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A novel ionic diffusion strategy to fabricate high-performance

anode-supported solid oxide fuel cells (SOFCs) with proton-conducting
Y-doped BaZrO3 films
Lei Bi, Emiliana Fabbri, Ziqi Sun and Enrico Traversa*

Published on 18 November 2010. Downloaded by Tufts University on 27/10/2014 19:13:02.

Received 11th August 2010, Accepted 8th October 2010

DOI: 10.1039/c0ee00353k

A stable Y-doped BaZrO3 electrolyte film, which showed a good

performance in proton-conducting SOFCs, was successfully fabricated using a novel ionic diffusion strategy.
Intermediate temperature solid oxide fuel cells (SOFCs) require
electrolyte materials with high ionic conductivity and negligible
electronic conductivity at low working temperatures.13 In the past
three decades, high temperature proton conductors received more
and more attention because of their high ionic conductivities and low
activation energies, and they provide an alternative solution for
SOFC electrolyte materials compared with oxygen-ion conductors.4,5
Until now, the most widely investigated high temperature protonconducting materials are doped BaCeO3 and BaZrO3.6 BaCeO3based materials with high proton conductivity show poor chemical
stability against H2O and CO2, which makes difficult their practical
applications.7,8 Instead, BaZrO3-based materials are regarded as good
electrolyte candidates for proton-conducting SOFCs as they show
better chemical stability9 and high proton conductivity in bulk.10
However, the poor sinteractivity and low grain boundary conductivity of BaZrO3 hinder its applications.1113 To solve these problems,
high sintering temperatures (up to 1700  C1800  C) are needed to
densify BaZrO3 membranes.14 The aggressive preparation conditions
not only lead to high costs, but also result in several drawbacks for
fuel cell applications, especially for anode-supported fuel cells; in fact,

International Research Center for Materials Nanoarchitectonics

(MANA), National Institute for Materials Science (NIMS), 1-1
Namiki, Tsukuba, Ibaraki, 305-0044, Japan. E-mail: TRAVERSA.
Enrico@nims.go.jp; Fax: +81-29-860-4706; Tel: +81-29-860-4896
Electronic supplementary information (ESI) available: Experimental
section and detailed results. See DOI: 10.1039/c0ee00353k

high sintering temperatures lead to Ba evaporation and make difficult

the choice of electrode substrate materials to keep enough porosity
after sintering and to avoid severe reactions between electrolyte
and electrode materials.13,15 The use of sintering aids (such as ZnO
and NiO) can promote the densification of doped BaZrO3 at low
temperatures,11,12 but it also reduces proton conductivity,11 making
desirable the use for fuel cell applications of BaZrO3-based electrolytes without sintering aids. Because of these difficulties, studies on
BaZrO3 film SOFCs are less numerous than for other electrolyte
materials, despite the anode-supported cell design is currently
preferred.16,17 Very recently some film BaZrO3 electrolyte membranes
have been prepared on electrode substrates, but either high firing
temperatures,18 or highly sinteractive but unstable substrates (such as
BaCeO3-based anode),19 or advanced small-scale techniques (such as
pulsed laser deposition, PLD)20 were used for their preparation. In
addition, the cell performances of the BaZrO3 anode-supported fuel
cells reported in the literature are not as attractive as expected.
Therefore, the fabrication of stable BaZrO3 film fuel cells with
reasonable performance still remains a challenge.
We attempted to fabricate BaZr0.8Y0.2O3 d (BZY20) electrolyte
films on NiOBZY20 anodic substrates with a diameter of 13 mm by
using a traditional processing technique, the co-pressing method. A
BZY20 powder was co-pressed on a NiOBZY20 substrate and fired
at high temperatures with the hope of preparing an anode supported
BZY20 electrolyte layer. However, the BZY20 membrane was not
dense after sintering at 1450  C for 10 h and could not be used as
electrolyte in fuel cell applications (Fig. S1, ESI). In-doping has been
reported to help BaZrO3 densification, but lowering its conductivity21
because of proton mobility lower for In-doped than for Y-doped
samples.22 Here, we report a novel ionic diffusion strategy that takes
advantage of the high sinteractivity of In-doped BaZrO3, of the In

Broader context
The development of clean energy with new technologies becomes one of the major issues for the modern society as the state-of-theart standard technologies based on fossil fuel combustion will not guarantee the future energy requirements. Solid oxide fuel cell
(SOFC) technology producing electricity with high efficiency and low impact to environment offers a great potential. However,
conventional SOFCs need high operating temperatures which increase the costs and reduce the lifetime for the cells. In the development of intermediate temperature SOFCs, proton-conducting oxides provide a promising option as electrolyte materials because
of their high ionic conductivity and low activation energy. Y-Doped BaZrO3 (BZY) is a very good candidate as electrolyte material
because of its excellent chemical stability and high bulk conductivity, but its poor sinteractivity and large grain boundary resistance
lead to low fuel cell performance, limiting its applications. In this study, a novel ionic diffusion strategy was used to prepare BZY
electrolyte films on NiOBZY anodes. The performance of the cell based on the BZY electrolyte film was very encouraging: a peak
power density of 254 mW cm 2 at 700  C was obtained and this power output was the largest ever measured for BZY electrolyte
films.
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evaporation from the electrolyte membrane, and of the Y diffusion

from the substrate to the electrolyte membrane, to form a dense
Y-doped BaZrO3 (BZY) electrolyte film on anodic substrates,
showing promising performance in anode-supported protonconducting SOFCs.
Fig. 1 shows a schematic illustration of the basic idea of the
ionic diffusion strategy. An In-doped BaZrO3 (BZI) powder
layer is co-pressed on a NiOBZY anode substrate. During the
subsequent high temperature firing process, sintering of BZI
occurs, followed by In3+ ions evaporation from the electrolyte
layer in the form of In2O3 (Fig. S2, ESI) and Y3+ ions migration
from the anode to the electrolyte layer, to occupy the In3+ sites.
This process results in fabricating a dense BZY layer, instead of
the original BZI layer, as electrolyte for fuel cell applications.
The BaZr0.7In0.3O3 d (BZI30) powder was synthesized by a wet
chemical route and its element composition after firing was analyzed
by inductively coupled plasma optical emission spectrometer (ICPOES). The ICP-OES results showed that the initial In molar ratio in
the BZI30 powder was about 14.3% which is close to the theoretical
value of that in BZI30 (15%). A BZI30 electrolyte film was fabricated
on a NiOBaZr0.8Y0.2O3 d (BZY20) anode to form a bi-layer by copressing method. Fig. 2 shows the X-ray diffraction (XRD) pattern
and the scanning electron micrograph (SEM) of the electrolyte layer
surface after firing at 1450  C for 10 h. The electrolyte layer was made
of a single perovskite phase and dense. The lattice parameter of the
 The electrolyte surface
perovskite phase was calculated to be 4.206 A.
element composition before and after sintering was confirmed by

energy dispersive X-ray spectroscopy (EDS) analysis. The SEM-EDS

results of the green electrolyte layer confirmed that its composition
was made of Ba, Zr, In and O (Fig. S3, ESI). However, the SEMEDS results of both spot and area scans of the electrolyte after
sintering revealed that the In content was below the detection limit,
implying that most of In3+ was evaporated from the electrolyte layer
(Fig. S4, ESI). Instead, Y can be found in the electrolyte at
a concentration of around 10%, as measured from EDS quantitative

analysis. Though affected by errors, this value agrees with the 4.206 A

lattice parameter calculated for the electrolyte, quite close to 4.205 A
reported for 10% Y-doped BaZrO3.23
Fig. 3 shows the EDS results of the electrolyte layer and anode
elemental mapping. Ba, Zr and O elements are well distributed in
the electrolyte/anode bi-layer after firing, while Ni could only be
detected in the anode, indicating little Ni diffusion from the anode to
the electrolyte. In could not be found in either the electrolyte or the
anode, suggesting that most of the In element was lost during firing.
Instead, EDS mapping showed that Y was uniformly distributed in
the anode and electrolyte layers, implying that the Y3+ ions migrated
from the anode to the electrolyte during the co-firing process. Thus,
the electrolyte layer consisted of Ba, Zr, Y and O elements, instead of
Ba, Zr, In and O. This evidence was further confirmed by SEM-EDS
line-scan result (Fig. S5, ESI).
With this strategy, we took advantage of the good sinteractivity of
BZI30 to form a dense layer, which during high temperature firing
was transformed in Y-doped BaZrO3 (BZY10). This is beneficial for
SOFC applications since protonic conductivity of BZY is larger than

Fig. 1 Schematic diagram of the procedure for preparing an anode

supported BZY electrolyte film via an ionic diffusion strategy.

Fig. 2 XRD pattern and SEM micrograph of the electrolyte surface

after firing. The reflection lines of undoped BaZrO3 (JCPDS Card No.
06-0399) are also included as reference.

410 | Energy Environ. Sci., 2011, 4, 409412

Fig. 3 (a) SEM cross-sectional view of the anode supported electrolyte

bi-layer and (b) EDS elemental mapping of the bi-layer shown in (a).

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that of BZI. The amount of materials in the anodic substrate with

respect to the electrolyte is large enough to expect a very limited
change in BZY composition in the anodic substrate.
We also examined the chemical stability of the formed electrolyte
layer as a critical requirement for fuel cell applications. The XRD
patterns of the surface of the sintered electrolyte layer before and after
being treated in boiling water and in flowing 100% CO2 at 700  C
showed that the electrolyte layer structure remained unchanged
after the treatments in these aggressive conditions (Fig. S6, ESI).
These results demonstrate the excellent chemical stability of the BZY
electrolyte film prepared by the ionic diffusion strategy.
Using PrBaCo2O5+dBaZr0.7Y0.2Pr0.1O3 d (ref. 24) as the cathode
material, a single cell was tested with humidified hydrogen (3%
H2O) as the fuel and static air as the oxidant. The SEM micrographs
of the cell after fuel cell testing indicated that a well-sintered electrolyte membrane about 20 mm thick was fabricated (Fig. S7, ESI).
The membrane was dense and free of any interconnected pores and
cracks. Moreover, the adhesion with anode and cathode layers was
very good, without any cracking after testing. Fig. 4 shows the IV
and power density curves for the cell at different temperatures. Peak
power densities of 92, 133, 169, 216, and 254 mW cm 2 were obtained
at 500, 550, 600, 650, and 700  C, respectively. The output of the
cell is at least one order of magnitude larger than that of electrolytesupported BZY cells (about several mW cm 2 at elevated temperatures),8,25,26 as expected by reducing the electrolyte thickness.
Moreover, it should be highlighted that the power output obtained in
the present study is also the largest when compared with the
performance of electrode-supported cells using BZY electrolytes

Fig. 4 Performance of the anode-supported BZY film cell measured at

different temperatures.

reported in the literature, as summarized in Table 1. For most of the

previous studies, despite the electrolyte thickness was reduced to tens
of microns, the power density was only improved at about tens of
mW cm 2, while the performance of the cell in this study shows
a dramatic improvement. The current cell even shows an advantage
in fuel cell performance when compared with a cell with a much
thinner BZY electrolyte (4 mm) prepared by PLD method, indicating
that the ionic diffusion strategy is not only an effective way to
fabricate dense and stable BZY membranes on anodic substrates, but
also beneficial to increase the cell performance. It is worth noticing
that this strategy can be easily deployed in other ceramic processing
techniques, such tape-casting, slip-casting or suspension spray, suitable to fabricate larger scale cells.
Electrochemical impedance spectroscopy (EIS) measurements
were used to investigate the cell resistances under open circuit voltage
conditions. From the typical EIS plot of the cell measured at 700  C
(Fig. S8, ESI), it can be seen that the intercept with the real axis at
high frequency represents the ohmic resistance of the cell (Rohmic),
which includes the electrolyte resistance, some resistances associated
with interfaces and lead wires. The low frequency intercept corresponds to the total resistance of the cell. Therefore, the difference
between the high frequency and low frequency intercepts with the real
axis represents the total interfacial polarization resistance (Rp) of the
cell. The measured Rohmic was 1.53 U cm2 at 500  C, 1.16 U cm2 at
550  C, 0.88 U cm2 at 600  C, 0.66 U cm2 at 650  C and 0.53 U cm2
at 700  C, while the Rp of the cell were measured to be 1.18 U cm2 at
500  C, 0.51 U cm2 at 550  C, 0.26 U cm2 at 600  C, 0.13 U cm2 at
650  C and 0.073 U cm2 at 700  C (Fig. S9, ESI). The low Rohmic and
Rp values made the cell show promising performance, suggesting
that the BZY electrolyte film prepared by the ionic diffusion
method maintained good conductivity and PrBaCo2O5+dBaZr0.7Y0.2Pr0.1O3 d composite cathode showed desirable performance in
proton-conducting SOFC applications.
In summary, a novel ionic diffusion strategy was presented to
fabricate an anode-supported BZY electrolyte layer. The strategy
overcame the sintering problems for BaZrO3-based materials and
took the advantage of the sinteractivity improvement of In-doping
for BaZrO3. Due to In evaporation and Y migration to the electrolyte
layer, a dense BZY electrolyte membrane was finally formed during
the firing process, which avoided the problem of BZI lower
conductivity. Besides keeping good chemical stability, the BZY
electrolyte film showed the largest fuel cell performance ever reported
for BZY-based electrolytes, to the best of our knowledge, suggesting
that the ionic diffusion strategy provided an effective and interesting
way to fabricate BaZrO3 electrolyte films with desirable performance
and could be beneficial to the application of stable proton-conducting
SOFCs.

Table 1 Comparison of the fuel cell performance of anode-supported cells using BZY electrolyte films reported in the literature and in the present study

Year [reference]

BZY Electrolyte
thickness/mm

Electrolyte fabrication technique

Electrode substrate and its chemical

stability

Peak power
density/mW cm

2009 [18]
2009 [27]
2010 [19]
2010 [20]
Present work

10
30
20
4
20

Spin-coating
Direct co-pressing
Direct co-pressing
Pulsed laser deposition (PLD)
Co-pressing with ionic diffusion

LSMBZYZn,a stable
NiOBZY, stable
NiOBaCe0.7Zr0.1Y0.2O3 d, moderate
NiOBZY, stable
NiOBZY, stable

26 (at 800  C)
23 (at 600  C)
70 (at 600  C)
110 (at 600  C)
169 (at 600  C)

LSM: (La0.8Sr0.2)0.98MnO3 d; BZYZn: Zn-doped BZY.

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Acknowledgements
This work was financially supported in part by the World Premier
International Research Center Initiative of MEXT, Japan. ZQS was
supported by a NIMS Postdoctoral Fellowship. The authors thank
Dr Hidehiko Tanaka for his invaluable technical assistance.

Published on 18 November 2010. Downloaded by Tufts University on 27/10/2014 19:13:02.

Notes and references

1 B. C. H. Steele and A. Heinzel, Nature, 2001, 414, 345.
2 D. J. L. Brett, A. Atkinson, N. P. Brandon and S. J. Skinner, Chem.
Soc. Rev., 2008, 37, 1568.
3 W. Zhou, Z. P. Shao, R. Ran, W. Q. Jin and N. P. Xu, Chem.
Commun., 2008, 5791.
4 T. Norby, Solid State Ionics, 1999, 125, 1.
5 J. W. Phair and S. P. S. Badwal, Ionics, 2006, 12, 103.
6 E. Fabbri, D. Pergolesi and E. Traversa, Chem. Soc. Rev., 2010, 39,
4355.
7 K. Katahira, Y. Kohchi, T. Shimura and H. Iwahara, Solid State
Ionics, 2000, 138, 91.
8 E. Fabbri, A. DEpifanio, E. Di Bartolomeo, S. Licoccia and
E. Traversa, Solid State Ionics, 2008, 179, 558.
9 K. D. Kreuer, Annu. Rev. Mater. Res., 2003, 33, 333.
10 D. Pergolesi, E. Fabbri, A. DEpifanio, E. Di Bartolomeo,
A. Tebano, S. Sanna, S. Licoccia, G. Balestrino and E. Traversa,
Nat. Mater., 2010, 9, 846.
11 P. Babilo and S. M. Haile, J. Am. Ceram. Soc., 2005, 88, 2362.
12 S. W. Tao and J. T. S. Irvine, Adv. Mater., 2006, 18, 1581.

412 | Energy Environ. Sci., 2011, 4, 409412

13 J. M. Serra and W. A. Meulenberg, J. Am. Ceram. Soc., 2007, 90,

2082.
14 Z. M. Zhong, Solid State Ionics, 2007, 178, 213.
15 M. Asamoto, H. Shirai, H. Yamaura and H. Yahiro, J. Eur. Ceram.
Soc., 2007, 27, 4229.
16 C. D. Zuo, S. W. Zha, M. L. Liu, M. Hatano and M. Uchiyama, Adv.
Mater., 2006, 18, 3318.
17 X. Z. Fu, J. L. Luo, A. R. Sanger, N. Danilovic and K. T. Chuang,
Chem. Commun., 2010, 46, 2052.
18 C. Peng, J. Melnik, J. X. Li, J. L. Luo, A. R. Sanger and
K. T. Chuang, J. Power Sources, 2009, 190, 447.
19 W. P. Sun, L. T. Yan, Z. Shi, Z. W. Zhu and W. Liu, J. Power Sources,
2010, 195, 4727.
20 D. Pergolesi, E. Fabbri and E. Traversa, Electrochem. Commun.,
2010, 12, 977.
21 N. Ito, H. Matsumoto, Y. Kawasaki, S. Okada and T. Ishihara, Solid
State Ionics, 2008, 179, 324.
22 F. Giannici, A. Longo, A. Balerna, K. D. Kreuer and A. Martorana,
Chem. Mater., 2007, 19, 5714.
23 A. K. Azad, C. Savaniu, S. W. Tao, S. Duval, P. Holtappels,
R. M. Ibberson and J. T. S. Irvine, J. Mater. Chem., 2008, 18, 3414.
24 E. Fabbri, L. Bi, H. Tanaka, D. Pergolesi, E. Traversa, Adv. Funct.
Mater., DOI: 10.1002/adfm.201001540.
25 E. Fabbri, D. Pergolesi, A. DEpifanio, E. Di Bartolomeo,
G. Balestrino, S. Licoccia and E. Traversa, Energy Environ. Sci.,
2008, 1, 355.
26 A. DEpifanio, E. Fabbri, E. Di Bartolomeo, S. Licoccia and
E. Traversa, Fuel Cells, 2008, 8, 69.
27 Y. M. Guo, Y. Lin, R. Ran and Z. P. Shao, J. Power Sources, 2009,
193, 400.

This journal is The Royal Society of Chemistry 2011