CYOeBZCYO composites with enhanced proton conductivity:

Candidate electrolytes for low-temperature solid oxide fuel

cells
Jianbing Huang
a,
*, Li Zhang
b
, Cheng Wang
c
, Ping Zhang
b
a
State Key Laboratory of Multiphase Flow in Power Engineering, School of Energy and Power Engineering, Xian Jiaotong University,
Xian 710049, PR China
b
Faculty of Material Science and Chemical Engineering, China University of Geosciences, Wuhan 430074, PR China
c
Institute of Nuclear and New Energy Technology, Tsinghua University, Beijing 100084, PR China
a r t i c l e i n f o
Article history:
Received 20 December 2011
Received in revised form
9 May 2012
Accepted 10 May 2012
Available online 12 June 2012
Keywords:
Ce
0.8
Y
0.2
O
1.9
(CYO)
BaZr
0.1
Ce
0.7
Y
0.2
O
2.9
(BZCYO)
Composite electrolyte
Proton conductivity
Low-temperature solid oxide fuel
cells (LT-SOFCs)
a b s t r a c t
Novel composite oxide ion conductors were developed based on a uorite-type Ce
0.8
Y
0.2
O
1.9
(CYO) and a perovskite-type BaZr
0.1
Ce
0.7
Y
0.2
O
2.9
(BZCYO) synthesized by the carbonate co-
precipitation route at 700

C and the solegel process at 1000

C, respectively. When sintered
at 1400

C, CYO and BZCYO showed an ac conductivity of 1.60 10
2
S cm
1
and
1.21 10
2
S cm
1
at 600

C, respectively, in dry air and wet hydrogen. CYOeBZCYO
composites sintered at 1400

C showed much lower conductivity than CYO and BZCYO in
dry air, but they showed enhanced conductivity in wet hydrogen. The highest conductiv-
ities of 3.27 10
2
S cm
1
at 500

C and 9.40 10
3
S cm
1
at 400

C were achieved in wet
hydrogen by the composite containing 30wt.% BZCYO, which are 3e5 times higher than
those of CYO and BZCYO, making this composite material a promising candidate as an
electrolyte for low-temperature solid oxide fuel cells (LT-SOFCs).
Copyright 2012, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights
reserved.
1. Introduction
To accelerate the commercialization of solid oxide fuel cell
(SOFC) technology, enormous efforts have been made to
reduce the operating temperature from a traditional high
temperature of around 1000

C down to intermediate
(600e800

C) and low (400e600

C) temperature range [1e3].
This reduced-temperature operation will allow easier cell &
stack construction, enable cheaper materials to be used, and
improve long-term cell stability and stack durability. By
reducing the operating temperature to 500

C or below, due to
its capability to start up rapidly, SOFC has the potential as
power source for electric vehicle applications in combination
with energy storage devices, e.g. rechargeable batteries or
electrochemical supercapacitors. However, electrolyte resis-
tance and electrode polarization increase greatly with the
decreasing temperature, which reduce the performance of
SOFC. Improving the electrolyte performance for low
temperature operation is achieved by reducing the electrolyte
thickness and using new electrolyte materials with high ion
(O
2
/H

) conductivity at low temperatures [4e6].

Fluorite-type ceria (CeO
2
) based oxides have been exten-
sively studied as electrolyte materials for low-temperature
solid oxide fuel cell (LT-SOFC) operating at 500e600

C and
* Corresponding author. Tel.: 86 29 82665591; fax: 86 29 82669033.
E-mail address: huangjb@mail.xjtu.edu.cn (J. Huang).
Available online at www.sciencedirect.com
j ournal homepage: www. el sevi er. com/ l ocat e/ he
i nt e r na t i ona l j o ur na l o f hy d r o g e n e ne r g y 3 7 ( 2 0 1 2 ) 1 3 0 4 4 e1 3 0 5 2
0360-3199/$ e see front matter Copyright 2012, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.
doi:10.1016/j.ijhydene.2012.05.040
made much progress [7e10]. It has been reported that some
singly doped ceria, such as Ce
1x
Gd
x
O
2d
(CGO),
Ce
1x
Sm
x
O
2d
(CSO) and Ce
1x
Y
x
O
2d
(CYO) show an oxygen-
ion conductivity as high as 10
2
S cm
1
at 600

C [4], corre-
sponding to that of conventional yttria-stablized zirconia
(YSZ) at 800

C. While doped ceria exhibits mixed ionic-
electronic conducting behavior in the anodic environment
due to the reduction of Ce
4
to Ce
3
. This reduction causes
internal electronic transport in the electrolyte and expan-
sion of the lattice, resulting in signicant decrease in cell
voltage and mechanical strength. The electronic conduction
can be suppressed by lowering the operating temperature,
and doped ceria becomes a predominantly ionic conductor
below 450

C even in the fuel atmosphere [11], but its ionic
conductivity needs further improvement for LT-SOFC
application.
Oxide proton conductors are also being applied as elec-
trolytes for LT-SOFC because of their lowactivation energy for
proton conduction. Many perovskite-type oxides show high
proton conductivity in reducing and humid atmospheres at
low temperature [12]. Doped barium cerate (BaCeO
3
) such as
BaCe
0.8
Y
0.2
O
2.9
(BCYO) possesses a proton conductivity of
10
2
S cm
1
at 600

C, and it is a pure ion conductor not
suffering from the reduction at low oxygen partial pressure.
Ito et al. [13] had demonstrated the highest fuel cell perfor-
mances at 400e600

C based on a 0.7 mm thick BCYO electro-
lyte. However, BaCeO
3
is not chemically stable in an
atmosphere containing CO
2
and H
2
O, which makes it inade-
quate as electrolyte for fuel cell application, especially for use
with hydrocarbon or syngas fuels. The chemical stability can
be improved by the introduction of Zr to partially replace Ce,
but the proton conductivity is normally reduced due to its
poor sinterability [14]. BaZr
0.1
Ce
0.7
Y
0.2
O
3d
(BZCYO) achieves
high proton conductivity, as well as sufcient chemical and
thermal stability over the wide range of LT-SOFC operating
conditions, which is regarded as candidate electrolyte for LT-
SOFC [15].
Two-phase composite electrolyte based on doped ceria
phase and doped barium cerate phase has been successfully
prepared using ceramic composite technology by Zhu et al.
[16] for the rst time and excellent fuel cell performances has
been demonstrated below 600

C based on an approximately
0.3e0.5 mm thick electrolyte. It is found that doped barium
cerate phase can block the internal electron current caused by
the reduction of doped ceria phase and improve the total ion
conductivity in SOFC operation [17]. This composite effect has
been proved by some doped ceria-based composites. For
example, doped ceriaecarbonate composites show hybrid
oxygen-ion and proton conduction with extremely enhanced
ion conductivity in fuel cell environment accounting for
interfacial proton conduction [18]. In contrast, doped ceria-
doped barium cerate composites have better thermal
stability than doped ceriaecarbonate composites. However,
the study on such functional two-phase composites based on
oxide ion conductors for SOFC electrolytes is very limited. To
our knowledge, Ce
0.8
Y
0.2
O
1.9
(CYO) and BaZr
0.1
Ce
0.7
Y
0.2
O
2.9
(BZCYO) composites have never been studied. These
composites are expected to possess mixed ion conduction,
enhanced ion conductivity, suppressed electron conductivity
and improved chemical stability.
In this work, novel CYOeBZCYOcomposites were prepared
using ceramic composite technology and their electrical
conductivities under dry air and wet hydrogen (3% H
2
O)
atmospheres at 400e700

C were investigated to evaluate their

feasibility as LT-SOFC electrolytes. The phase stability of
CYOeBZCYO composites was studied to determine the sin-
tered temperature.
2. Experimental
2.1. Materials preparation
Ce
0.8
Y
0.2
O
1.9
(CYO) powders were synthesized by the
carbonate co-precipitation route. Stoichiometric amounts of
Ce(NO
3
)
3
$6H
2
O(A.R.) and Y
2
O
3
(A.R.) were dissolved in distilled
water and dilute nitric acid, respectively, then the Y(NO
3
)
3
solution was added to the Ce(NO
3
)
3
solution to form 0.5 M
metal nitrate solution. According to the molar ratio of metal
ion to carbonate ion in 1:2, a certain amount of Na
2
CO
3
was
dissolved in distilled water to form 0.5 M Na
2
CO
3
solution.
Then the metal nitrate solution was dropwise added into
Na
2
CO
3
solution under vigorous stirring to form a white
precipitate at room temperature. The precipitate was
vacuum-ltered, washed for three times with hot deionized
water and anhydrous ethanol, followed by drying at 80

C for
12 h to obtain CYOprecursor. Finally, the precursor was lightly
crushed in an agate mortar and calcined at the temperature
between 600

C and 800

C in air for 2 h to obtain pure CYO
powders.
BaZr
0.1
Ce
0.7
Y
0.2
O
2.9
(BZCYO) powders were synthesized by
the solegel process. The starting materials were Ba(NO
3
)
2
(A.R.), ZrO
2
(A.R.), Ce(NO
3
)
3
$6 H
2
O (A.R.), Y
2
O
3
(A.R.) and EDTA
(ethylenediamietetraacetic acid, A.R.). ZrO
2
and Y
2
O
3
were
dissolved in nitric acid to form 1 M solution, respectively.
Stoichiometric amounts of Ba(NO
3
)
2
and Ce(NO
3
)
3
$6H
2
O were
dissolved in distilled water, then the Zr(NO
3
)
4
and Y(NO
3
)
3
solutions were added into the above solution to form metal
precursor solution with the molar ratio of Ba
2
:Zr
4
:Ce
3
:Y
3
as 1:0.1:0.7:0.2. The molar ratio of EDTA to the total metal ion
was set at 2:1. Ammonium hydroxide (NH
3
33%) was added to
promote the dissolution of EDTA in deionized water, and
adjust the pH value to 9 when the metal precursor solution
was added dropwise to the EDTA solution. A polymeric gel
was obtained after evaporating the water at 80

C under
continuous stirring. The gel was heat-treated at 250

C in air
for 6h, and then the resultant was ground thoroughly and
calcined at the temperature between 800

C and 1200

C in air
for 4 h to obtain pure BZCYO powders.
CYOeBZCYO composite powders containing 20wt.%,
30wt.%, 50wt.% and 70wt.% BZCYO phase were prepared by
mixing pure CYO and BZCYO powders in anhydrous ethanol,
and dispersing the mixture by ultrasonic oscillation, then
grinding the suspensions thoroughly in an agate mortar, fol-
lowed by drying in an infrared oven. All composite powders
and pure CYO and BZCYO powders were uniaxially pressed
into pellets with 13 mm in diameter and 1 mm in thickness
under a pressure of 300 MPa. Then the pellets were sintered in
air at the temperature from 1200 to 1450

C for 5 h.
i nt e r na t i o na l j our na l o f hy d r og e n e ne r g y 3 7 ( 2 0 1 2 ) 1 3 0 4 4 e1 3 0 5 2 13045
2.2. Characterization measurements
The crystal structure and phase purity of calcined CYO and
BZCYO powders were characterized using an X-ray diffrac-
tometer (XRD, D8 Advance, Bruker AXS Corp., German) with
CuKa radiation (l 0.15406 nm 40 kV and 100 mA). The
densities of sintered CYO and BZCYO electrolyte pellets were
measured by the standard Archimedes method. The surface
morphology of CYO and BZCYO electrolyte pellets sintered at
different temperatures were characterized using a scanning
electron microscope (SEM, JSM-4500, JEOL, Japan). The phase
stability of sintered CYOeBZCYO composite samples was also
studied by XRD.
The electrical conductivity of CYOeBZCYO composite
electrolytes as well as pure CYO and BZCYO electrolytes was
measured in dry air and wet hydrogen (3% H
2
O), respectively,
using the standard two-probe ac impedance spectroscopy
(IM6E, Zahner, Germany). Silver paste was painted onto either
side of the electrolyte pellets and red at 600

C for 1 h to act as
electrodes. Impedance data were taken from 700

C to 400

C
(50

C at intervals) and a frequency range of 0.1 Hze1 MHz
using an excitation voltage of 10 mV.
3. Results and discussion
3.1. Calcination of CYO and BZCYO powders
Fig. 1 shows the XRDpatterns of CYO powders calcined at 600,
700, and 800

C, respectively. These patterns conrm the
formation of the cubic uorite structure for all three samples.
The degree of XRD peak broadening decreased with the
increasing calcination temperature from 600 to 800

C, which
indicates the increase of the crystallite size. The crystallite
sizes of the particles are calculated from FWHM data for (111)
crystal face using Scherrer formula D 0.9l/bcosq, where D is
the crystallite size in nm, l the radiation wavelength
(0.15406 nm in present case, Cu target), q the diffraction angle,
and b is the corrected line widthat half peak intensity, b canbe
calculated using the formula b
2
b
2
m
b
2
s
, where b
m
is the
measured FWHM and b
s
(taken as 0.1704) is the FWHM of
a standard silicon sample. The calculated particle sizes of CYO
powders calcined at 600, 700 and 800

C are 18, 30, and 57 nm,
respectively. Here, CYO powder calcined at 700

C for 2 h was
chosen as one constituent phase for CYOeBZCYOcomposites.
Fig. 2 shows the XRD patterns of BZCYO powders calcined
at 800, 1000 and 1200

C, respectively. As evidence from the
patterns, BaCO
3
phase and uorite phase were detected in
BZCYO powder after calcination at 800

C. As the calcination
temperature increased up to 1000

C, XRD showed pure
BaCeO
3
with orthorhombic perovskite structure as a result of
the solid solution formation with Ce, Zr and Y statistically
distributed in the lattice. It indicates that solegel process is
effective to lower the phase formation temperature of BZCYO,
compared with conventional solid-state reaction method [19].
The crystallite sizes of BZCYO particles are also calculated
from FWHM data for (002) crystal face using Scherrer formula.
The calculated particle sizes of BZCYO powders calcined at
800, 1000 and 1200

C are 15, 20, and 23 nm, respectively. Here,

BZCYO powder calcined at 1000

C for 4 h was selected as the
second phase for CYOeBZCYO composites.
3.2. Sintering of CYO and BZCYO electrolytes
The surface microstructures of CYO electrolytes prepared
fromCYOpowder calcined at 700

C and sintered at 1200, 1300

and 1400

C for 5 h, respectively, were observed by SEM, as
shown in Fig. 3aec. Seen fromFig. 3a, the sintering necks were
born at 1200

C between the neighboring particles, and the
grain sizes ranged from about 0.2 to 1 mm. In the meantime,
many small pores were distributed in the grain boundaries.
When the sintered temperature increased to 1300

C (Fig. 3b),
the grain sizes grew up to about 0.5e1.5 mm, and the pore size
and number decreased signicantly. The grain sizes increased
to about 1.5e3 mm at the sintered temperature of 1400

C, and
the surface structure became rather dense with the formation
of isolated close pores. In general, large grain sized material
showed a high conductivity, due to a signicant increase in
10 20 30 40 50 60 70
(
4
0
0
)
(
2
2
2
)
(
3
1
1
)
(
2
2
0
)
(
2
0
0
)
(
1
1
1
)
800
o
C
700
o
C
600
o
C
I
n
t
e
n
s
i
t
y

(
a
.
u
.
)
2 (degree)
Fig. 1 e XRD patterns of CYO powders after being calcined
at 600, 700, and 800

C for 2 h.
Fig. 2 e XRD patterns of BZCYO powders after being
calcined at 800, 1000 and 1200

C for 5 h.
i nt e r na t i ona l j o ur na l o f hy d r o g e n e ne r g y 3 7 ( 2 0 1 2 ) 1 3 0 4 4 e1 3 0 5 2 13046
grain boundary conductivity (s
gb
), but a small decrease in
grain interior conductivity (s
gi
) [20]. Thus, CYO electrolyte
should be sintered at high temperatures to promote grain
growth and reduce the number of defects and pores along
grain boundaries in order to minimize grain boundary
resistance.
Shown in Fig. 3def are the surface views of BZCYO elec-
trolytes prepared from BZCYO powder calcined at 1000

C and
sintered at 1300, 1400, and 1450

C for 5 h, respectively. It can
be observed in the micrograph (Fig. 3d) that the sample sin-
tered at 1300

C was not fully dense. The grain size is esti-
mated to be about 0.3 mm showing uniform distribution in the
sintered body. With the increasing of sintered temperature,
the grains grew up gradually due to the diffusion and transfer
of cations, and the connected open pores were compressed
and deformed to isolated close pores. At the sintering
temperature of 1450

C (Fig. 3f), the number of pores on the
surface of the sample decreased evidently, and the contact
between adjacent particles became much tighter resulting in
an average grain size of about 1 mm. But the sample sintered at
1450

C was still not fully densied.
The effect of sintered temperature on the density of the
CYO and BZCYO specimens from the corresponding powders
calcined at 700

C and 1000

C, respectively, is illustrated in
Table 1. The relative densities of CYO and BZCYO electrolytes
were calculated according to the theoretical densities derived
from the XRD data referring to the corresponding crystal
structures and the densities measured by Archimedes
method. As the sintered temperature increased, all sintered
samples became increasingly dense. It is noted that a relative
density of 95.1% was obtained by the CYO sample sintered at
1400

C, which is about 200

C lower than that by conventional

solid-state reaction method [21]. Low sintered temperature of
electrolyte facilitates the selection of electrode materials for
SOFC application and the reduction of cell fabrication cost.
However, the BZCYO sample had comparatively low relative
density, below90%at 1450

C, due to lowrates of graingrowth.

The poor sinterablity of BZCYO electrolyte will inevitably
affect grain boundary resistance and gas permeability, which
restricts its application in SOFC.
3.3. Electrical conductivity of sintered CYO and BZCYO
electrolytes
Fig. 4 shows the Arrhenius plot of the electrical conductivity in
dry air for CYO electrolyte pellets from the powder calcined at
700

C sintered at 1200, 1300 and 1400

C for 5 h, respectively.
An almost linear relationship is found in the measured
temperature range of 400e700

C for each sample. It can be
seen that the electrical conductivity of CYO electrolyte
increases with the measured temperature studied. This trend
is consistent with the behavior of ion conductors. Therefore,
CYO electrolyte pellets sintered at different temperatures are
proposed to be oxygen-ion conductors in air via the migration
Fig. 3 e SEM micrographs of the surface views of the CYO pellets sintered at (a) 1200

C, (b) 1300

C and (c) 1400

C, and the
BZCYO pellets sintered at (d) 1300

C, (e) 1400

C, and (f) 1450

C for 5 h.
Table 1 e The relative densities of the CYO and BZCYO
pellets sintered at different temperatures.
Sample Relative density (%)
1200

C 1300

C 1400

C 1450

C
CYO 69.8 85.3 95.1
BZCYO 66.1 80.7 89.3
i nt e r na t i o na l j our na l o f hy d r og e n e ne r g y 3 7 ( 2 0 1 2 ) 1 3 0 4 4 e1 3 0 5 2 13047
of oxygen vacancies. These vacancies are produced from the
defect reaction (1) using Kro gereVink notation as follows:
Y
2
O
3
!
CeO
2
2Y
0
Ce
3O

O
V

O
(1)
Fig. 4 also exhibits an increase in the oxygen-ion conduc-
tivity withthe sintered temperature. The CYOsample sintered
at 1400

C shows the highest oxygen-ion conductivity,
0.016 S cm
1
at 600

C, which is much higher than that of the
CYO pellet prepared by the oxalate co-precipitation route and
sintered at 1500

C for 5 h [20]. The increase in electrical
conductivity with sintered temperature from1200 to 1400

C is
attributed to the increase in the grain size (Fig. 3aec) resulting
in the decrease of grain boundary resistance. The activation
energies for oxygen-ion conduction in CYO electrolytes sin-
tered at different temperatures are calculated from the
Arrhenius equation s A/Texp(E
a
/kT ). It is seen from Fig. 4
that the activation energy (E
a
) for oxygen-ion conduction
decreases from 0.943 eV for CYO sample sintered at 1200

C to
0.873 eV at 1400

C, indicating that sintering at 1400

C is
benecial for ion conduction at much lower temperature.
Note that the CYO sample sintered at 1400

C shows compa-
rable activation energy with the CYO samples prepared by
citric acidenitrate combustionprocess [22], but the former has
higher oxygen-ion conductivity than the latter.
Fig. 5 shows the Arrhenius plot of the electrical conduc-
tivity in wet hydrogen (3% H
2
O) for BZCYO electrolytes from
the powder calcined at 1000

C sintered at 1300, 1400 and
1450

C, respectively. An approximately linear relationship is
also found in the measured temperature range for each
BZCYO sample and the electrical conductivity increases with
the measured temperature, indicating that the sintered
BZCYO electrolyte pellets are pure proton conductors in wet
hydrogen atmosphere. As to A

O
3
perovskite-type oxides,
oxygen vacancies are introduced into the perovskite structure
by aliovalent doping. The doping reaction for an acceptor Y on
the B site of BaCeO
3
in dry atmospheres during the synthesis
process can be written as follows:
Y
2
O
3
2BaO!
CeO
2
2Ba

Ba
2Y
0
Ce
5O

O
V

O
(2)
When the sample is sintered under oxygen-containing
atmospheres the reaction (3) may occur
V

O

1
2
O
2
g5O

O
2h

(3)
In dry hydrogen, the proton can be produced in the form of
hydroxyl according to the reaction (4)
H
2
2O

O
2h

52OH

O
(4)
In wet hydrogen, the proton conduction may appear due to
incorporation of water into the sample to form hydroxyl
species according to the reactions (5) and (6)
H
2
Og 2O

O
2h

52OH

1
2
O
2
g (5)
H
2
Og O

O
V

O
52OH

O
(6)
It is believed that protons can migrate by hopping from the
OH

O
site to O

O
site nearby causing this material to exhibit the
proton conductivity. From Fig. 5, it is seen that the proton
conductivity of BZCYO samples increases with the sintered
temperature from1300

C to 1450

C. This agrees with the SEM

analysis (Fig. 3def) that showed an increasing grain size with
increasing sintered temperature. A larger grain size leads to
a smaller grain boundary surface, resulting in higher electrical
conductivity for the samples with increasing sintered
temperature. At 600

C, the proton conductivity values were
measured at 7.89 10
3
S cm
1
for the sample sintered at
1300

C, increasing up to 1.21 10
2
S cm
1
at 1400

C and
1.28 10
2
S cm
1
at 1450

C. Fromthe tted Arrhenius curves

1.0 1.1 1.2 1.3 1.4 1.5
-2
-1
0
1
2
3
4
750 700 650 600 550 500 450 400
t (
o
C)
1200
o
C
1300
o
C
1400
o
C
l
n
(
T
)
(
S
c
m
-
1
K
)
1000/T (K
-1
)
0.873eV
0.916eV
0.943eV
Dry air
Fig. 4 e Arrhenius plot of the electrical conductivity in dry
air for CYO electrolyte pellets from the powder calcined at
700

C sintered at 1200, 1300 and 1400

C for 5 h,
respectively.
1.0 1.1 1.2 1.3 1.4 1.5
0.0
0.5
1.0
1.5
2.0
2.5
3.0
3.5
4.0
750 700 650 600 550 500 450 400
0.381eV
0.391eV
l
n
(
T
)

(
S
c
m
-
1
K
)
1000/T (K
-1
)
1300
o
C
1400
o
C
1450
o
C
0.378eV
Wet hydrogen (3% H
2
O)
t (
o
C)
Fig. 5 e Arrhenius plot of the electrical conductivity in wet
hydrogen (3% H
2
O) for BZCYO electrolyte pellets from the
powder calcined at 700

C sintered at 1300, 1400 and
1450

C for 5 h, respectively.
i nt e r na t i ona l j o ur na l o f hy d r o g e n e ne r g y 3 7 ( 2 0 1 2 ) 1 3 0 4 4 e1 3 0 5 2 13048
shown in Fig. 5, the activation energies are 0.378 eV, 0.381 eV,
and 0.391 eV, respectively when the sintered temperature of
BZCYO electrolyte increases from 1300

C to 1450

C. The
proton conductivity for BZCYO sample sintered at 1400

C in
this study are much higher than that for BZCYO samples
prepared by gel-casting and sintered at 1550

C [23] in the
measured temperature range of 400e700

C, and the activa-
tion energy for the former is much lower than that for the
latter, although the relative density of the former (80.7%) is
lower than that for the latter (95%).
3.4. Phase stability of CYOeBZCYO composite
electrolytes
Fig. 6 shows the XRD patterns of CYOeBZCYO composite
electrolytes containing 20wt.% BZCYO sintered at 1300, 1400,
and 1450

C for 5 h, respectively. The diffraction pattern of the
composite sample sintered at 1300

C consisted of two phases:

the pure uorite phase from CYO and the pure perovskite
phase fromBZCYO. After sintered at 1400

C for 5 h, a minor of
additional Ba
2
YZrO
6
phase (JCPDS Card Number 47-0385) and
Ba
2
ZrO
4
$2.15H
2
O phase (JCPDS Card Number 43-0653) is
detected, indicating that phase segregation and interdiffusion
arose in the two-phase system during high temperature sin-
tering and hygroscopic absorption occurred when exposed in
ambient atmosphere. When the sintered temperature
increased to 1450

C, the proportion of Ba
2
YZrO
6
cubic phase
in the composite electrolyte increased signicantly, in
contrast, the proportions of CeO
2
uorite phase and BaCeO
3
perovskite phase decreased.
3.5. Electrical conductivity of CYOeBZCYO composite
electrolytes
Fig. 7 presents the Arrhenius plots of the electrical conduc-
tivity in dry air for CYOeBZCYO composite electrolytes con-
taining 20wt.% BZCYO sintered at 1300, 1400 and 1450

C,
respectively. It is obvious that all the tted Arrhenius curves
can be separated into two straight lines at about 500

C for
each sample sintered from 1300

C to 1450

C, indicating that
the conduction mechanism of the composite alters at this
temperature. Ceria phase exhibits pure oxygen-ion conduc-
tion in dry air. For doped barium cerate in dry air, oxygen-ion
conductivity is suggested to be dominant at lowtemperatures,
while electron hole conductivity is suggested to be dominant
at elevated temperatures [24]. Thereby, the composite acts as
oxygen-ion conductor at lower temperatures and mixed
oxygen-ion and electron hole conductor at higher tempera-
tures in dry air.
It can be seen in Fig. 7 that the composite electrolyte sin-
tered at 1400

C showed the highest electrical conductivity
compared with the samples sintered at 1300

C and 1450

C in
the measured temperature range, which can be attributed to
the comprehensive effect of grainsizes and impurities. Onone
hand, the grain sizes of both CYOphase and BZCYOphase will
increase with increasing sintered temperature, leading to
higher electrical conductivity. On the other hand, the
increasing content of impurities including Ba
2
YZrO
6
and
Ba
2
ZrO
4
may cause the deterioration of ion conduction espe-
cially in the interfacial regions.
Fig. 8 shows the Arrhenius plots of the electrical conduc-
tivity in wet hydrogen (3% H
2
O) for CYOeBZCYO composite
electrolytes containing 20wt.% BZCYO sintered at 1300, 1400
and 1450

C, respectively. It is evident that the conduction
mechanism alters at about 600

C in wet hydrogen atmo-
sphere. It is well known that electron conduction can be
introduced into doped ceria at low oxygen partial pressure
and high temperature according to the reaction (7).
O

O
52e
0
V

O

1
2
O
2
(7)
In wet hydrogen environment, ceria phase exhibits a mixed
oxygen-ion, proton and electron conduction [25], and barium
cerate phase exhibits pure proton conduction. At lower
Fig. 6 e XRD patterns of CYOeBZCYO composite
electrolytes containing 20wt.% BZCYO sintered at 1300,
1400, and 1450

C for 5 h, respectively.
1.0 1.1 1.2 1.3 1.4 1.5
-2
-1
0
1
2
3
4
t (
o
C)
1300
o
C
1400
o
C
1450
o
C
l
n
(
T
)

(
S
c
m
-
1
K
)
1000/T (K
-1
)
Dry air
0.772eV
0.718eV
0.752eV
0.672eV
0.751eV
0.631eV
750 700 650 600 550 500 450 400
Fig. 7 e Arrhenius plots of the electrical conductivity in dry
air for CYOeBZCYO composite electrolytes containing
20wt.% BZCYO sintered at 1300, 1400 and 1450

C,
respectively.
i nt e r na t i o na l j our na l o f hy d r og e n e ne r g y 3 7 ( 2 0 1 2 ) 1 3 0 4 4 e1 3 0 5 2 13049
temperatures (below 600

C), the electron conduction of CYO
phase is not signicant and it can be blocked by the pure
proton conductor BZCYO, thus CYOeBZCYO composite con-
taining 20wt.% BZCYO shows hybrid oxygen-ion and proton
conduction in this condition. The composite sample sintered
at 1400

C has the lowest activation energy 0.756 eV below
600

C, which is higher than that of pure BZCYO in wet
hydrogen atmosphere. At higher temperature (above 600

C),
the electron conduction becomes innegligible, thus the
composite is a mixed ion-electron conductor. Among the
three composite samples, the sample sintered at 1400

C still
exhibits the highest electrical conductivity in wet hydrogen.
This conrms that the presence of impurities will deteriorate
the electrical conductivity of the composite. Hence, the
appropriate sintered temperature is set at 1400

C for
CYOeBZCYO composite electrolytes.
It is seem from Figs. 7 and 8 that the composite sample
shows much higher electrical conductivities in wet hydrogen
than in dry air at the measured temperature range of
400e700

C. In dry air, the conductivity is only 1.03 10
2
and
7.0 10
4
S cm
1
at 600

C and 400

C, respectively; while it
increases to 8.49 10
2
and 5.9 10
3
S cm
1
in wet hydrogen
at the sametemperatures, respectively. Similar result has been
reported by Sun et al. [26] for the BaCe
0.8
Sm
0.2
O
3d
eCe
0.8
Sm
0.2
O
2d
composite (weight ratio 1:1); however, this
compositeelectrolyteshows muchlower conductivitythanthe
BaZr
0.1
Ce
0.7
Y
0.2
O
3d
eCe
0.8
Y
0.2
O
2d
composite (weight ratio 1:4)
in this study either in dry air or in wet hydrogen atmosphere.
Fig. 9 shows the electrical conductivity measured in dry air
as a function of temperature for CYOeBZCYO composite
electrolytes with different compositions sintered at 1400

Cfor
5 h. It is clear from Fig. 9 that the activation energies decrease
gradually with the increase of BZCYO content in the
CYOeBZCYO system, but the conductivities of CYOeBZCYO
composite electrolytes are muchlower thanthose of pure CYO
and BZCYOelectrolytes at elevated temperatures. This may be
caused by the increasing amount of impurities including
Ba
2
YZrO
6
and Ba
2
ZrO
4
in the composites with increasing
BZCYO content. For the composites containing 20wt.% and
30wt.% BZCYO, both CYO phase and BZCYO phase can
conduct oxygen-ion via oxygen vacancies. Moreover, consec-
utive two-phase interfaces can be formed in the matrix of CYO
phase which facilitates the interfacial conduction, despite of
the presence of small amount of impurities.
1.0 1.1 1.2 1.3 1.4 1.5
-1
0
1
2
3
4
5
6
750 700 650 600 550 500 450 400
1450
o
C
1400
o
C
1300
o
C
l
n
(
T
)

(
S
c
m
-
1
K
)
1000/T (K
-1
)
t (
o
C)
0.439eV
0.462eV
0.756eV
Wet hydrogen (3% H
2
O)
0.853eV
0.580eV
0.930eV
Fig. 8 e Arrhenius plots of the electrical conductivity in wet
hydrogen (3% H
2
O) for CYOeBZCYO composite electrolytes
containing 20wt.% BZCYO sintered at 1300, 1400 and
1450

C, respectively.
1.0 1.1 1.2 1.3 1.4 1.5
-6
-5
-4
-3
-2
-1
0
1
2
3
4
750 700 650 600 550 500 450 400
t (
o
C)
x =0wt.%
x =20wt.%
x =30wt.%
x =50wt.%
x =70wt.%
x =100wt.%
l
n
(
T
)
(
S
c
m
-
1
K
)
1000/T (K
-1
)
(1-x)CYO-xBZCYO
Dry air
0.873eV
0.416eV
0.756eV
0.705eV
0.652eV
0.607eV
0.580eV
Fig. 9 e Electrical conductivity measured in dry air as
a function of temperature for CYOeBZCYO composite
electrolytes with different compositions sintered at 1400

C
for 5 h.
1.0 1.1 1.2 1.3 1.4 1.5
-6
-5
-4
-3
-2
-1
0
1
2
3
4
5
6
750 700 650 600 550 500 450 400
0.414eV
0.711eV
t (
o
C)
Wet hydrogen (3% H
2
O)
l
n
(
T
)

(
S
c
m
-
1
K
)
1000/T (K
-1
)
x =0wt.%
x =20wt.%
x =30wt.%
x =50wt.%
x =70wt.%
x =100wt.%
(1-x)CYO-xBZCYO
0.579eV
0.756eV
0.525eV
0.381eV
0.399eV
0.895eV
0.439eV
Fig. 10 e Electrical conductivity measured in wet hydrogen
(3% H
2
O) as a function of temperature for CYOeBZCYO
composite electrolytes with different compositions
sintered at 1400

C for 5 h.
i nt e r na t i ona l j o ur na l o f hy d r o g e n e ne r g y 3 7 ( 2 0 1 2 ) 1 3 0 4 4 e1 3 0 5 2 13050
Fig. 10 shows the electrical conductivity measured in wet
hydrogen (3% H
2
O) as a function of temperature for
CYOeBZCYO composite electrolytes with different composi-
tions sintered at 1400

C for 5h. At lowtemperatures (<600

C),
the activation energies decrease gradually with the increasing
of BZCYO content, but at high temperatures (600

C), the
difference in activation energy for the CYOeBZCYOcomposite
electrolytes is not marked. Composition dependences of
conductivity measured in wet hydrogen for the CYOeBZCYO
system are also illustrated in Fig. 10. With increasing amount
of BZCYO, the conductivity of the composite electrolytes
rstly increases to a maximum value then decreases sharply
especially when the BZCYO content exceeds 50wt.%. The
minimum conductivity is obtained by the composite electro-
lyte containing 70wt.% BZCYO, and the maximum conduc-
tivities are achieved by the composite electrolyte containing
20wt.% BZCYO at 550e700

C and the composite electrolyte
containing 30wt.% BZCYO at 400e500

C. Comparing the
composite electrolyte containing 30wt.% BZCYO with pure
BZCYO, the conductivity is greatly enhanced at low temper-
atures. The highest conductivities of 3.27 10
2
S cm
1
and
9.40 10
3
S cm
1
are achieved at 500

C and 400

C, respec-
tively, which are about 3e5 times higher than those of pure
CYO and BZCYO, implying the composite effect is functioned
in the CYOeBZCYO system. The composite effect can be
ascribed to the interfacial proton conduction via oxygen
vacancy or/and electron hole. Further studies will be carried
out to explore the detailed conduction mechanism in the
CYOeBZCYO system.
4. Conclusion
Novel composite electrolytes were developed based on a uo-
rite-type CYO synthesized by the carbonate co-precipitation
route at 700

C and a perovskite-type BZCYO synthesized by
the solegel process at 1000

C. The appropriate sintered
temperature for the composite electrolyte should not exceed
1400

C to maintain phase stability and high conductivity.
Compared with CYO and BZCYO, the composite electrolytes
showed much lower conductivity in dry air, however, they
showed greatly enhanced conductivity in wet hydrogen (3%
H
2
O). The highest conductivities of 3.27 10
2
S cm
1
and
9.40 10
3
S cm
1
were achieved at 500

C and 400

C in wet
hydrogen by the composite containing 30wt.% BZCYO, indi-
cating that this highly proton-conductive composite is
a promising candidate as electrolyte for LT-SOFCs.
Acknowledgments
This work was nancially supported by the National Natural
Science Foundation (NSFC) of China (No. 50902083), the NSFC
Fund for Creative Research Groups (No. 50821064), the
National Basic Research Program of China (No. 2012CB215401)
and the fundamental research funds for the central
universities.
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