Chemical degradation of La

1x
Sr
x
MnO
3
/Y
2
O
3
-stabilized ZrO
2
composite
cathodes in the presence of current collector pastes
Christopher Chervin
a,b
, Robert S. Glass
c
, Susan M. Kauzlarich
a,
*
a
Department of Chemistry, University of California at Davis, One Shields Ave, Davis, CA 95616, USA
b
University Outreach, Lawrence Livermore National Laboratory, Livermore, CA 94550, USA
c
Energy and the Environment Directorate, Lawrence Livermore National Laboratory, Livermore, CA 94550, USA
Received 26 March 2004; received in revised form 4 June 2004; accepted 9 June 2004
Abstract
The chemical reactivity of current collector pastes, utilized in electrode performance measurements, were investigated with respect to the
solid oxide fuel cell composite cathode, (La
85
Sr
15
)
.98
MnO
3
/8 mol% Y
2
O
3
-stabilized ZrO
2
(LSM/YSZ). Anode substrate single cells were
prepared with Pt or Ag paste current collectors applied to the electrodes. Phase purity of the cathodes before and after sintering the current
collectors were examined with powder X-ray diffraction (XRD) and the performance of the cells determined with current-potential
measurements. XRD experiments provided evidence that Pt paste, containing a bismuth flux, reacted with the composite cathode at
temperatures above 800 jC leading to formation of the pyrochlore phase, La
2
Zr
2
O
7
. Cathodes coated with Ag paste, which did not contain a
bismuth flux, showed no sign of chemical degradation. Synthesized Bi-subnitrate and commercial Bi
2
O
3
were shown to have similar
chemical reactions with LSM/YSZ powders leading to pyrochlore phase formation. Current-potential experiments on single test cells
demonstrated that samples prepared with paste containing bismuth flux had a decrease in initial performance.
D 2004 Elsevier B.V. All rights reserved.
Keywords: Current collector; Fuel cell; La
1x
Sr
x
MnO
3
; Bi subnitrate; Bismuth oxide; La
2
Zr
2
O
7
; Lanthanum zirconate; SOFC; LSM; YSZ; Cathode; ZrO
2
1. Introduction
Development of solid oxide fuel cell cathodes for high
temperature operation (8001000 jC) has focused on
materials compatible with the electrolyte Y
2
O
3
-stabilized
ZrO
2
(YSZ) [13]. The most promising cathode material to
date for direct use with YSZ is La
1 x
Sr
x
MnO
3
(LSM) with
f15% [1,411]. Composite LSM/YSZ cathodes are
formulated to improve electrode performance since oxygen
ion transport is negligible in LSM. These composite cath-
odes have increased gas electrodeelectrolyte reaction
zones [3,1220]; however, there are still controversies
regarding details of the electrode kinetics because differ-
ences in experimental conditions (grain/particle size distri-
bution, microstructure, cell fabrication, etc.) play an
important role. The choice of current collector used has
been identified as an important component to consider in
SOFC when studying the electrochemical behavior of an
electrode. Generally, mesh electrodes are preferred over
pastes because of reduced performances reported for pastes
[21,22]. Diffusion of the metal into the grain boundaries and
compound formation has been suggested [21]. Variation in
performance has been observed with paste current collectors
in the case of LSM-YSZ composite electrodes [22], but the
factors responsible for this variation in performance have
not been identified.
LSM-YSZ is well studied and a short review of its
chemical reactivity and corresponding structural data is
provided. In composite LSM-YSZ electrodes with short
heating times above 1150 jC, chemical reactivity between
LSM and YSZ leads to the formation of the pyrochlore,
La
2
Zr
2
O
7
(LZO) [23]. The formation of LZO reduces
cathode performance because it has significantly lower
conductivity than LSM or YSZ at fuel cell operating
temperatures [2427]. The LZO formation is reported to
occur through solid state diffusion of Mn and La cations into
the YSZ phase [2830]. Diffusion of Mn ions into the YSZ
leaves the LSM phase rich in La at the LSM/YSZ interface.
When La
2
O
3
is no longer soluble in LaMnO
3
, the La oxide
forms and reacts readily with the YSZ phase [25,28,31]. It
0167-2738/$ - see front matter D 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.ssi.2004.06.004
* Corresponding author. Tel.: +1-530-7584542; fax: +1-530-7528995.
E-mail address: smkauzlarich@ucdavis.edu (S.M. Kauzlarich).
www.elsevier.com/locate/ssi
Solid State Ionics 176 (2005) 1723
has been reported that A-site deficiency in La
1 x
Sr
x
MnO
3
helps prevent degradation to LZO [23,25,32], presumably
by inhibiting La
2
O
3
formation at the LSM/YSZ interface.
Although temperatures above 1150 jC ensure LZO
formation, the phase has also been detected in LSM/YSZ
composites heated at 1000 jC for greater than 100 h [30].
This indicates that long-term chemical stability is problem-
atic at higher temperature operation. The same study [30]
did not find detectable degradation when samples were
heated at 900 jC for similar time periods. The fabrication
process of cells requires several high-temperature sintering
steps which may lead to LZO formation. Therefore, cells are
generally fabricated in a manner such that the LSM/YSZ
composite electrode is not heated above 1150 jC for
extended periods of time.
Performance testing of fabricated cells requires the use of
noble metal current collectors sintered to each electrode in
order to ensure good electrical contact and reduce resistive
losses across the electrodes. The metal, generally Pt, is
applied to the electrodes in the form of a paste, as a metallic
mesh, or both a paste and mesh. Platinum pastes contain
finely divided Pt, organic solvents, and often bismuth
flux compounds, such as Bi subnitrate, to lower sintering
temperatures.
Bismuth subnitrate, also known as bismuth hydroxide
nitrate oxide with the formula Bi
5
O(OH)
9
(NO
3
)
4
, decom-
poses to orthorhombic Bi
5
O
7
NO
3
between 350 and 515 jC
and finally to Bi
2
O
3
at 630 jC [33]. Bi
2
O
3
exhibits a room
temperature monoclinic a phase, which transforms to a high
temperature cubic d phase at 730 jC [34]. Metastable h and
g phases are also known to exist below 730 jC. Bi
2
O
3
(up
to 10%) is reported to form solid solutions with LSM at
temperatures as low as 800 jC [35]. Having a similar radius
to La
3 +
, the Bi
3 +
cation substitutes for La in the A-site,
thereby enhancing La diffusion [35]. Increased La diffusion
and removal of A-site deficiency may potentially enhance
chemical degradation at LSM/YSZ interfaces.
This study reports the identification of an impurity phase
formed at temperatures higher than 800 jC in composite
LSM/YSZ cathodes coated with Pt pastes containing Bi
subnitrate. For comparison, the reactivity of Ag paste, not
containing Bi compounds, was also investigated. Synthe-
sized Bi subnitrate and commercial Bi
2
O
3
were also reacted
with LSM/YSZ powders to further investigate the role of
Bi
3 +
in the formation of this impurity phase. Single cell
electrochemical performance data were collected for nomi-
nally identical cells prepared with either Pt or Ag current
collectors.
2. Experimental
2.1. Materials
Commercial polycrystalline powders were utilized as raw
materials for all anode supported single cell fabrication.
Cathodes were prepared from a composite of (La
85
Sr
15
)
98
MnO
3
(Praxair, USA) and 8 mol% Y
2
O
3
-stabilized ZrO
2
(Tosoh, Japan) powders. Electrolytes were prepared from
YSZ powders and anode substrates from tape cast composite
NiO/8 mol% Y
2
O
3
-stabilized ZrO
2
(NiO/YSZ from Mistler,
USA). Current collectors were made from either Pt (Engle-
hardt, USA) or Ag (Alfa Aesar, USA) pastes.
2.2. Synthesis of bismuth subnitrate
Bismuth subnitrate was synthesized by hydrolysis of a
bismuth nitrate aqueous solution. Approximately 1.76 g of
Bi metal (Alfa Products, USA) was dissolved in 8 ml of hot
concentrated nitric acid. The resulting bismuth nitrate was
hydrolyzed by the addition of 1 M sodium bicarbonate until
the pH was in the range 3.55. The white precipitated
bismuth subnitrate was filtered, washed, and dried under
vacuum over night.
2.3. Single cell preparation
Fig. 1 is a cross-section schematic of the fuel cell test
configuration. The single cell samples were prepared by
stepwise colloidal spray deposition of polycrystalline elec-
trolyte and cathode powders onto anode substrates. The tape
cast NiO/YSZ substrates were pressed into 1.72 cm diam-
eter disks with an approximately 0.25 cm thickness and pre-
sintered at 1050 jC. The cathodes were prepared from a
45:55 wt.% composite of YSZ and LSM. Colloidal solu-
tions for depositing the electrolyte and cathode layers were
prepared from the respective polycrystalline powders, along
with a surfactant (PC33) dispersed in 50:50 vol.% ethanol/
water solutions. A robotic spray coater with an ultrasonic
atomizing nozzle, developed at Lawrence Livermore Na-
tional Laboratory [36], was utilized for the spray deposition.
The cells were sintered after each deposition step in order to
ensure good adhesion and density.
By way of this stepwise process, each cell was prepared
with a 10-Am dense YSZ (electrolyte) layer deposited on the
anode substrate, followed by sintering at 1450 jC. Next, a
10-Am dense LSM/YSZ (cathode) layer was deposited onto
the electrolyte and the cells were sintered at 1050 jC. The
final step, deposition of a 40-Am porous cathode layer,
required an LSM/YSZ colloidal solution containing a pore
Fig. 1. Cross-sectional diagram of the anode supported single cell
configuration.
C. Chervin et al. / Solid State Ionics 176 (2005) 1723 18
former (starch). The cells were sintered at 1150 jC, burning
off the organic pore former, leaving a porous cathode layer
suitable for oxygen diffusion.
Pt or Ag pastes were painted onto the anode and cathode
of each cell to serve as current collectors. Samples with Pt
paste were fired at 900 jC for 30 min. One additional Pt
coated sample was fired for 24 h to determine the effects of
longer firing time on cell performance. Samples painted
with Ag ink were sintered at 800 jC for 30 min. Control
samples were prepared as above without the addition of
current collector inks. Additionally, bismuth-free Pt control
samples were prepared by painting a solution of Pt-black
dispersed in a-turpineol onto cathodes followed by sintering
at 900 jC for 30 min.
2.4. Fuel cell testing
Testing of single cells was accomplished by attaching
cells to the end of alumina tubes with cement sealant. Each
cell was placed such that the anode side faced into the tube.
The alumina tube was placed in a secondary quartz tube
with proper gas attachments to allow for hydrogen flow to
the anode and airflow to the cathode. Platinum leads were
fed to the anode and cathode through secondary alumina
fixtures and pressed to the electrodes to ensure good contact.
Proper contact, as verified by resistance measurement, is
retained at fuel cell test temperatures because the Pt leads
fuse to the Pt or Ag current collectors. The entire apparatus
was placed in a tube furnace and slowly heated to 800 jC
before fuel cell testing. Polarization measurements were
conducted using a Solartron SI 1287 Electrochemical Inter-
face with pure hydrogen passed over the anode and air
passed over the cathode.
2.5. Phase identification
Chemical degradation of the cathodes before and after
fuel cell testing was determined with powder X-ray diffrac-
tion using a Scintag PAD V diffractometer operating at 40 A
and 45 keV with Cu K
a
radiation. Because it is undesirable
and difficult to powder the test cells, a plastic sample holder
was machined to allow proper positioning of the cathode
portion in the X-ray beam. Preferred orientation is assumed
to be limited in a colloidal spray deposited powder and the
cathode layer (50 Am) was the only portion of the sample
diffracting X-rays. For samples with current collector or
dispersed Pt-black sintered to the electrodes, it was neces-
sary to remove the current collector layer with fine grit
sandpaper before taking diffraction patterns.
2.6. Reaction of bismuth compounds with LSM/YSZ
The reactivity of the flux compound, bismuth subnitrate,
with the composite LSM/YSZ cathode material was deter-
mined through solid state reaction. LSM (Praxair) and YSZ
(Tosoh), mixed in a 55:45 wt.% ratio in an agate mortar and
pestle, were sintered as a loose powder at 1150 jC. The
loose LSM/YSZ powder was subsequently mixed with 9.4
wt.% bismuth subnitrate and calcined at 900 jC for 30 min.
To further test bismuth reactivity, a second mixture of LSM/
YSZ was mixed with 6.4 wt.% Bi
2
O
3
(Aldrich, USA) and
fired at 900 jC for 30 min. The reactivity of bismuth in
these two mixtures, as well as with each component, LSM
and YSZ, separately, was determined with powder X-ray
diffraction using the Scintag diffractometer.
The chemical reactivity of Bi
2
O
3
with LSM/YSZ (6.4
wt.% Bi
2
O
3
) was also measured in situ with temperature
profile XRD using an INEL diffractometer equipped with a
furnace heated sample holder and a position sensitive
detector covering 120j. Diffraction patterns were measured
at 100j steps from 100j to 1000 jC and finally at room
temperature after the heat treatment with a 30-min dwell
time for each scan. The INEL diffractometer was operated at
30 A and 30 keV with Cu K
a
radiation. Thermogravimetric
analysis/differential scanning calorimetry (TGA/DSC) of
the Bi
2
O
3
-LSM/YSZ powder was measured from room
temperature to 1000 jC under flowing oxygen with a 10
jC/min ramp using a Netzsch 449 Thermal Analyzer.
3. Results and discussion
Fig. 2 compares powder X-ray diffraction data for the
cathodes of two single cells: one prepared with a Pt current
collector and tested under fuel cell conditions and the other
prepared without a Pt current collector and untested. The
cathode portion of the cell prepared without a current
collector only shows peaks associated with the LSM and
YSZ phases. The cathode tested under fuel cell conditions,
however, shows additional peaks associated with the cubic
pyrochlore structure. These additional peaks correspond
Fig. 2. X-ray diffraction patterns of LSM-YSZ cathodes before and after
fuel cell testing. The bottom pattern is for before testing the cathode. Note
the untested sample did not have Pt paste sintered to it. The phases are
marked: LSM, *; YSZ, +; LZO, x; and Pt, O.
C. Chervin et al. / Solid State Ionics 176 (2005) 1723 19
with La
2
Zr
2
O
7
[23], which is surprising because the cell did
not reach temperatures above 900 jC after applying the Pt
paste. As discussed in the Introduction, the formation of
LZO has only been identified in composites heated above
1150 jC or heated at 1000 jC for over 100 h [30]. These
cathodes were not exposed to such conditions so the
presence of the pyrochlore phase is unexpected. Additional
peaks associated with remaining Pt are also detected in the
X-ray pattern and are marked in the figure.
Various stages of the fabrication process were investi-
gated for several cathodes prepared simultaneously. Fig. 3
shows the powder X-ray diffraction patterns for the cathode
portions of three cells: one prepared with commercially
purchased Pt paste, a second cell prepared with Ag paste,
and a third cell coated with Pt black dispersed in a-turpineol
(no Bi flux). The cell coated with Pt black served as a
control for the commercial Pt paste and did not show
pyrochlore formation. In all cases, the pyrochlore phase
only became present after sintering the commercial Pt paste
to the cathode. Cathodes prepared with Ag current collectors
did not display this phase before or after fuel cell testing.
The data in Fig. 3 provide evidence that there is a
compound present in the Pt paste that may be responsible
for pyrochlore formation in the LSM/YSZ composite cath-
ode. The absence of this phase in the control sample coated
with Pt black dispersed in a-turpineol eliminates Pt as a
possible contributor to cathode degradation. The Ag and Pt
pastes contain similar solvents with the exception of the flux
compound, bismuth subnitrate, present in the Pt paste,
suggesting Bi subnitrate may be involved in lowering the
temperature required for pyrochlore formation. Bi
2
O
3
is
known to be one of the aides for sintering, effectively
lowering the sintering temperature of YSZ [3739]. The
presence of Bi in the paste for the LSM-YSZ system
contributes to the lowering of the temperature required for
phase formation of La
2
Zr
2
O
7
, LZO.
The XRD results of the solid-state reaction between
synthesized bismuth subnitrate and loose LSM/YSZ powder
is presented in Fig. 4. The data show evidence of LZO
pyrochlore formation, which was not detected in loose
LSM/YSZ powder heated simultaneously without bismuth
subnitrate (data not shown). Because bismuth subnitrate
decomposes to Bi
2
O
3
at approximately 630 jC, well below
the final sintering temperature of the Pt paste, the reactivity
of Bi
2
O
3
with LSM/YSZ was also investigated. The results,
shown in Fig. 4, demonstrate pyrochlore formation also
occurs in the presence of Bi
2
O
3
. Additionally, each compo-
nent, LSM and YSZ, was heated in the presence of Bi
2
O
3
and did not result in the pyrochlore formation. This is
consistent with the literature regarding the chemical reac-
tivity of Bi
2
O
3
with each of the components and supports
the hypothesis that the reaction only occurs in the presence
of both components.
Fig. 5 shows the TGA/DSC for the reaction of Bi
2
O
3
with LSM/YSZ. The presence of a broad endotherm below
235 jC, an endothermic peak with a maximum at 735 jC
and a broad, poorly defined endotherm between 800 and
900 jC is observed. The total weight percent loss is
approximately 1.5% from room temperature to 1000 jC.
The broad endotherm below 235 jC is likely due to loss of
tightly bound water in the sample. The endothermic peak at
735 jC is attributed to a phase transition in Bi
2
O
3
from the
a to the y form, corresponding well with the literature
reported temperature of 730 jC [34]. The poorly defined
endotherm between 800 and 900 jC is attributed to the
melting of Bi
2
O
3
(825 jC) and the formation of the
pyrochlore, LZO, phase. The observed temperature of the
peak and the poorly defined endotherm correspond well
with in situ temperature profile XRD data that will be
discussed next. DSC of LSM/YSZ without Bi
2
O
3
(data
not shown) shows a similar endotherm below 235 jC but
does not have the endothermic peak at approximately 735
Fig. 3. X-ray diffraction patterns of LSM-YSZ cathodes with Pt paste (top),
Ag paste (middle) and Pt-black dispersed in a-turpineol (bottom). The
phases are marked: LSM *; YSZ +; LZO x; Pt, O; and Ag ^.
Fig. 4. X-ray diffraction patterns of LSM-YSZ powders mixed with 9 wt./
wt.% Bi-subnitrate (bottom) and 6.4 wt./wt.% Bi
2
O
3
(top). The reflections
attributed to the phases are marked: LSM *; YSZ, +; and LZO, x.
C. Chervin et al. / Solid State Ionics 176 (2005) 1723 20
jC, nor the broader poorly defined high temperature endo-
therm, further indicating these are associated with the Bi
2
O
3
phase. The weight loss percent determined from TGA for
LSM/YSZ with and without Bi
2
O
3
are almost identical
suggesting that the Bi remains in the composite after heating
up to 1000 jC.
The results from in situ temperature profile XRD are
shown in Fig. 6. The Bi
2
O
3
phase undergoes structural
changes from 300 to 700 jC before the final phase transition
to y-Bi
2
O
3
at 735 jC. The y phase has a cubic fluorite
structure similar to YSZ, and therefore the peaks are over-
lapped. The phase transition corresponds well with the
endothermic peak from DSC. Major changes in the LSM
and YSZ phases are undetectable except for peak splitting
due to an increase in crystallite size with heating. This effect
is particularly notable for the LSM phase at 32.5j 2h which
initially appears as one peak due to crystallite size broad-
ening effects but after heating the two overlapping peaks are
identifiable with maximum at 32.3j and 32.5j 2h. The
appearance of the LZO phase at temperatures greater than
800 jC is consistent with the hypothesis that the broad
endotherm is the migration and crystallization of compo-
nents to form the LZO phase.
Fig. 5. TGA/DSC scan of LSM/YSZ powder mixed with 6.4 wt./wt.% Bi
2
O
3
.
Fig. 6. In situ temperature profile XRD of LSM/YSZ powder mixed with
6.4 wt./wt.% Bi
2
O
3
heated from room temperature to 1000 jC. The top
profile was taking at 100 jC after the heat treatment. Reflections attributed
to LZO are marked with an x.
Fig. 7. Voltage vs. current density for single cells fabricated with either Ag
or Pt current collectors. Measurements were carried out at 800 jC in
flowing air.
C. Chervin et al. / Solid State Ionics 176 (2005) 1723 21
The data herein provide strong evidence that Bi subni-
trate flux reacts with LSM/YSZ leading to the formation of
LZO at sintering temperatures above 800 jC. The degrada-
tion process occurs through decomposition of bismuth
subnitrate to Bi
2
O
3
, which readily forms solid solutions
with the LSM phase. Bismuth substitution for La in the A-
site of the perovskite material would allow for enhanced La
diffusion and removal of A-site deficiency. Diffusion of La,
along with La
2
O
3
formation at the LSM/YSZ interface has
been previously identified as a mechanism for La
2
Zr
2
O
7
formation [25,2830]. This supports observations in the
literature that paste generally give poorer electrochemical
performance based on polarization resistance than mesh
[21,22].
To verify that this phase is responsible for reduced cell
performance, the polarization curves of Pt and Ag coated
cells under fuel cell conditions were investigated. The
current-potential measurements are plotted in Fig. 7. The
samples displayed similar open circuit voltages greater than
1.2 V, indicating good gas seals and crack-free electrolytes.
With applied current beyond the activation polarization
region the potential of the Pt-coated cells dropped off more
significantly than that of the Ag-coated cell, indicating
larger cell resistances. The maximum power density for
the Ag coated cell was found to be 0.85 W/cm
2
, while the
Pt cells sintered at 30 min and 24 h had power densities of
0.51 and 0.54 W/cm
2
, respectively. The cells were fabri-
cated under the same conditions and are nominally identi-
cal. The lower power density observed for the Pt coated
cells are attributed to increased resistance in the cathode due
to the LZO pyrochlore formation. The performance was not
significantly effected by the firing time of the current
collector as can be seen from the similar power densities
of the cells prepared with Pt paste sintered for 30 min and
24 h.
Considering the sensitive nature of interfacial impurities,
such as LZO, on electrochemical measurements, the choice
of current collector is an important part of experimental
design. The evidence of LZO phase formation in LSM/YSZ
composites, caused by Bi flux compounds, at temperature
above 800 jC eliminates some Pt pastes as acceptable
current collectors. Ag pastes are available as a non-reactive
alternative provided the experiment temperature does not go
above 800 jC. For operation over 800 jC, Pt mesh current
collectors or Pt pastes without Bi flux compounds are
required.
Acknowledgements
This work was supported by the National Science
Foundation (Grant DMR-0120990), the University of
California Energy Institute and the Department of Energy
(Student Employee Graduate Research Fellowship). The
authors thank Quoc Pham, Brandon Chung, Richard
Baldwin, and Dave Lenz for technical support, Alexandra
Navrotsky for use of the X-ray diffractometer and TGA/
DSC, and Peter Martin for technical discussion. This work
was performed under the auspices of the United States
Department of Energy by the University of California
Lawrence Livermore National Laboratory under contract
No. JC-155023.
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