Solid State Ionics 181 (2010) 12941302

Contents lists available at ScienceDirect

Solid State Ionics

j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / s s i

Evaluation of Co and perovskite Cr-blocking thin lms on SOFC interconnects

Robert Lacey a, Abhijit Pramanick a, Jae Chun Lee b, Jae-Il Jung a, Bo Jiang a, Doreen D. Edwards a,
Robert Naum c, Scott T. Misture a,
a
b
c

Kazuo Inamori School of Engineering, Alfred University, Alfred, NY 14802, USA

Materials Sci. & Eng., Myongji University, Kyunggi-do, Republic of Korea
Applied Coatings, Inc. Rochester, NY, USA

a r t i c l e

i n f o

Article history:
Received 18 February 2010
Received in revised form 6 July 2010
Accepted 16 July 2010
Keywords:
SOFC
Interconnect
Chromium blocking

a b s t r a c t
The viability of perovskite (LSC, LSCF, LNF and BSCF) and metallic (Co) thin lm coatings to reduce Cr
migration from Crofer22, E-Brite and SS430 interconnect materials has been examined. Production-scale
physical vapor deposition (PVD) systems were used to obtain uniform lms with thickness near 1 m. The
LSC, LSCF, LNF and Co lms exhibited good adhesion, thermal stability and chemistry similar to the target
materials. Although the BSCF lms exhibited good initial adhesion, subsequent reactions caused blister
formation upon thermal cycling. Chromium migration upon extended thermal treatments of 168 h was
investigated using XPS depth proling through the lms. As a result of interdiffusion of elements across the
lmsubstrate interface, intermediate spinel layers were formed spontaneously in all thin lms, with
concurrent shifts in compositions of the perovskite lms. With the exception of the BSCF lms, the
combination of a perovskite or Co coating and the spontaneously-formed, chemically graded intermediate
spinel layers was highly effective in blocking Cr diffusion from the interconnect materials.
2010 Elsevier B.V. All rights reserved.

1. Introduction
Materials developments enabling operation of SOFCs at lower
temperatures have introduced a new challenge related to chromium
(Cr) poisoning of the cathode [19]. The Cr source in intermediate
temperature SOFCs is the high-Cr stainless steel interconnect wherein
the Cr content provides good oxidation resistance at high temperature
[10]. The most commonly studied commercial alloys of this kind
include Crofer22, E-Brite, and 430 stainless steel. Some newly
developed alloys and several promising oxide dispersion strengthened (ODS) alloys are also being considered.
The role of Cr poisoning in the degradation of the electrochemical
performance of SOFCs has been well documented [79]. To minimize
the effect of Cr contamination, engineers and component designers
have employed protective surface coatings on the interconnect
materials to act as barriers against outward diffusion of Cr. In recent
years, a variety of coating systems have been investigated, including:
perovskite oxides such as (La,Sr)MnO3, (La,Sr)CoO3, (La,Sr)CrO3 or
their combinations[4,1116]; spinels such as (Co,Mn)3O4 and (Mn,
Cr)3O4 [1720]; metallic coatings such as Co, Ni and Cu [21]; and other
complex oxide coatings[22].
A variety of techniques have been employed to deposit these
coatings including vacuum plasma spraying[15], wet powder spraying
[13], electrodeposition [2326] slurry dip coating, magnetron sputter Corresponding author. Tel.: +1 (607)871 2438; fax: +1 (607)871 2354.
E-mail address: misture@alfred.edu (R. Lacey).
0167-2738/$ see front matter 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.ssi.2010.07.007

ing[4,12,14,27], and ltered arc deposition[22]. A very recent review

article highlights differences among the performance of various
coating materials and processes[31], citing electrodeposition as
perhaps the most effective method reported to date. The most
commonly used methods allow deposition of oxide lms, but
electrodeposition yields dense metallic lms which can subsequently
be oxidized to produce high-density oxides.
The large-scale production of coated interconnects will require the
use of commercial-scale coating methods for depositing chromium
barrier layers. In this work we have adopted a commercial scale
physical vapor deposition (PVD) approach to deposit perovskite and
metallic Co coatings on commercial stainless steel substrates, at
thicknesses of 13 m. The deposited lms are characterized with
regard to their microstructure and phase content before and after
thermal treatments in order to dene the roles of the chemical
constituents in mitigating Cr diffusion from the stainless steel.
2. Experimental methods
Thin lms were deposited on commercial alloys using commercial
electron-gun PVD coaters, equipped with crystal thickness monitors
and residual gas analyzers, by Applied Coatings, Inc., Rochester, NY.
Specimens were coated then cut to size, yielding specimens with a
coating on one face only. Eight coating materials were tested,
including La0.3Sr0.7CoO3- (LSC37), La0.6Sr0.4CoO3- (LSC64), La0.8Sr0.2CoO3- (LSC82), La0.6Sr0.4Co0.2Fe0.8O3- (LSCF), Ba0.5Sr0.5Co0.2Fe0.8O3-
(BSCF), LaNi0.5Fe0.5O3- (LNF55), LaNi0.6Fe0.4O3- (LNF64), and Co

R. Lacey et al. / Solid State Ionics 181 (2010) 12941302

1295

metal. During each coating run, the thin lms were deposited on ve
different substrates, including E-Brite, Crofer22, SS430, sapphire and
borosilicate glass substrates. All coatings were deposited with
nominal thickness of ~ 1000 nm, except the Co coatings which were
deposited at nominal thickness of 3000 nm. Prior to deposition, the
substrates were sequentially wiped with alcohol, ultrasonicated in a
mild soap solution, rinsed with hot deionized water (16 M
resistance), and again wiped with alcohol. During deposition, the
substrates were held on counter-rotational tooling and positioned in
the coating chamber to control deposition uniformity and maximize
control of coating chemistry.
The microstructures of the lms were examined using eld
emission gun (FEG) scanning electron microscopy (SEM). Cross
sections of the lms and substrates were examined using semiquantitative energy dispersive x-ray spectroscopy (EDS). In-situ x-ray
diffraction using a Co K source was used to study the evolution of the
crystalline phases, up to a maximum temperature of 1000 C
with heating and cooling rates of 30 C/min in a custom diffraction
furnace [28]. The diffraction data were collected over a 2-theta range
of 10 to 85. The crystalline phases were identied using the full scale
(10902) diffraction patterns using a commercial software package
JADE.
Post-situ analysis was also performed for lms heat treated under
two conditions: 1000 C for 3 h or 1000 C for 3 h followed by 168 h
(1 week) at 850 C. X-ray diffraction, SEM, and x-ray photoelectron
spectroscopy (XPS) depth proling were used to characterize the
lms after heat treatment. XPS was performed using monochromatic
Al K radiation in a Phi Quantera SXM instrument. The spectra were
collected from a region 100 m in diameter. It was noted that the XPS
depth proles do not provide high accuracy depth analysis. This is the
result of inherent roughness of the various metal substrates and
differences in chemical composition and density of the deposited
lms. Nevertheless, the depth proles provide sufcient information
to understand the general trends in diffusion of the different elements
across the lmsubstrate interface.
To verify the expected equilibrium phase assemblage in the thin
lms, bulk reactions of the perovskite phases with Cr2O3 and Crofer22
in powder form were investigated. Powder mixtures at a ratio of 50:50
by weight were annealed at 850 C in air for 168 h and then
characterized using XRD.
The in-plane electrical conductivity of oxide lms (LSC37, LSC64,
LSC82, LSCF, LNF55, and LNF64 deposited on glass substrates was
measured from 50 C to 500 C using impedance spectroscopy with Pt
electrodes. Samples were heated at a rate of 10 C/min, and held
isothermally at 50 C increments for 20 min prior to taking the
impedance measurements. Impedance spectra were collected by
scanning from 10 MHz to 1 Hz with a 1 V excitation signal using a
Solatron 1260 impedance analyzer.

3. Results and discussion

Fig. 1. Cross-sectional view of lms of composition LSC82 on (a) glass, (b) sapphire (offaxis view), and (c) Crofer22 substrates.

3.1. Microstructure and electrical behavior of as-deposited lms

The PVD process produced uniform, homogeneous lms of
submicron thicknesses, which was conrmed from SEM micrographs
of the coatings as illustrated in Fig. 1 for a thin lm coating of LSC82.
Coatings deposited on glass or sapphire were dense, uniform and
smooth. Coatings deposited on the steel substrates, which had a
rougher surface, followed the contour of the substrate.
The oxide lms were amorphous and remained so upon heating to
~ 600 C as determined by XRD, shown later. The electrical conductivity of the amorphous lms at 50 C ranged from 2 104 S/cm for
LSC37 to 3 S/cm to LNF55. At 500 C the conductivities ranged from
4 S/cm for LSC37 to 102 S/cm for LSCF. The conductivity of the
amorphous LSC lm is some 2.5 orders of magnitude lower than for

bulk crystalline LSC at 500 C[29]. However, both crystalline and

amorphous LSCF display similar total conductivity at 500 C [30].
The amorphous LNF, LSC, and LSCF lms exhibited thermally
activated conductivity with either one or two activation energies. The
LSC37 and LSC64 exhibited a single activation energy (~ 0.40.5 eV)
whereas LSC82 exhibited two activation energies (0.2 eV below
200 C and 1.2 eV above). LNF and LSCF behaved similarly, with
activation energies of 0.16 or 0.17 eV below 200 C and 0.55 and 0.74
above, respectively. The structural origin of the change in activation
energy near 200 C remains unclear, and additional work is underway
to establish the interfacial resistance of the crystalline coatings after
long term annealing.

1296

R. Lacey et al. / Solid State Ionics 181 (2010) 12941302

3.2. Short term crystallization and phase evolution

Fig. 2(a) shows a cross section and composition gradient of an
LSC82 thin lm on a Crofer22 substrate after heat treatment at
1000 C for 3 h. The thickness of the lm is ~ 1 m, as can be estimated
from the contrast in the cross-sectional micrograph and the
distribution of the chemical elements shown in the EDS line scan.
The particle size is in the range of ~ 100 nm, as can be observed from

the top-view of the microstructure shown in Fig. 2(b). The evolution

of the different phases during heat treatment is shown in the in-situ
diffraction data in Fig. 2(c). At room temperature, the lms are
amorphous, and the perovskite phase (La,Sr)CoO3 starts to crystallize
at ~ 600 C. The XRD patterns are typical of a random powder,
demonstrating that the amorphous lms crystallize without any
preferred crystallite orientation. A spinel phase begins to form at
~800 C, which is most likely of the form (Cr,Co,Mn)3O4, though the

Fig. 2. (a) Cross-sectional view of LSC82 lm on Crofer22 substrate, along with line EDS scan across the lmsubstrate interface; (b) microstructure of LSC82 lm: (A) as-deposited,
(B) after crystallization at 1000 C, (C) after isothermal heat treatment at 850 C for 168 h; (c) in situ X-ray diffraction showing evolution of crystalline reaction products SrCrO4,
spinel, M2O3 where M is transition metal, and (La,Sr)CoO3- in the deposited lm on Crofer22 substrate.

R. Lacey et al. / Solid State Ionics 181 (2010) 12941302

exact composition of the spinel phase cannot be determined using

only diffraction data. In addition to the primary phases of (La,Sr)CoO3
and spinel phase, the formation of an appreciable fraction of SrCrO4
was also observed, beginning at ~750 C.
Phase evolution for the LSC37 and LSC64 lms was similar to
LSC82, with the rst crystallization of the perovskite phase also
occurring at ~ 600 C. For LSCF, formation of (La,Sr)(Co,Fe)O3, a spinel
phase, and SrCrO4 from the amorphous lm was observed upon heat
treatment, again similar to the LSC lms.
The results for LSC, in a general sense, agree with earlier results of
Fujita et al. [11] who also used a PVD process but found only the spinel
phase as a reaction product after heating to 750 C. The more
aggressive heat treatment used in the current work shows that
SrCrO4 also forms given ample time at elevated temperatures.
The LNF64 and LNF55 thin lms were similar in microstructure to
the LSC thin lms, regardless of the interconnect alloy used as a
substrate. Fig. 3(a) shows a cross section of an LNF64 lm after heat
treatment at 1000 C for 3 h on E-Brite and the composition gradient
of the elements present. The contrast in the cross-sectional micrograph and the distribution of the thin lm composition elements in
the EDS plot suggest that the lm thickness is ~ 1 m. Fig. 3(b) shows
the in-situ diffraction patterns for LNF55 during thermal treatment of
the thin lm on Crofer22 to 1000 C. Similar to the phase formation
sequence in LSC lms, perovskite La(Ni,Fe)O3 begins to form at
~ 600 C and a spinel phase begins to form at ~ 800 C. In addition,
minor diffraction peaks begin to appear from the formation of M2O3
(M = Cr, Fe, Ni, Mn, Co, etc.) at ~800 C. The EDS line scans show some
Cr enrichment at the metal-oxide interface (also clearly detected
using XPS as discussed later) which is likely due to the formation of
Cr2O3.
Fig. 4(a) shows the microstructure of the BSCF thin lm after heat
treating at 1000 C for 3 h. The blisters formed on the surface are likely
the result of thermal mismatch between the reaction products formed
and the substrate. The in-situ diffraction patterns at various
temperatures are shown in Fig. 4(b). In this case, the large relative
content of Ba and/or Sr results in crystallization of major fractions of
(Ba,Sr)CrO4, in addition to the expected spinel phase. It is likely that
the large quantity of (Ba,Sr)CrO4, with its large CTE mismatch, is
responsible for the blistering.
LSC, LSCF, and BSCF all react to form chromate phases of the form
(Ba,Sr)CrO4 because of the divalent A-site cations, but LNF does not.
To verify the expected equilibrium phase assemblage in the thin lms
with longer heat treatments, bulk reactions of the perovskite phases
with Cr2O3 and Crofer22 in powder form were investigated. The
results for mixtures with LSC37, LSC64, LSC82, LSCF6428, BSCF5582
and LNF46 are summarized in Table 1. With the exception of BSCF, all
of the reaction mixtures produced the same phases observed in the
thin lms. In the case of BSCF, several additional phases were noted in
the bulk samples that were not detected in the thin lm. Two
additional observations can be made from the data in Table 1. First,
the phase assemblage for reaction with Crofer22 and Cr2O3 is nearly
identical in all cases (ignoring any Fe in solid solution in the various
phases). Second, the LNF is nearly inert to Cr, forming only trace
amounts of spinel and NiO.
Examination of the Co thin lm indicates that the microstructure
and phase evolution sequences differ appreciably from the perovskites. A cross section of the lm after heat treatment at 1000 C for 3 h
is shown in Fig. 5(a). The thickness of the lm on average was ~ 3 m,
as estimated from the contrast in the cross-sectional micrograph and
the distribution of Co in the EDS plot. The heat treated lm showed a
dendritic morphology with subsequent transformation to equiaxed
grains as shown in Fig. 5(b). The evolution of the crystalline phases in
the lm upon heat treatment was determined from the in-situ
diffraction patterns, as shown in Fig. 5(c). The as-deposited lm
contained some crystalline Co, and upon heating in air oxidation
occurs to form rst CoO, beginning at ~500 C and then Co3O4. On

1297

Fig. 3. (a) Cross-sectional view of LNF64 lm on Ebrite substrate, along with line EDS
scan across the lmsubstrate interface; (b) in situ X-ray diffraction pattern of LNF55
lm on Crofer22 substrate, showing evolution of crystalline reaction products spinel,
M2O3 where M is transition metal, and La(Ni,Fe)O3- in the deposited lm on Crofer22
substrate.

1298

R. Lacey et al. / Solid State Ionics 181 (2010) 12941302

Fig. 4. (a) Microstructure of crystallized BSCF lm showing formation of blisters on the lm surface (marked by dotted circles). A close-up of the blisters is shown on the right,
whereas the inset in the picture on the left shows crystalline nature of the lms. (b) In situ X-ray diffraction pattern showing evolution of crystalline reaction products (Ba,Sr)CrO4,
spinel, (Ba,Sr)MO3 and M2O3 where M is transition metal in the deposited lm on Crofer22 substrate.

further heating, Co3O4 reacts with the Crofer22 to form a spinel-type

phase and excess CoO, which is chemically reasonable from a mass
balance analysis.
3.3. Long-term stability and chemical interdiffusion
LSC82, LNF55 and Co lms on Crofer22, E-Brite, and SS430
substrates were studied in detail using XPS depth proling. The

Table 1
Thin lm and bulk reaction products of different coating compositions with Cr2O3 and
Crofer22.
LSC

LSCF

BSCF

LNF

Cr2O3

(La,Sr)CoO3-
SrCrO4
Spinel

(La,Sr)FeO3-
SrCrO4
Spinel

La(Ni,Fe)O3-
Trace spinel
Trace NiO

Crofer22

(La,Sr)CoO3-
SrCrO4
Spinel

(La,Sr)FeO3-
SrCrO4
Spinel

BaCrO4
Sr3Cr2O8
Spinel
Ba12Co11O33
(Sr,Ba)2M2O5
BaCrO4
Sr3Cr2O8
Spinel
Ba12Co11O33
(Sr,Ba)2M2O5

La(Ni,Fe)O3-
Spinel
Trace NiO

inherent rough surface nish of the substrates (see for example Fig. 1
(c)) prevents accurate determinations of the sputtered depth, but the
proles nonetheless show trends in chemical interdiffusion.
Fig. 6 shows the XPS depth proles for several samples, which
highlights similarities in the Cr diffusion behavior:
Cr enrichment at the oxidemetal interface, with oxygen present
The Cr diffusion prole from the metal into the oxide is welldened, and reaches a concentration of zero at a depth of 350
400 nm below the surface of the oxide (~1100 nm for the thicker Co
lm)
Small Cr concentrations are noted on the surface of each specimen,
which we attribute to vapor phase transport of Cr from the uncoated
regions of the specimens rather than from Cr diffusion through the
coatings.
Fig. 6(a) shows the concentration depth prole for the LSC82 thin
lm on Crofer 22 substrate after heat treating at 1000 C for 3 h and
850 C for 168 h. Outward diffusion of Fe, Mn and Cr from the Crofer
22 substrate toward the lm is clear, even after the short periods of
exposure to high temperature environments. Concurrent inward
diffusion of Co from the lm toward the substrate is also evident.
The composition proles for the LSC82 lms treated at 168 and 3 h
are remarkably similar, with no signicant amount of Cr noted at or
near the surface and indistinguishable Cr concentration proles. The

R. Lacey et al. / Solid State Ionics 181 (2010) 12941302

1299

Fig. 5. (a) Cross-sectional view of Co lm on Crofer22 substrate, along with line EDS scan across the lmsubstrate interface; (b) microstructure of Co lm: after crystallization at
1000 C (A), and after isothermal heat treatment at 850 C for 168 h (B); (c) in situ X-ray diffraction pattern showing evolution of crystalline reaction products Co3O4, spinel, and
CoO in the deposited lm on Crofer22 substrate.

1300

R. Lacey et al. / Solid State Ionics 181 (2010) 12941302

primary differences between the depth proles for long and short
heat treatments are the increased Mn content below the lm and the
nearly complete diffusion of Co from the lm toward the substrate. An

analysis of the La proles suggests that the initial reaction of the lm

with Crofer22 results in a largely stable phase assemblage that traps
the Cr below the initial thin lm boundary.

Fig. 6. XPS proles for (a)LSC 82 on Crofer22, (b)LNF55 on Crofer22, (c)LNF64 on EBrite, (d)LNF64 on 430SS, and (e)Co lms on Crofer22. The plots marked A are for sample heat
treated at 1000 C for 3 h, the plots marked B are for samples heat treated at 850 C for 168 h subsequent to treatment at 1000 C for 3 h.

R. Lacey et al. / Solid State Ionics 181 (2010) 12941302

1301

incorporating some Mn in place of Co, while concurrently shifting

toward lower Sr content as a result of the partial reaction to form
SrCrO4. Indeed, it is also possible that the SrCrO4 layer may
incorporate some Mn, as hexavalent Mn and Cr have very similar
ionic radii in tetrahedral coordination (0.255 vs. 0.250 ). Heating the
samples for 168 h does not result in any notable changes in
microstructure, as shown in Fig. 2(b). The microstructures are similar
to the as-deposited lms, even maintaining the nano-scale grain size
after one week at 850 C.
A comparison of the concentration depth proles for the LNF55
thin lm before and after the long heat treatment is shown in Fig. 6
(b). The diffusion behavior is similar to that found for the LSC82 thin
lm, with outward diffusion of Fe, Mn and Cr toward the lm from the
Crofer 22 substrate, and inward diffusion of Ni from the lm toward
the substrate. A large increase in Mn concentration is detected near
the surface of the lm. Similar to LSC82, the LNF55 thin lm is shown
to be effective in mitigating diffusion of Cr from the substrate to the
sample surface.
For both LSC82 and LNF55, the La prole exhibited an exceedingly
sharp concentration boundary between La on the surface and the
underlying oxides, even after 168 h at 850 C. X-ray diffraction data
for the lms before and after the 168 h heat treatments are
qualitatively identical, with the formation of a perovskite phase, a
spinel phase, and either M2O3 or SrCrO4. Evidence that the diffusion of
the various cations simply changes the compositions of the various
solid solutions of the perovskite, spinel, and M2O3 phases can be
conrmed with an XRD measurement that probes the entire depth of
the lm. Again, the XRD results show substantial mass transport
through the depth without changing the phases present.
The XPS depth proles of LNF lms on E-Brite and SS430 substrates
after heating for 3 h at 1000 C are qualitatively similar, as shown in
Fig. 6(c) and (d), respectively. This result suggests that minor changes
in the alloy composition have little effect on cation diffusion and that
chemical differences can be accommodated by shifting solid solution
compositions without altering the phase assemblage. Fig. 6(e) shows
the concentration prole through the Co thin lm on Crofer 22
substrate. The Co lm is observed to be highly effective in preventing
diffusion of Cr to the surface of the lm, in agreement with recent
work by Stanislowski et al. [21] who studied lms of ~ 10 m thickness
prepared by sputtering. The effectiveness of the PVD Co coating is
clearly demonstrated, with only 3 m resulting in a spinel phase
capped by CoO/ Co3O4 oxides.

4. Conclusions

Fig. 6 (continued).

Qualitative XRD analyses of the LSC82 lms before and after the
168 h heat treatments show that identical phases are present. From
this result, it is clear that the diffusion of a fraction of the Co toward
the Crofer22 substrate, in concert with outward diffusion of Mn, does
not require decomposition of the perovskite coating. Instead, the
chemical composition of the initial LSC82 lm changes with time,

The PVD process produced LSC, LSCF, LNF and Co lms on Crofer22,
SS430 and E-Brite that are each highly effective in blocking Cr
diffusion from the steel substrate. BSCF lms were reactive and
formed blisters upon thermal cycling in air, so were not considered
further. All of the perovskite lms formed a similar phase assemblage
after heat treatment, consisting of the target perovskite, a spinel
intermediate layer, and minor fractions of M2O3 or SrCrO4 phases,
depending on the initial chemistry. Reactions of the as-deposited
lms with the substrate occurred rapidly, with little or no difference
in the chemical diffusion, microstructure, or phase assemblage found
between samples heat treated for 3 vs. 168 h.
The chemical depth proles clearly demonstrate that diffusion of the
perovskite B-site cations (Ni, Fe, Co) and the transition metals from the
steel (Fe, Cr, Mn) occurs rapidly at high temperature to spontaneously
form chemically graded lms with stable spinel and perovskite phases
that inhibit outward diffusion of Cr. The wide range of solid solution
accommodated by the spinel, perovskite, and M2O3 phases allows this
extensive chemical interdiffusion without changing the phases present.
In the case of the Co metal coating, heat treatment results in
oxidation and reaction to form a compositionally graded spinel layer

1302

R. Lacey et al. / Solid State Ionics 181 (2010) 12941302

and a CoO/ Co3O4 surface. This lm is also highly effective in blocking

Cr diffusion.
Overall, the results suggest that these PVD lms are effective for
mitigating diffusion of Cr from SOFC metal interconnects and that
renements in lm chemistry and processing might improve their
performance even further.
Acknowledgments
Financial support for this work was provided by the New York
State Foundation for Science, Technology and Innovation, NYSTAR,
under contract C030093, and Applied Coatings, Inc.
References
[1] T. Brylewski, M. Nanko, T. Maruyama, K. Przybylski, Solid State Ionics 143 (2001)
131.
[2] K. Huang, P.Y. Hou, J.B. Goodenough, Solid State Ionics 129 (2000) 237.
[3] T. Horita, Y. Xiong, K. Yamaji, N. Sakai, H. Yokokawa, Journal of The
Electrochemical Society 150 (2003) A243.
[4] J.H. Zhu, Y. Zhang, A. Basu, Z.G. Lu, M. Paranthaman, D.F. Lee, E.A. Payzant, Surface
and Coatings Technology 177178 (2004) 65.
[5] S.P.S. Badwal, R. Deller, K. Foger, Y. Ramprakash, J.P. Zhang, Solid State Ionics 99
(1997) 297.
[6] S. Taniguchi, M. Kadowaki, H. Kawamura, T. Yasuo, Y. Akiyama, Y. Miyake, T.
Saitoh, Journal of Power Sources 55 (1995) 73.
[7] S.P. Jiang, J.P. Zhang, K. Foger, Journal of The Electrochemical Society 147 (2000)
3195.
[8] S.C. Paulson, V.I. Birss, Journal of The Electrochemical Society 151 (2004) A1961.
[9] S.P. Jiang, S. Zhang, Y.D. Zhen, Journal of The Electrochemical Society 153 (2006)
A127.
[10] Z. Yang, K.S. Weil, D.M. Paxton, J.W. Stevenson, Journal of The Electrochemical
Society 150 (2003) A1188.

[11] K. Fujita, K. Ogasawara, Y. Matsuzaki, T. Sakurai, Journal of Power Sources 131

(2004) 261.
[12] C. Johnson, R. Gemmen, N. Orlovskaya, Composites Part B: Engineering 35 (2004)
167.
[13] S. Linderoth, Surface and Coatings Technology 80 (1996) 185.
[14] N. Orlovskaya, A. Corotalo, C. Johnson, R. Gemmen, Journal of the American
Ceramic Society 87 (2004) 1981.
[15] W.J. Quadakkers, H. Greiner, M. Hnsel, A. Pattanaik, A.S. Khanna, W. Mallner,
Solid State Ionics 91 (1996) 55.
[16] Y. Larring, T. Norby, Journal of the Electrochemical Society 147 (2000) 3251.
[17] X. Chen, P.Y. Hou, C.P. Jacobson, S.J. Visco, L.C. De Jonghe, Solid State Ionics 176
(2005) 425.
[18] W. Qu, L. Jian, J.M. Hill, D.G. Ivey, Journal of Power Sources 153 (2006) 114.
[19] Z. Yang, G. Xia, J.W. Stevenson, Electrochemical and Solid-State Letters 8 (2005)
A168.
[20] Z. Yang, G. Xia, S.P. Simmer, J.W. Stevenson, Journal of The Electrochemical Society
152 (2005) A1896.
[21] M. Stanislowski, J. Froitzheim, L. Niewolak, W.J. Quadakkers, K. Hilpert, T. Markus,
L. Singheiser, Journal of Power Sources 164 (2007) 578.
[22] P. Gannon, M. Deibert, P. White, R. Smith, H. Chen, W. Priyantha, J. Lucas, V.
Gorokhovsky, International Journal of Hydrogen Energy 33 (2008) 3991.
[23] W. Wei, W. Chen, D.G. Ivey, Chemistry of Materials 19 (2007) 2816.
[24] W. Wei, W. Chen, D.G. Ivey, Journal of Power Sources 186 (2009) 428.
[25] X. Deng, P. Wei, M.R. Bateni, A. Petric, Journal of Power Sources 160 (2006) 1225.
[26] J. Wu, C.D. Johnson, R.S. Gemmen, X. Liu, Journal of Power Sources 189 (2009)
1106.
[27] D.O. Klenov, W. Donner, L. Chen, A.J. Jacobson, Journal of Materials Research 18
(2003) 188.
[28] S.T. Misture, Measurement Science and Technology 14 (2003) 1091.
[29] V.V. Kharton, E.V. Tsipis, A.A. Yaremchenko, I.P. Marozau, A.P. Viskup, J.R. Frade, E.
N. Naumovich, Materials Science and Engineering: B 134 (2006) 80.
[30] L.W. Tai, M.M. Nasrallah, H.U. Anderson, D.M. Sparlin, S.R. Sehlin, Solid State Ionics
76 (1995) 273.
[31] N. Shaigana, W. Qua, D.G. Iveyb, W. Chen, Journal of Power Sources 195 (2010)
1529.