel Cells Air Electrode Lii,,,Ca,,d
MnOJYSZ,” J. Elrctrochcvn S o c . , 138, 1867-73 (1991).
586 Journal of the American Ceramic Society-Minh
2x3L.G. J. de Haart, K. J. de Vries, A. I? M. Carvalho, J. R . Frade, and
F. M. B. Marques, “Evaluation of Porous Ceramic Cathode Layers for Solid
Oxide Fuel Cells,”Muter. Res. Bull., 26, 507-17 (1991).
2xaL.G. J. de Haart, R. A. Kuipers, K. J. de Vries, and A. J . Burggraaf,
“Deposition and Electrical Properties of Thin Porous Ceramic Electrode Layers
for Solid Oxide Fuel Cell Application,” J . Electrochem. Soc., 138, 1970-75
( I99 I ) .
laso. Yamamoto, Y. Takeda, R. Kanno, and M. Noda, “Cathodic Polarization
Phenomena of Oxide Electrodes with Stabilized ZrO, Electrolyte”; see Ref. 7,
pp. 829-35.
2R6M.Aizawa, H. Nishiyama, A. Ueno, C. Kobayashi, S . Suzuki, K. Eguchi,
and H. Arai, “Study on Air Electrode Made of La-Based Materials”; see Ref. 14,
pp. 803-1 1.
28’K. Tsuneyoshi, K. Mori, A. Sawata, J. Mizusaki, andH. Tagawa, “Kinetic
Studies on the Reaction at the L&, ,MnO,/YSZ Interface as an SOFC Air
Electrode,” SolidStare lonics, 35,263-68 ( I 989).
IRXW.Feduska and A. 0. Isenberg, “High-Temperature Solid Oxide Fuel
Cell-Technical Status,” J . Power Sources, 10, 89-102 (1983).
’*)A. 0. Isenberg, “Cell Performance and Life Characteristics of Solid Oxide
Electrolyte Fuel Cells”; see Ref. 75, pp. 5-15.
24Westinghouse Electric Corp., “Solid Oxide Fuel Cell Power Generation
System, The Status of the Cell Technology-A Topical Report,” Rept. No.
DOE/ET/17089-15, U.S. Dept. of Energy, Washington, DC, 1984.
2y’J.T. Brown, “High-Temperature Solid-Oxide Fuel Cell,” Energy, 11,209-
29 (1986).
2”2S.C. Singhal, “Solid Oxide Fuel Cell Development at Westinghouse”; see
Ref. 14. pp. 25-33.
zy’W.J . Dollard, “The Westinghouse Solid Oxide Fuel Cell Progralk-A 1989
Progress Report”; see Ref. 3 I , pp. 1- I I .
’%D. C. Fee, S . A. Zwick, and J . F! Ackennan, “Solid Oxide Fuel Cell Perfor-
mance”; see Ref. 75, pp. 29-38.
”X J. Bratton, P. Reichner, and L. W. Montgomery, “Fuel Cell Production
Process Control and Qualification of Finished Cells”; see Ref. 55, pp. 80-83.
2“G. E. Zymboly, I? Reichner, and J. M. Makiel, “Cell Fabrication, Design,
and Operation of a Solid Oxide Fuel Cell Generator”; see Ref. 95, pp. 95-101.
2”7B.R. Rossing, “Microstructure-Property Relationships for Porous CaO-
Stabilized 210, Support Tubes”; see Ref. 75, pp. 45-55.
29RWestinghouseElectric Corp., “High-Temperature Solid Oxide Electrolyte
Fuel Cell Power Generation System, Quarterly Technical Report April-June
1984,” Rept. No. DOE/ET/17089-2218, U. S . Dept. of Energy, Washington,
DC, 1984.
2V)A.0. fsenberg, “Growth of Refractory Oxide Layers by Electrochemical
Vapor Deposition (EVD) at Elevated Temperatures”; pp. 572-83 in Proceedings
of the Symposium on Electrode Materiuls and Processes for Energy Conversion
ond Storage. Edited by J. D. E. Mclntyre, S. Srinivasan, and F. G. Will. The
Electrochemical Society, Pennington, NJ, 1977.
“‘R. Draper, “Progress in Solid Oxide Fuel Cell Technology Utilizing Multi-
Stage Vacuum Pumping Systems in Electrochemical Vapor Deposition Process,”
fnd.Heut., [Dec.]4446(1991).
“”A. 0. Isenberg, “Energy Conversion via Solid Oxide Electrolyte Electro-
chemical Cells at High Temperatures,”Solid Stale lonics, 3/4,43 1-37 (198 I).
’“*U.B. Pal and S. C. Singhal, “Electrochemical Vapor Deposition of Yttria-
Stabilized Zirconia Films”; see Ref. 27, pp. 41-56.
’”U. B . Pal and S . C. Singhal, “Electrochemical Vapor Deposition of Yttria-
Stabilized Zirconia Films,” J . Electrochem. Soc., 137, 293741 (1990).
’N. J. Kiwiet and J. Schoonman, “Electrochemical Vapor Deposition: The-
ory and Experiment”; see Ref. 43, pp. 240-45.
“”J. I? Dekker, N. J . Kiwiet, and J. Schoonman, ‘‘Electrochemical Vapor
Deposition of SOFC Components”; see Ref. 27, pp. 57-66.
%J. Schoonman, J . P. Dekker, J. W. Broers, andN. J. Kiwiet, “Electrochemi-
cal Vapor Deposition of Stabilized Zirconia and Interconnection Materials for
Solid Oxide Fuel Cells,” Solid State lonics, 46, 299-308 (1991).
’“’Y.S . Lin, L. G. J. de Haart, K. J . de Vries. and A. J. Burggraaf, “Thin
Electrolyte Layers for SOFC via Modification of Ceramic Membranes by CVD
and E V D ; see Ref. 27, pp. 67-70.
’““Y.S. Lin, L. G. J. de Haart, K. J . de Vries, and A. J . Burggraaf, “A Kinetic
Study of the Electrochemical Vapor Deposition of Solid Oxide Electrolyte Films
on Porous Substrates,” J . Electrochem. Soc., 137, 3960-66 (1990).
’wM. F. Carolan and J. N. Michaels, “Chemical Vapor Deposition of Yttria-
Stabilized Zirconia on Porous Supports,’’ Solid State lonics, 25,207-16 (1987).
” O M . E Carolan and J. N. Michaels, “Growth Rates and Mechanism of Elec-
trochemical Vapor Deposited Yttria-Stabilized Zirconia Films,’’ Solid State lon-
ics, 37, 189-95 (1990).
”‘M. F. Carolan and J. N. Michaels, “Morphology of Electrochemical Vapor
Deposited Yttria-Stabilized Zirconia Thin Films,’’ Solid State lonics, 37, 197-
202 ( 1990).
’12G. Dietrich and W. Schafer, “Advances in the Development of Thin-Film
Cells for High-Temperature Electrolysis,” lnr. J . Hydrogen Energy, 9, 747-52
(1984).
Vol. 76, No. 3
”’J. H. Enloe and G . P. Wirtz, “Characterization of Vapor-Deposited Tin-
Doped Indium Oxide Films,’’ J. Electrochem. Soc., 133, 1583-87 (1986).
”““Abar lpsen Makes Reactors for Fuel Cell Fabrication,” Cerum. lnd., 130
[2] 13 (1988).
’15A. 0. Isenberg, “Recent Advances in Solid Electrolyte Fuel Cell Technol-
ogy”; pp. 154-56 in lY82 Fuel Cell Seminur Abstracts (Newport Beach, CA,
Nov. 14-18, 1982). Courtesy Associates, Washington. DC, 1982.
”‘A. 0. Isenberg, “Advancing from Single Cell Technology to Generator
Engineering (A SOFC Status Report)”; pp. 78-81 in 1983 Fuel Cell Seminar
Abstracts (Orlando, FL, Nov. 13-16, 1983). Courtesy Associates, Washington,
DC. 1983.
“’N. J . Maskalick, “Design and Performance of Tubular Solid Oxide Fuel
Cells”; see Ref. 27, pp. 279-87.
”‘Westinghouse Electric Cop., “High-Temperature Solid Oxide Electrolyte
Fuel Cell Power Generation System, Quarterly Technical Progress Report April-
June 1983,” Rept. No. DOE/ET/17089-12, U.S. Dept. of Energy, Washington,
DC, 1985.
”’Westinghouse Electric Corp., “High-Temperature Solid Oxide Electrolyte
Fuel Cell Power Generation System, Quarterly Summary Report July-Septem-
ber 1983,” Rept. No. DOE/ET/17089-1972. U . S . Dept. of Energy, Washington,
DC. 1985.
’?“A. 0. Isenberg, “Performance and Life Test of a Solid Oxide Fuel Cell
Stack”; see Ref. 95, pp. 102-106.
“IF? Reichner and J. M. Makiel, “Development Status of Multi-Cell Solid
Oxide Fuel Cell Generators”; see Ref. 55, pp. 32-35.
”’S. E. Veyo, “SOFC Field Experiments, a Learning Experience”; see Ref.
26, pp. 13-17.
’?’E. R. Ray, “High-Temperature Solid Oxide Electrolyte Fuel Cell Power
Generation System”; see Ref. 178, pp. 123-26.
‘24W.G. Parker, “Westinghouse Solid Oxide Fuel Cell Program-A 1990 Sta-
tus Report”; see Ref. 43, pp. 213-17.
’”L. A. Shockling and P. Reichner, “Development of a Commercially Practi-
cal Natural Gas Fueled SOFC Generator”; see Ref. 212, pp. 106-17.
’2hA. 0. Isenberg, “Thin-Film High-Temperature Solid Electrolyte Fuel
Cells”; see Ref. 299, pp. 682-91.
‘?’Y. Ohno, S . Nagata, and H. Sato, “Development of a High-Temperature
Solid Electrolyte Fuel Cell”; pp. 88 1-85 in Proceedings of the 15th lntersoriery
Energy ConverJion Engineering Conference. American Institute of Aeronautics
and Astronautics, New York, 1980.
””H. Sato, “High-Temperature Solid Electrolyte Fuel Cell,” Energy Dev.
Jpn.,4, Il1-28(1981).
12’)S.Nagata, Y. Ohno, Y. Kasuga, Y. Kaga, and H. Sato, “Development of
High-Temperature Solid Oxide Electrolyte Fuel Cells”; pp. 827-32 in Proceed-
ings of the 1Yrh Intersociety Energv Conversion Engineering Conference,
Vol. 2. American Nuclear Society, La Grange Park, IL, 1984.
““D. H. Archer, R. L. Zahradnik, E. F. Sverdrup, W. A. English, L. Elikan,
and J. J . Alles, “Solid Electrolyte Batteries”; pp. 3 6 4 0 in Proceedings of the
18th Annual Power Sources Conference (Fort Monmouth, NJ, May 19-21,
1964). PSC Publications Committee, Red Bank, NJ, 1964.
‘“D. H. Archer, E. F. Sverdrup, and R. L. Zahradnik, “Coal-Burning Fuel
Cell Systems,” Chem. Eng. Prog., 60 [6] 64-68 (1964).
332 H . J . Bohme, H. Eysel, W. Fischer, H. Kleinschmager, E J. Rohr, and
R. Steiner, ”High-Temperature Fuel Cells: Component Development, System
Analysis, and Application”; pp. 5-59-5-64 in ENERGY 70, Proceedings of
Intersociety Energy Conversion Engineering Conference, Vol. I , 1970.
Society of Automotive Engineers, Warrendale, PA, 1970.
”’W. Fischer, H. Kleinschmager, E J. Rohr, R. Steiner, and H. H. Eysel,
“Hochtemperatur-Brennstoffzellen mit Keramischem Elektrolyten zum Umsatz
billiger Brennstoffe. Teil 1,” Chem.-1ng.-Tech.,43, 1227-32 (1971j.
“‘W. Fischer, H. Kleinschmager, F. J. Rohr, R. Steiner, and H. H. Eysel,
“Hochtemperatur-Brennstoffzellen mit Keramischem Elektrolyten zum Umsatz
billiger Brennstoffe, Teil 11,”Chem.-1ng.-Tech.,44, 726-32 (1972).
”‘R. Steiner. “Festelektrolytzellen auf ZQ-Basis und deren Anwendungen,”
Chem.-lng.-Tech.,44, 152-54 (1972).
”“F. J. Rohr, “High-Temperature Solid Oxide Fuel Cells: Present State and
Problems of Development”; see Ref. 181, pp. 122-38.
”’I? J. Rohr, “High-Temperature Fuel Cells”; pp. 431-50 in Solid Electro-
lytes. Edited by P. Hagenmuller and W. van Cool. Academic Press, New York,
1978.
““W. Danitz, G. Dietrich, E. Erdle, and R. Streicher, “Electrochemical High-
Temperature Technology for Hydrogen Production or Direct Electricity Genera-
tion,”Int. J . Hydrogen Energy, 13,283-87 (1988).
’”W. Donitz, E. Erdle, W. Schafer, R. Schamm, and R. Spah, “Status of
SOFC Development at Dornier”; see Ref. 14, pp. 75-84.
““F. Umemura, H. Ota, K. Amano, S . Kaneko, T. Gengo, S. Uchida,
N. Murakami, and A. Notoni, “Development of Solid Oxide Fuel Cell”; see
Ref. 31, pp. 25-32.
’‘‘Y. Ohno, Y. Kaga, and S. Nagata, “A Study on the Fabrication and the Per-
formance of the Solid Electrolyte Fuel Cell,’’ Elecrr. Eng. Jpn., 107, 5 9 4 7
(1987) (translated from Denki Gakkai Ronbunshi, 106B, 693-700 (1986)).
March 1993 Ceramic Fuel Cells
342K.Tsukamoto, F. Uchiyama, Y. Kaga, Y. Ohno, T. Yanagisawa, Y. Taka-
hagi, M. J. Lain, T. Nakajima, and A. Monma, “A New Ceramic Coating Tech-
nique for the SOFC Using the ETL Laser Spraying Process”; presented at the 7th
International Conference on Solid State lonics, Hakone, Japan, Nov. 5-1 I ,
1989.The Solid State lonics Society of Japan, 1989.
343Y.Ohno, “The Fabrication and Application of Sintering Materials for
Energy Conversion Technique”; pp. I179-84 in Proceedings of International
Institute for the Science of Sintering Symposium (Tokyo, Japan, Nov. 4-6, 1987)
Elsevier Applied Science, London, U.K., 1987.
344Y.Kaga, Y.Ohno, and T. Nakajima, “A Study on the Gas Permeation Per-
formance of Solid Oxide Fuel Cell Components,” Trans. fnst. Electr. Eng. Jpn.,
IWB, 145-52 (1989).
345Y.Ohno, Y. Kaga, A. Monma, K. Tsukamoto, F. Uchiyama, and T. Okuo,
“Evaluation of Gas Permeabilities of Solid Oxide Fuel Cell Components”; see
Ref. 14, pp. 4 5 5 4 2 .
‘&W. Donitz and R. Schmidberger, “Concepts and Design for Scaling Up
High-Temperature Water Vapour Electrolysis,” Int. J. Hydrogen Energy, 7,
321-30(1982).
147S. Nagata, Y. Kasuga, K. Hayashi, Y. Kaga, Y. Ohno, and R. Fukuda,
“Development of Solid Oxide Fuel Cell”; see Ref. 26, pp, 74-77.
?j. Kaneko, T. Gengo, S. Uchida, and Y. Yamauchi, ”Research and Devel-
opment of Solid Oxide Fuel Cells”; see Ref. 14, pp. 3 5 4 2 .
Umemura, H. Ohta. K. Amano, T. Saishoji, S. Kaneko, N. Murakami,
T. Gengo, and S . Uchida, “Research and Development of SOFC’; see Ref. 236,
pp. 127-30.
35”J. l? Ackerman and J. E. Young, “Solid Oxide Fuel Cell Having Monolithic
Core,” U.S. Pat. No. 4476 198, Oct. 9 , 1984.
”‘R. B. Poeppel and J. T. Dusek, “Solid Oxide Fuel Cell Having Monolithic
Cross Flow Core and Manifolding,” U.S. Pat. No. 4476 196, Oct. 9, 1984.
Iq2N.Q . Minh, “Monolithic Solid Oxide Fuel Cells,” J. lnst. Electr. Eng.
Jpn., 109,826-30 (1989).
353. Majumdar, “Stress and Fracture Behavior of Monolithic Fuel Cell
Tapes”; see Ref. 55. pp. 60-63.
”“C. C. McPheeters and T. D. Claar, “Tape-Casting High-Density Electrolyte
for Solid Oxide Fuel Cells”; see Ref. 55, pp. 6 4 4 7 .
’5sN.Minh, E Liu, I? Staszak, T. Stillwagon, and J. Van Ackeren, “Mono-
lithic Solid Oxide Fuel Cell Fabrication Development”; see Ref. 26, pp. 105-
108.
3s6U. Balachandran, S. E. Dorris, J. J. Picciolo, R. B. Poeppel, C. C.
McPheeters, and N. Q. Minh, “Material and Fabrication Challenges in the
Development of Monolithic Solid Oxide Fuel Cells”; see Ref. 232, pp. 154145.
3”C. C. McPheeters, D. W. Dees, S. E. Doms, and J. J. Picciolo, “Argonne
Monolithic Solid Oxide Fuel Cell Fabrication”; see Ref. 26, pp. 29-32.
358N.Q. Minh, C. R. Home, F. Liu, I? R. Staszak, T. L. Stillwagon, and J . J.
Van Ackeren, “Forming and Processing of Monolithic Solid Oxide Fuel Cells”;
see Ref. 27, pp. 307-16.
”’B. D. Sawicka, W. A. Ellingson, and C. McPheeters, “High-Resolution
Computed Tomography for Flaw Detection in Advanced Thin-Layer Ceramics
for Fuel Cells,” Ceram. Ens. Sci. Proc., 8 [7-81525-37 (1987).
IMD. C. Fee, I? E. Blackbum, D. E. Busch, T. D. Claar, D. W. Dees,
J. Dusek, T. E. Easler, W. A. Ellingson, B. K. FLandermeyer, R. J. Fousek,
I . I . Heiberger, T. E. Kraft, S . Majumdar, C. C. McPheeters, F. C. Mrazek, J. J .
Picciolo, R. B. Poeppel, and S. A. Zwick, “Monolithic Fuel Cells”; pp. 1634-
37 in Proceedings of the 21sf Intersociety Energy Conversion Engineering Con-
ference, Vol. 3. American Chemical Society, Washington, DC, 1986.
’n’D. C. Fee, M. C. Billone, D. E. Busch, D. W. Dees, J . Dusek, T. E. Easler,
W. A. Ellingson, B. K. Flandermeyer, R. J. Fousek, J. J. Heiberger,
S. Majumdar, C. C. McPheeters, F. C. Mrazek, J . I . Picciolo, and R. B. Poep-
pel, “Monolithic Fuel Cells”; pp. 803-807 in Proceedings of the 22nd Intersoci-
ety Energy Conversion Engineering Conference, Vol. 11. American Institute of
Aeronautics and Astronautics, Washington, DC, 1987.
M2N.Q. Minh, “Monolithic Solid Oxide Fuel Cells: Green Body Prepara-
tion”; pp. 2 13-2 1 in Thirty-Seventh Sagamore Materials Research Conference
Proceedings, Structural Ceramics. Edited by D. J . Viechnicki. Army Materials
Technology Laboratory, Watertown, MA, 1990.
“’N. Q. Minh, T. R. Armstrong, J. V. Guiheen, C. R. Home, F. S . Liu. D. M.
Moffatt, T. L. Stillwagon, and J. I. Van Ackeren, “Monolithic Solid Oxide Fuel
Cell Technological Status”; see Ref. 236, pp. 524-26.
3MD.C. Fee, P. E. Blackbum, D. E. Busch, T. D. Claar, D. W. Dees, 1.
Dusek, T. E. Easler, W. A. Ellingson, 8. K. Flandermeyer, R . I. Fousek, J . J.
Heiberger, T. E. Kraft, S. Majumdar, C. C. McPheeters, F. C. Mrazek, J. J. Pic-
ciolo, R. B. Poeppel, and S. A. Zwick, “Monolithic Fuel Cell Development”;
see Ref. 55, pp. 4 W 3 .
’65C.C. McPheeters, U. Balachandran, P. E. Blackburn, D. E. Busch, D. W.
Dees, S. E. Dorris, J. Dusek, J. J. Heiberger, H. Leu, S. Majumdar, F. C. Mra-
zek, K. M. Myles, J. 3. Picciolo, and R. B. Poeppel, “Recent Advances in
Monolithic Solid Oxide Fuel Cell Development”; pp. 279-82 in Proceedings of
the 23rd lntersociery Energy Conversion Engineering Conference, Vol. 2 .
American Society of Mechanical Engineers, New York, 1988.
587
IhOD. C. Fee, S. K. Bhattacharyya, D. E. Busch, L. W. Carlson, T. D. Claar,
D. W. Dees. J. Dusek, T. E. Easler, W. A. Ellingson, B. K. Flandermeyer, R. J.
Fousek, H. K. Geyer, J. J. Heiberger, K. D. Kuczen, S. Majumdar, C. C.
McPheeters. F. C . Mrazek, J. J. Picciolo, and R. B. Poeppel, “Monolithic Fuel
Cell Based Power Source for Burst Power Generation”; pp, 209-14 in Space
Nuclear Power Systems 1986. Edited by M. S. El-Genk and M. D. Hoover.
Orbid Book Co., Malabar, FL, 1987.
lh7R.C. Ruhl, “Solid Electrolyte Fuel Cell and Assembly,” U.S. Pat. No.
4770955, Sept. 13, 1988.
’“J. E. Herceg, “Integral Manifolding Structure for Fuel Cell Core Having
Parallel Gas Flow,” U.S. Pat. No. 4476 197, Oct. 9, 1984.
’““M. S. Hsu, “Compact, Light-Weight, Solid-Oxide Electrochemical Con-
verter,”U.S. Pat. No. 4629537, Dec. 16, 1986.
’“M. S. Hsu, “Efficiency Doubling Using Solid Oxide Fuel CelllSteam Power
Plant Integration”; see Ref. 31, pp. 76-82.
’”M. S. Hsu, “Zirconia Fuel-Cell Power System”; see Ref. 95, pp. 115-18.
’”H. Takagi, S. Kobayashi, A. Shiratori, K. Nishida, and Y. Sakabe, “Fabri-
cation and Performance of Monolithic Solid Oxide Fuel Cell”; see Ref. 14,
pp. 99-103.
”’Ceramatec, Inc., “Development of Planar Geometry Solid Oxide Fuel
Cell Technology, Phase 1 Final Report, July 1986-July 1987,” Rept. No.
GRI-87/0297, Gas Research Institute, Chicago, IL, 1987.
374A.Khandkar and S.-aargovan, “Development of Planar SOFC Technol-
ogy: Progress and Problems,” Denki Kagaku, 58,551-56 (1990).
’75Ceramatec,Inc., “Development of Planar Geometry Solid Oxide Fuel Cell
Technology, Phase 11, Annual Report October 1987-October 1988,” Rept. No.
GRI-8910161, Gas Research Institute, Chicago, lL, 1989
37‘’J. I? I? Huijsmans, E. J. Sewers, F. H. van Heuveln, and J. l? de Jong,
“Fabrication of Planar SOFC Components at ECN”; see Ref. 14, pp. 113-18.
377T.Hoshina, T. Yoshida, and S. Sukurada, “Tonen Test of Planar SOFC’;
see Ref. 236, pp. 25-28.
’7RS.Murakami, Y. Akiyama, N. Ishida, T. Yasuo, T. Saito, and N. Furu-
kawa, “Development of a Planar Solid Oxide Fuel Cell”; see Ref. 14, pp. 59-65.
37yL.W. Tai and l? A. Lessing, “Plasma Spraying of Porous Electrodes for a
Planar Solid Oxide Fuel Cell,” J . Am. Ceram. Soc., 74, 501-504 (1991).
‘*“H. Michibata, H. Tenmei, T. Namikawa, and Y. Yamaraki, “Preparation of
LaMnO, Thin Film Electrode for Solid Oxide Fuel Cells by Vacuum Evapora-
tion”; see Ref. 27, pp. 188-96.
”‘B. Gharbage, M. Henault, T. Pagnier, and A. Hammou, “Preparation of
La, _,Sr,MnO, Thin Films by a Pyrosol Derived Method,”Mater. Res. Bull., 26,
1001-1007 (1991).
’”M. Dokiya, N. Sakai, T. Kawada, H. Yokokawa, T. Iwata, and M. Mori,
“Fabrication of a Planar Solid Oxide Fuel Cell”; see Ref. 232, pp. 1547-51.
Dokiya, N. Sakai, T. Kawada, H. Yokokawa, and I. Anzai, “Wet Pro-
cess for Planar SOFC’; see Ref. 14, pp. 127-34.
‘‘&P. A.Lessing, L. W. Tai, and K. A. Klemm, “Fabrication Technologies for a
Planar Solid Oxide Fuel Cell”; see Ref. 27, pp. 3 3 7 4 0 .
’“’Y. Akiyama, N. Ishida, S. Murakami, and T. Saito, “Solid Oxide Electro-
lyte Fuel Cell,” U.S. Pat. No. 4 997 726, Mar. 5, 1991.
’XbT.Yoshida, T. Shima, F. Ishizaki, H. Iwasaki, 1. Mukaizawa, Y. Someya,
S. Sakurada, and 0. Yamamoto, “Solid Electrolyte Type Fuel Cells,” U.S. Pat.
No. 4950562, Aug. 21,1990.
JB7J.Jung, Th. Martens, H. Runge, and M. Turwitt, “Fabrication Results and
Operating Experience with a Planar SOFC Design”; see Ref. 14, pp. 144-5 I .
’Y E. J. van Dieten, I? H. M. Walterbos, and J. Schoonman. “Advanced
Deposition Techniques for Solid Oxide Fuel Cell Components”; see Ref. 14,
pp. 183-91.
’”T. Setoguchi, M. Sawano, K. Eguchi, and H. Arai, “Application of the Sta-
bilized Zirconia Thin Film Prepared by Spray Pyrolysis Method to SOFC,” Solid
State lonics, 40/41, 502-505 (1990).
‘VOH. Michibata, T. Namikawa, and Y. Yamazaki, “Preparation of LaCoO,
Thin-Film Electrode by Vacuum Evaporation for Solid Oxide Fuel Cells,” Denki
Kagaku, 57,255-56 (1989).
3y‘Y.Yamazaki, T. Namikawa. and H. Michibata. “Preparation of Ultra-Thin
Solid Oxide Fuel Cells Using Nickel Foil Substrates”; see Ref. 14, pp. 175-81.
3y2N.Nakagawa, C. Kuroda, and M. Ishida, “Preparation of Thin-Film Zirco-
nia Electrolyte Fuel Cell by RF Sputtering,”Denki Kagaku, 57, 215-18 (1989).
3y’N.Nakagawa, C. Kuroda, and M. Ishida, “A Thin-Film YSZ Fuel Cell Set
on a Porous Alumina Substrate by RF Sputtering Technique”; see Ref. 3 I,
PPiq1846.
A. Negishi, K. Nozaki, and T. Ozawa, “Thin-Film Technology for Solid
Electrolyte Fuel Cells by the RF Sputtering Technique,” Solidstate lonics, 314,
443-46 (1981).
’”’H. Uyama, N. Oka, I. Ono, and 0. Matsumoto, “Formation of Yttria-Stabi-
lized Zirconia Film by Plasma MOCVD,”Denki Kagaku, 5 8 , 5 6 4 4 6 (1990).
‘“K. J. de Vries, R. A.Kuipers, and L. G. J. de Haart, “Planar Solid Oxide
Fuel Cells Based on Thin YSZ Electrolyte Layers”; see Ref. 14, pp. 135-43.
3Y7H,Nakagawa, S. Kosuge, H. Tsuneizumi, E. Matsuda, H. Mihara, and
Y. Sato, “Characteristics of Electrolyte Processed by CO, Laser Evaporation
Techniques”; see Ref. 27, pp. 71-78.
588 Journul ofthe Americun Ceramic Society-Minh Vol. 7 6 , No. 3

’““S. Fukami, M. Kitoh, A . Bunya, H. Saitoh, T. Itoh, Y. Kaga, Y. Ohno,
ti. Eguchi. and H. Arai, “Preoaration
‘ of Electrolyte Film by Plama Spraying”;
see Ref. 14. pp. 205-14.
’”D. Stover, R. Hecker, H. Jansen, and W. Mallencr, “Shaping of SOFC
Components by Use of Plasma Spraying”: see Ref. 14, pp. 21.5-20.
“X’ti. Okiai, S. Yoshida. I . Kaji. M . Hasegawa, H. Yamanouchi, and
M. Nagdta, “Application (11 Plasma Spray Process for Porous Electrodes”: see
Ref. 31. pp. 191-96.
“‘H. Hamatani, T. Okiida. and 1. Yoshida, “Developmcnt of Consistent
Fabrication Process for SOFC by Hybrid Plasma Spraying”: see Ref. 3 I,
197-202.
ppil’Z. Ogumi, Y. Tsuji, Y. Uchimoto, and 2. Tdkehara, “Plasma Electrolytic
Deposition for the Preparation of Thin Stabilized Zirconia Films”; see Ref. ?I,
pp 203-206
“”Z. Oguini. Y. Tsuji, Y. Uchimoto, and Z. Takehara. “Preparation of Thin
Yttria-Stahilired Zirconia Filina by Vapor-Phase Electrolytic Deposition and its
Application to SOFC”; see Ref. 14, pp. 201-204.
“5. Sakurada and T Yoshida, “Results of Solid Oxide Fuel Cell at Tonen”:
see Ref. 14, pp. 45-54.
“”S Elangovan, C Milliken. M. ’limper, and A. Khandkar, “Commercializ-
ing Planar SOFC Technology: Phase Il-Status and Overview”; prcsentcd at an
EPRliGRI Fuel Cell Workshop on Fuel Cell Technology Research & Develop-
ment (San Francisco. CA, April 29-30. 1992). Electric Powcr Research Initi-
lute, Palo Alto, C A . 1992.
“‘*H. Shundo, H. Shiniizu, N. Kusuiiose. ‘r. Iwata, S. Maruyama, and K .
Koseki, “Substrate-Type Planar SOFC ‘Technology”;see Ref. 14, pp. 119-26.
“”T. lnoue, H. Yoshida, Y. Esaki. H. Miyanioto. M. Ishibashi, H. Haneda,
and K.Takcnobu, “Development of MOLB-‘Type Solid Oxide Fuel Cell”: \ee
Ref. 236, pp. 520-23.
*“H. Iwahara, T. Esaka. H. Uchida, and N . Maeda, “Proton Conduction in
Sintered Oxides and its Application to Steam Electrolysis for Hydrogen Produc-
tion.”SolrdSEa/~, lonics, 3/4, 359-63 (19x1 ).
“”’H. Iwahara, H. Uchida, and N . Maeda, “HighTemperature Fuel and Steam
Electrolysis Cells Using Proton Conductive Solid Electrolytes,“ J . Power
Sourccs, 7, 293-301 (1982).
““H. Iwahara, H. Uchida, and S. Tanaka. “High-Temperature-Type Proton
Conductive Solid Oxide Fuel Cells Using Various Fuels,” J . Appl. Elcctro-
chem., 16,663-68 ( I 986).
“ ‘ H . Iwahara, H . Uchida, K. Morimoto, and S. Hosogi, “High-Temperature
C,-Gas Fuel Cells Using Proton-Conducting Solid Electrolytes,” J. Appl. Elec-
/roc-huri.. 19, 448-52 (1989).
‘l2H. Uchida, H. Yoshikawa, and H Iwahara, “Dissolution of Water Vapor
(or Hydrogen) and Proton Conduction in SrCe0,-Based Oxides at High Temper-
ature.“ S d i d Sruw iorrics, 35, 229-34 (1989)
“IT Yajima. H . Iwahara, H . Uchida, and ti. Koide, “Relation between Pro-
ton Conduction and Concentration of Oxide Ion Vacancy in SICeO,-Based Sin-
tered Oxides,”SolrdS/circ. lonics, 40/41, 914-17 (1990).
““H. Iwahara, H Uchida, and K . Morimoto, “High-Temperature Solid Elec-
trolyte Fuel Cells Using Perovskite-Type Oxide Based on BaCc@,,” J. Elecrro-
i,hcm. Soc., 137, 462-65 (1990).
‘“J. R . Jewulski. T. L. Osil, and R. J . Remick. “Solid-State Proton Conduc-
tors.” Rept. No. DOEIMCI242lX-2957. U.S. Dept. o f Energy, Washington,
DC, 1990. ri

Nguyen Q. Minh is with Allied-Signal Aerospace Company, AiResearch Los Angeles

Division, in Torrance, California. At Allied-Signal, he participates in various ceramic
R&D efforts and is responsible for overseeing and coordinating technical activities
associated with solid-oxide fuel cell programs. Before joining Allied-Signal, he worked
at Argonne National Laboratory, Argonne, Illinois. His current research interests
include fuel cells and other electrochemical energy systems, high-temperature electro-
chemistry, and ceramic material processing. Dr. Minh holds several patents and has
authored and coauthored two book chapters and more than fifty publications. He is a
member of the American Ceramic Society, the Electrochemical Society, and the Miner-
als, Metals, and Materials Society.