Composite oxygen electrode LSM-BCZYZ

impregnated with Co
3
O
4
nanoparticles for steam
electrolysis in a proton-conducting solid oxide
electrolyzer
Shisong Li
a
, Ruiqiang Yan
b
, Guoijan Wu
a
, Kui Xie
a,
*, Jigui Cheng
a,
*
a
School of Materials Science and Engineering, Hefei University of Technology, No. 193, Tunxi Road, Hefei, Anhui
230009, China
b
Department of Polymer Science and Engineering, Zhejiang University, Hangzhou 310027, China
a r t i c l e i n f o
Article history:
Received 15 July 2013
Received in revised form
14 September 2013
Accepted 15 September 2013
Available online 10 October 2013
Keywords:
Proton conductor
Solid oxide electrolyzer
Steam electrolysis
Electrode improvement
a b s t r a c t
A composite oxygen electrode based on Co
3
O
4
-loaded La
0.8
Sr
0.2
MnO
3
(LSM)-
BaCe
0.5
Zr
0.3
Y
0.16
Zn
0.04
O
3d
(BCZYZ) is investigated for steam electrolysis in a proton-
conducting solid oxide electrolyzer. The conductivity of LSM is studied with respect to
temperature and oxygen partial pressure and correlated to the electrochemical properties
of the composite oxygen electrodes in symmetric cells and solid oxide electrolyzers at
800

C. The optimal Co
3
O
4
loading in the composite oxygen electrode is systematically
investigated in symmetric cells; loading catalytically active Co
3
O
4
signicantly enhances
the electrode performance, unlike the bare LSM-BCZYZ electrode. Steam electrolysis was
then performed using LSM-BCZYZ and 6 wt.% Co
3
O
4
-loaded LSM-BCZYZ oxygen electrodes,
respectively. The Co
3
O
4
-loaded catalyst signicantly improves the electrode process and
enhances the current density below a certain applied voltage. The current efciencies
reach approximately 46% with a 10% H
2
O/air feed for the oxygen electrode.
Copyright 2013, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights
reserved.
1. Introduction
Hydrogen attracts research interest because it may be created
using renewable resources before storage and transportation;
moreover, it is an environmentally friendly source of energy
[1e6]. There are many sources used to produce hydrogen,
including fossil fuels, biomass, and electrochemistry. From a
long-term perspective, using water (steam) electrolysis
(H
2
O/H
2
1/2O
2
) in a solid oxide electrolyzer (SOE) to pro-
duce hydrogen has become more popular because the high
temperature contributes energy to the steam dissociation,
leading to favorable kinetic and thermodynamic properties
[7e12].
Proton-conducting solid oxide electrolyzers (SOE) are
inverted proton-conducting solid oxide fuel cells (SOFC); they
convert electrical energy directly into chemical energy [13e16]
and can efciently produce pure hydrogen via high tempera-
ture steam electrolysis. Using external electricity, steam is
split into oxygen and protons. The protons diffuse across the
proton-conducting electrolyte to the fuel electrode, where
pure hydrogen forms from protons with in the three-phase
boundary. Hydrogen formation only occurs in the fuel
* Corresponding authors.
E-mail addresses: xiekui@hfut.edu.cn (K. Xie), jgcheng63@sina.com (J. Cheng).
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 o na l j our na l o f hy d r og e n e ne r g y 3 8 ( 2 0 1 3 ) 1 4 9 4 3 e1 4 9 5 1
0360-3199/$ e see front matter Copyright 2013, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.ijhydene.2013.09.082
electrode compartment, making it unnecessary to separate
the hydrogen from the steam.
In a proton-conducting solid oxide electrolyzer, the oxygen
electrode is under strongly oxidizing conditions during the
steam electrolysis, conditions under which a purely redox
active metal cannot operate. Stable oxygen electrode mate-
rials with efcient catalytic performances must still be
developed. We have recently reported a composite oxygen
electrode based on La
0.6
Sr
0.4
Co
0.2
Fe
0.8
O
3d
, Ba
0.5
Sr
0.5
Co
0.8
Fe
0.2
O
3d
and (La
0.75
Sr
0.25
)
0.95
Mn
0.5
Cr
0.5
O
3d
for direct steam elec-
trolysis in a proton-conducting solid oxide electrolyzer [15,16].
However, the electrode polarization resistance of the elec-
trolyzer is still considerable, and the steam electrolysis re-
mains limited by the kinetics processes of the electrode.
Enhancing the electro-catalytic performance of the electrode
is aneffective way to improve the electrolytic process. Co
3
O
4
is
reportedly an efcient electro-catalyst for oxygen evolution
reactions (OER) in metal-air batteries [17e19] and alkaline
water electrolyzers [20e22]. In the oxygen electrode of a
proton-conducting electrolyzer, the H
2
O molecules are split
into O
2
ions and protons under an external electrolysis po-
tential, and the O
2
ions are oxidized to O
2
gas before being
released from the electrode. This process is also a typical ox-
ygen evolution reaction that occurs on the electrode of an
electrolyzer. Therefore, a Co
3
O
4
electro-catalyst might equally
enhance the electrode electro-catalytic performance of an
electrolyzer.
In this work, composite electrodes based on LSM-BCZYZ
and Co
3
O
4
-loaded LSM-BCZYZ are systematically investi-
gated as oxygen electrodes for steam electrolysis in proton-
conducting solid oxide electrolyzers. The electrical conduc-
tivity of La
0.8
Sr
0.2
MnO
3
is studied with respect to temperature
and oxygen partial pressure and correlated to the electro-
chemical properties of the composite oxygen electrodes in the
symmetric cells and solid oxide electrolyzers. The electro-
chemical performance of the composite electrodes based on
LSM-BCZYZ and Co
3
O
4
catalyst-loaded LSM-BCZYZ are sys-
temically studied in proton-conducting solid oxide electro-
lyzers for steam electrolysis.
2. Experimental
The La
0.8
Sr
0.2
MnO
3
powder was synthesized using a solid-
state reaction with an appropriate mixture of La
2
O
3
, SrCO
3
and MnO
2
powders. The mixture was ball-milled in acetone
before being dried and pressed into pellets at room tempera-
ture; subsequently, the material was treated at 1400

C for 10 h
in air. The pellets were then ground, repelletized and red at
same temperature for 10 h in air. The LSMpowder loaded with
10 wt.% Co
3
O
4
was generated by impregnating the LSM pow-
der with a Co(NO
3
)
2
solution followed by a heat treatment at
500

C for 30 min in air. All of the reagents (Chemical grade)
were purchased from the SINOPHARM Chemical Reagent Co.,
Ltd (China). X-ray diffraction (Rigaku, Japan) was conducted to
analyze the phase formation of the LSM and Co
3
O
4
-loaded
LSM powders. Appropriate amounts of the LSM powders were
pressed into a bar, followed by a 10 h heat treatment at 1400

C
in air before the conductivity test. The relative sample density
reached 76%. Conductivity tests were performed in air using
the dc four-terminal method from room temperature to
800

C; conductivity was recorded versus temperature with an
online system in 0.4

C steps. The relationship between con-
ductivity and oxygenpartial pressure was tested at 800

Cwith
oxygen partial pressures ranging from 0.2 to 10
20
atm, which
were adjusted by owing dry 5% H
2
/Ar at 20 ml min
1
.
BaCe
0.5
Zr
0.3
Y
0.16
Zn
0.04
O
3d
(BCZYZ) was synthesized using
a solid-state reaction method. The mixture of BaCO
3
, CeO
2
,
ZrO
2
, Y
2
O
3
and ZnO powders was ball-milled at room tem-
perature and subsequently red at 1300

C in air for 10 h. A 2-
mm-thick BCZYZ disc for an electrolyte support was prepared
by dry-pressing the BCZYZ powders into a green disk with a
20 mm diameter before sintering at 1400

C for 10 h. The
composite oxygen electrode slurry was prepared by milling
LSMwith BCZYZ (60:40 in weight ratio) in alpha-terpineol with
the proper amount of cellulose additive. Similarly, the com-
posite fuel electrode slurry was prepared using NiO and
BCZYZ (60:40 in weight ratio) with the method described
above. The solid oxide symmetric cell and solid oxide elec-
trolyzer with LSM-BCZYZ/BCZYZ/LSM-BCZYZ and LSM-
BCZYZ/BCZYZ/NiO-BCZYZ congurations were coated with
electrode slurry in symmetrical positions on electrolyte sup-
ports within a 1 cm
2
area followed by an appropriate heat
treatment (1400

C for the NiO-BCZYZ electrode; 1100

C for
the LSM-BCZYZ electrode) for 3 h in air. Different contents of
Co
3
O
4
-loaded LSM electrodes were achieved by impregnating
the LSM electrodes with an appropriate Co(NO
3
)
2
nitrate so-
lution several times, with a 30 min heat treatment at 500

C in
air after each impregnation. The maximal content of each
impregnation treatment was 2 wt.%. Silver paste was printed
onto both electrode surfaces followed by a 500

C heat treat-
ment (3

C

min
1
) for 30 min in air for current collection. Sil-
ver electrical wire (0.2 mmin diameter) was then connected to
both current collectors using silver paste followed by ring at
500

C (3

C

min
1
) for 30 min in air. The microstructures of
the LSM-BCZYZ and 6 wt.% Co
3
O
4
-LSM electrodes of the
symmetric cell were observed with a scanning electron mi-
croscope (SEM, SU8020, HITACHI, Japan). The LSM-BCZYZ
electrode symmetric cell and the Co
3
O
4
-loaded LSM-BCZYZ
electrode symmetric cells with different Co
3
O
4
contents
were tested at different applied current densities in air, as well
as under different oxygen partial pressures under OCV con-
ditions, at 800

C using an electrochemical workstation (IM6,
Zahner, Germany). All of the gas owrates were maintained at
30 ml

min
1
with a mass ow meter (D08-3F, Sevenstar, Bei-
jing, China).
The LSM-BCZYZ (40%) and (LSM-BCZYZ (40%))-Co
3
O
4
(6 wt.%) powders were produced by ball-milling LSM and
BCZYZ powders followed by the appropriate impregnation
treatment. The specic surface area (SSA) of these powders
was characterized by BET (Brunauer, Emmett and Teller)
measurements (SA 3100, Beckman Coulter).
The solid oxide electrolyzers based on the LSM-BCZYZ and
6 wt.% Co
3
O
4
-loaded LSM-BCZYZ oxygen electrodes were
sealed onto homemade testing jigs using ceramic paste (JD-
767, Jiudian, Dongguan, China) for the electrochemical mea-
surements. The electrolyzers were typically tested at 800

C
with 5% H
2
/Ar at 30 ml

min
1
fed into the fuel electrode and
10% H
2
O/Air (saturated steam concentration at 46

C [23]) at
30 ml

min
1
introduced to the oxygen electrode for
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 8 ( 2 0 1 3 ) 1 4 9 4 3 e1 4 9 5 1 14944
electrolysis. Currentevoltage (IeV) and short-term perfor-
mance under externally applied loads were tested at 800

C.
The AC impedances of the solid oxide electrolyzers were
tested with different applied voltages for electrode activation
using an electrochemical workstation (IM6, Zahner, Ger-
many). The gas ow rate was controlled with a mass ow
meter (D08-3F, Sevenstar, Beijing, China), and the product,
hydrogen, was detected using an online gas chromatograph
(GC9750II, Fuli, China).
3. Results and discussion
Fig. 1(a) and (b) display the XRD patterns for the LSM powders
with and without 10 wt.% Co
3
O
4
prepared via solid-state re-
actions and impregnation treatments, indicating that both
La
0.8
Sr
0.2
MnO
3
and Co
3
O
4
samples remain in pure phases
(LSM: PDF#86-1233; Co
3
O
4
: PDF#78-1969). The LSM is a p-type
electronic conductor that displays typical semiconducting
behavior with a positive temperature coefcient up to 800

C
in air, as illustrated in Fig. 2(a). The conductivity reaches
approximately 32 S

cm
1
at 800

C. The p-type behavior is also

observed in Fig. 2(b). The conductivity decreases when the
oxygen partial pressure decreases because there are signi-
cantly fewer charge carriers (h

) in reducing atmospheres. The

decreased oxygen partial pressure causes oxygen loss,
simultaneously decreasing the hole concentration [15].
The BET results indicate that the specic surface area (SSA)
of the LSM-BCZYZ (40 wt.%) powder is 1.938 m
2
/g. In contrast,
the SSAof the (LSM-BCZYZ (40 wt.%))-Co
3
O
4
(6 wt.%) powder is
6.574 m
2
/g. The SSA increases approximately 239% after the
Co(NO
3
)
2
solution (6 wt.% Co
3
O
4
) is added to the LSM-BCZYZ
powder before the 30 min, 500

Cheat treatment. The Co(NO

3
)
2
solution decomposes to form Co
3
O
4
nanoparticles that are
loaded on the electrode surface after the heat treatment,
enhancing the oxygen evolution reaction and ameliorating
the three-phase boundary of the electrode. Fig. 3(a) and (b)
reveal the microstructure of the electrodes based on LSM-
BCZYZ and LSM-BCZYZ-6 wt.%Co
3
O
4
. Fig. 3(a) presents the
electrode microstructure of LSM-BCZYZ electrode, revealing
the porosity of the electrode. Nano-occus Co
3
O
4
lled some
pores in the electrode, as shown in Fig. 3(b).
Fig. 4(a1)e(a3) displays the AC impedance of the solid oxide
symmetric cell with a LSM-BCZYZ/BCZYZ/LSM-BCZYZ
conguration that was tested at 800

C while passing
different current densities through two electrodes in air. The
series resistance (R
s
) is approximately 4.37 U

cm
2
at OCV and
is reasonable for the 2-mm-thick BCZYZ electrolyte at 800

C
in air. In Fig. 4, the series resistance gradually decreases at a
large current density; this trend might be related to the p-type
conducting properties of BCZYZ electrolyte because it is a
mixed conductor in air [15,16,24]. As shown in Fig. 6(a), the
electrode polarization resistance (R
p
) of the cell is approxi-
mately 0.1 U

cm
2
, and it decreases further when the current
Fig. 1 e The XRD patterns of the LSM powders (a) and 10 wt.% Co
3
O
4
-loaded LSM powders (b) prepared via solid-state
reaction and impregnation treatments.
Fig. 2 e The conductivity of La
0.8
Sr
0.2
MnO
3
versus (a) temperature in air and (b) oxygen partial pressure at 800

C.
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 8 ( 2 0 1 3 ) 1 4 9 4 3 e1 4 9 5 1 14945
densities increase, demonstrating that the activity of LSM-
BCZYZ electrode is efcient under different current densities
in air. The symmetric cell based on the 6 wt.% Co
3
O
4
-loaded
LSM-BCZYZ composite with a 6 wt.% Co
3
O
4
-LSM-BCZYZ/
BCZYZ/6wt.% Co
3
O
4
-LSM-BCZYZ conguration exhibits the
same phenomenon shown in Figs. 4(b1)e(b3) and 6(a). The R
s
is approximately 4.23 U

cm
2
, and the R
p
is approximately
0.03 U

cm
2
under the OCV conditions; it decreases further at
Fig. 3 e The electrode microstructure of symmetric cells based on LSM-BCZYZ (a) and 6 wt.% Co
3
O
4
-(LSM-BCZYZ) (b)
electrodes before testing.
Fig. 4 e AC impedance of the symmetric solid oxide cells LSM-BCZYZ/BCZYZ/LSM-BCZYZ (a1ea3) and 6 wt.% Co
3
O
4
-(LSM-
BCZYZ)/BCZYZ/6 wt.%Co
3
O
4
-(LSM-BCZYZ) (b1eb3) tested at 800

C in air under different current densities.
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 8 ( 2 0 1 3 ) 1 4 9 4 3 e1 4 9 5 1 14946
Fig. 5 e AC impedance of the symmetric solid oxide cells LSM-BCZYZ/BCZYZ/LSM-BCZYZ (a1)e(a3) and 6 wt.% Co
3
O
4
-(LSM-
BCZYZ)/BCZYZ/6 wt.% Co
3
O
4
-(LSM-BCZYZ) (b1)e(b3) tested at 800

C at different oxygen partial pressure under OCV
conditions.
Fig. 6 e The electrode polarization resistance (R
p
) of symmetric cells with different Co
3
O
4
-loaded LSM-BCZYZ composite
electrode contents versus (a) passing current density and (b) oxygen partial pressure.
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 8 ( 2 0 1 3 ) 1 4 9 4 3 e1 4 9 5 1 14947
large current densities. The electrode performance is signi-
cantly improved when the Co
3
O
4
catalyst is added; the Co
3
O
4
ameliorates the three-phase boundary of the electrode, im-
proves the reaction overpotential and enhances the oxygen
evolution reaction. The AC impedance of the LSM-BCZYZ and
6 wt.% Co
3
O
4
-LSM-BCZYZ composite oxygen electrodes in
symmetric cells are also tested under different oxygen partial
pressures at 800

C. As shown in Fig. 5(a1)e(a3) and (b1)e(b3),
the R
s
of both cells gradually decrease with the oxygen partial
pressure up to 20% (0.2 atm), demonstrating that a small
amount of p-type conduction might occur in BCZYZ electro-
lyte [24]. Similarly, the R
p
of the cells also improves when
increasing the oxygen partial pressure; this effect is closely
related to p-type conducting properties of LSM ceramics, as
discussed above.
To understand the changes in electrode performance,
symmetric cells with different Co
3
O
4
contents loaded into
LSM-BCZYZ electrodes are systemically studied. Fig. 6(a) il-
lustrates the relationship between the electrode polarization
resistance (R
p
) of LSM-BCZYZ composite electrode symmetric
cells loaded with different Co
3
O
4
contents and under different
passing current densities at 800

C in static air. The R
p
de-
creases with increased passing current densities in a cell, and
the R
p
is lowered as the Co
3
O
4
content loaded increases at a
xed passing current. When a considerable amount of Co
3
O
4
is loaded, the electrode polarization resistance (R
p
) decreases
signicantly and remains stable when the additive content
exceeds 6 wt.% because using the Co
3
O
4
as a catalyst possibly
improved the three-phase boundary of the electrode,
enhancing the overpotential and electrode electrochemical
process [25e30]. Similar regularity is observed in Fig. 6(b) in
the pattern of electrode polarization resistance (R
p
) in the
LSM-BCZYZ composite electrode symmetric cells loaded with
different Co
3
O
4
contents versus oxygen partial pressure at
800

C under OCV conditions. The R
p
gradually decreases
when the Co
3
O
4
content increases at a xed oxygen partial
pressure. The R
p
also decreases when the oxygen partial
pressure increases in one cell; this pattern is closely related to
the p-type conductivity of LSM ceramic, as discussed above.
To assess the seal on a single solid oxide electrolyzer based
on a LSM-BCZYZ composite oxygen electrode, 10% H
2
O/Air is
introduced to the oxygen electrode while the fuel electrode is
exposed to 5% H
2
/Ar. The open circuit voltage (OCV) reaches
0.92 V at 800

C, indicating a reasonable separation between
the anodic and cathodic gases. At this point, the electro-
chemical cell is a solid oxide fuel cell, and the OCV mainly
arises from the electrochemical potential (2H
2
O
2
/ 2H
2
O).
Fig. 7(a) displays the current density against the applied
voltage (IeV curve) at 800

C with 10% H
2
O/Air supplied to the
oxygen electrode while the fuel electrode is exposed to 5% H
2
/
Ar. The IeV curve is not linear, revealing the change in cell
resistance across the entire voltage region. The maximum
current density reaches 157 mA

cm
2
at 2 V. To study the
change in electrolyzer resistance under different applied
voltages, the dV/dI curve (cell total resistance) is plotted
versus voltage, as shown in Fig. 7(c). The resistance gradually
decreases when the voltage increases to 1.2 V, remaining
stable at approximately 6.5 U

cm
2
at higher voltages. In situ
Fig. 7 e IeV curve of the solid oxide electrolyzers based on LSM-BCZYZ (a) and 6 wt.% Co
3
O
4
-LSM-BCZYZ (b) composite
oxygen electrode for steam electrolysis with 10% H
2
O/Air fed to the oxygen electrode and 5% H
2
/Ar introduced to the fuel
electrode; the dV/dI (cell total resistance) of solid oxide electrolyzers based on LSM-BCZYZ (c) and 6 wt.% Co
3
O
4
-LSM-BCZYZ
(d) composite oxygen electrode.
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 8 ( 2 0 1 3 ) 1 4 9 4 3 e1 4 9 5 1 14948
AC impedance spectroscopy was also utilized under different
applied voltages to investigate the changes in R
s
and R
p
; R
s
and
R
p
correspond to the series resistance and polarization resis-
tance of the electrodes, respectively. As shown in Fig. 8(a1)
and (a2), the series resistance has its maximum value at the
OCV before decreasing relative to the applied voltage from
0.92 to 2.0 V due to the contribution of the p-type conduction
of the electrolyte [16,24]. The R
p
sharply decreases with
increasing voltage, most likely due to the reoxidation of the
LSM-BCZYZ electrode. The electrode polarization resistance
and total resistance are 0.38 U

cm
2
and 6.92 U

cm
2
at 2.0 V,
respectively. However, higher voltages improve the electrode
reactions, further enhancing the electrode process and
decreasing the electrode polarization resistance at higher
voltages.
The electrolyzer based on a 6 wt.% Co
3
O
4
-loaded LSM-
BCZYZ composite oxygen electrode is tested in a similar
manner as the electrolyzer with the LSM-BCZYZ oxygen
electrode. The OCV is 0.93 V at 800

C with 10% H
2
O/Air being
fed to oxygen electrode while the fuel electrode receives 5%
H
2
/Ar. The current density versus the applied voltage (IeV
curve) is displayed in Fig. 7(b); this curve is also nonlinear, and
the maximum current density is approximately 184 mA

cm
2
at 2 V. As shown in Fig. 7(d), the dV/dI (cell total resistance) is
approximately 4 U

cm
2
at a 2.0 V applied voltage. In Fig. 8(b1)
and (b2), the in situ AC impedance spectroscopy data for the
6 wt.% Co
3
O
4
-loaded LSM-BCZYZ composite oxygen electrode
electrolyzer reveals that the R
p
decreases signicantly when
the applied voltage increases because the reoxidation of LSM-
BCZYZ electrode enhances the conductivity of the LSM
ceramic. The electrode polarization resistance and the total
resistance are 0.24 U

cm
2
and 6.26 U

cm
2
at 2.0 V, respectively.
Fig. 8(c) compares the polarization resistance of the electro-
lyzers based on the LSM-BCZYZ and the 6 wt.% Co
3
O
4
-loaded
LSM-BCZYZ composite oxygen electrodes under different
applied voltages. Loading Co
3
O
4
onto the LSM-BCZYZ
Fig. 8 e AC impedance of the solid oxide electrolyzers based on LSM-BCZYZ (a1, a2) and 6 wt.% Co
3
O
4
-LSM-BCZYZ (b1, b2)
composite oxygen electrodes for steam electrolysis with 10% H
2
O/Air fed into the oxygen electrode and 5% H
2
/Ar introduced
to the fuel electrode; (c) the R
p
of electrolyzers versus applied voltages.
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 8 ( 2 0 1 3 ) 1 4 9 4 3 e1 4 9 5 1 14949
electrode greatly improves the electrode, enhancing the
electrode electrochemical process and decreasing the R
p
of the
electrolyzer.
Fig. 9 reveals the short-term performance of the electro-
lyzers based on LSM-BCZYZ and 6 wt.% Co
3
O
4
-loaded LSM-
BCZYZ composite electrodes for electrolyzing steam at 800

C
under different applied voltages. Fig. 9(a) and (b) displays the
current density versus time and applied voltage of the elec-
trolyzers based on LSM-BCZYZ and 6 wt.% Co
3
O
4
-loaded LSM-
BCZYZ electrodes tested at 800

C when 10% H
2
O/Air is fed
into the oxygen electrode and 5% H
2
/Ar is fed into the fuel
electrode, respectively. For the electrolyzer based on the LSM
electrode, the current densities are approximately 31, 53, 84,
113 and 152 mA

cm
2
at 1.2, 1.4, 1.6, 1.8 and 2.0 V, respectively.
Fig. 9(c) illustrates the H
2
production: 0.102, 0.166, 0.23, 0.279
and 0.348 ml

min
1
cm
2
at 1.2, 1.4, 1.6, 1.8 and 2.0 V, respec-
tively. The corresponding current efciencies are 46.6%, 45.3%,
38.9%, 33.8% and 32.6%. These values exceed the 22% current
efciency achieved by the La
0.75
Sr
0.25
Cr
0.5
Mn
0.5
O
3d
-based oxy-
gen electrode for steam electrolysis in a thin-membrane, pro-
ton-conducting, solid oxide electrolyzer [16] and are
comparable with La
0.6
Sr
0.4
Co
0.2
Fe
0.8
O
3d
and Ba
0.5
Sr
0.5
Co
0.8
Fe
0.2
O
3d
electrode electrolyzers during steam electrolysis in
proton-conducting solid oxide electrolyzers [15]. However, the
efciency decreases when the voltage improves. The current
efciency lost under higher voltages and currents are most
likely caused by the transportation of other ions or holes, as
well as the localized steam starvation at high voltages that
limits the electrochemical oxidation of steam in the oxygen
electrode [15,31]. For the electrolyzer based on the 6 wt.%
Co
3
O
4
-loaded LSM-BCZYZ electrode, the current densities are
approximately 41, 68, 98, 132 and 173 mA

cm
2
at 1.2, 1.4, 1.6,
1.8 and 2.0 V, respectively. The H
2
production is 0.131, 0.205,
0.266, 0.326 and 0.369 ml

min
1
cm
2
at 1.2, 1.4, 1.6, 1.8 and
2.0 V, respectively. The corresponding current efciencies are
45.4%, 43.3%, 38.4%, 34.8%and 30.8%and are comparable to the
cell based on the LSM-BCZYZ electrode. The lower current ef-
ciency in the electrolyzer is dictated by the ion conduction
from the proton-conducting electrolyte. The proton conduc-
tivity in the BCZYZ electrolyte relies on the partial lling of
vacant oxygen sites by water, yielding mobile protons bound to
the lattice oxide ions. The necessity of these oxide vacancies
complicates the transport properties. Under oxidative condi-
tions, atmospheric oxygen enters the lattice, creating hole-type
electronic conductionandlowering the current efciency of the
electrolyzer [24]. Consequently, the electrolyzer based on the
proton-conducting electrolyte has a lower current efciency
than that based on the oxide-ion conducting electrolyte.
There are two main electrochemical processes that occur
from OCV to 2 V during steam electrolysis: the reoxidation of
the LSM-BCZYZ electrode and steam electrolysis. The oxida-
tion of LSM is the major process below 1.2 V, while the elec-
trochemical oxidation of H
2
O dominates at high voltages.
Fig. 7(c) and (d) shows that the dV/dI (cell resistance) remains
constant above 1.2 V, indicating there is sufcient oxidation of
the oxygen electrode and a stable steam electrolysis process.
4. Conclusions
In this work, composite oxygen electrodes based on LSM-
BCZYZ and Co
3
O
4
-loaded LSM-BCZYZ were investigated for
steam electrolysis in proton-conducting solid oxide electro-
lyzers. The LSMsample has p-type conducting properties; this
Fig. 9 e Short-term performance of the solid oxide electrolyzers based on LSM-BCZYZ (a) and 6 wt.% Co
3
O
4
-LSM-BCZYZ (b)
composite oxygen electrodes for steam electrolysis at 800

C with 10% H
2
O/Air fed into the oxygen electrode and 5% H
2
/Ar
introduced to the fuel electrode; the H
2
production and current efciency of the electrolyzers based on LSM-BCZYZ (c) and
6 wt.% Co
3
O
4
-LSM-BCZYZ (d) composite oxygen electrodes.
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 8 ( 2 0 1 3 ) 1 4 9 4 3 e1 4 9 5 1 14950
material is investigated and correlated with the electro-
chemical properties of the symmetric cells and electrolyzers.
The optimal Co
3
O
4
loading in the composite oxygen electrode
is systematically investigated in symmetric cells: adding
catalytically active Co
3
O
4
signicantly enhances the electrode
performance compared to the bare LSM-BCZYZ electrode.
Steam electrolysis was conducted on electrolyzers using LSM-
BCZYZ and 6 wt.% Co
3
O
4
-loaded LSM-BCZYZ oxygen elec-
trodes; adding the Co
3
O
4
catalyst signicantly improves the
electrode processes and enhances the current density under a
certain applied voltage. The signicantly improved electrode
performance after adding the catalytically active Co
3
O
4
may
be because the Co
3
O
4
ameliorates the three-phase boundary
of electrode, improving the reaction overpotential and
enhancing the oxygen evolution reaction.
Acknowledgment
This work is supported by the Natural Science Foundation of
China No. 21303037, China Postdoctoral Science Foundation
No. 2013M53150 and the Fundamental Research Funds for the
Central Universities No. 2012HGZY0001.
r e f e r e n c e s
[1] Brisse A, Schefold J, Zahid M. High temperature water
electrolysis in solid oxide cells. Int J Hydrogen Energy
2008;33:5375e82.
[2] Hauch A, Ebbesen S, Jensen S, Mogensen M. Highly efcient
high temperature electrolysis. J Mater Chem
2008;18:2331e40.
[3] Schiller G, Ansar A, Lang M, Patz O. High temperature water
electrolysis using metal supported solid oxide electrolyser
cells (SOEC). J Appl Electrochem 2009;39:293e301.
[4] Jin C, Yang C, Zhao F, Cui D, Chen F. La
0.75
Sr
0.25
Cr
0.5
Mn
0.5
O
3
as hydrogen electrode for solid oxide electrolysis cells. Int J
Hydrogen Energy 2011;36:3340e6.
[5] Yang X, Irvine JTS. (La
0.75
Sr
0.25
)
0.95
Mn
0.5
Cr
0.5
O
3
as the cathode
of solid oxide electrolysis cells for high temperature
hydrogen production from steam. J Mater Chem
2008;18:2349e54.
[6] Ni M, Leung MKH, Leung DYC. Technological development of
hydrogen production by solid oxide electrolyzer cell (SOEC).
Int J Hydrogen Energy 2008;33:2337e54.
[7] Xie K, Zhang YQ, Meng GY, Irvine JTS. Direct synthesis of
methane from CO
2
/H
2
O in an oxygen-ion conducting solid
oxide electrolyser. Energy Environ Sci 2011;4:2218e22.
[8] Xie K, Zhang YQ, Meng GY, Irvine JTS. Electrochemical
reduction of CO
2
in a proton conducting solid oxide
electrolyser. J Mater Chem 2011;21:195e8.
[9] Doenitz W, Schmidberger R, Steinheil E, Streicher R.
Hydrogen production by high temperature electrolysis of
water vapour. Int J Hydrogen Energy 1980;5:55e63.
[10] Balthasar W. Hydrogen production and technology: today,
tomorrow and beyond. Int J Hydrogen Energy 1984;9:649e68.
[11] Dutta S. Technology assessment of advanced electrolytic
hydrogen production. Int J Hydrogen Energy 1990;15:379e86.
[12] Li SS, Li YX, Gan Y, Xie K, Meng GY. Electrolysis of H
2
O and
CO
2
in an oxygen-ion conducting solid oxide electrolyzer
with a La
0.2
Sr
0.8
TiO
3d
composite cathode. J Power Sources
2012;218:244e9.
[13] Iwahara H, Uchida H, Yamasaki I. High-temperature steam
electrolysis using SrCeO
3
-based proton conductive solid
electrolyte. Int J Hydrogen Energy 1987;12:73e7.
[14] Schober T. Applications of oxidic high-temperature proton
conductors. Solid State Ionics 2003;162:277e81.
[15] Li SS, Xie K. Composite oxygen electrode based on LSCF and
BSCF for steam electrolysis in a proton-conducting solid
oxide electrolyzer. J Electrochem Soc 2013;160:F224e33.
[16] Gan Y, Zhang J, Li YX, Li SS, Xie K, Irvine JTS. Composite
oxygen electrode based on LSCM for steam electrolysis in a
proton conducting solid oxide electrolyzer. J Electrochem Soc
2012;159:F763e7.
[17] Kong F. Synthesis of rod and beadlike Co
3
O
4
and bi-
functional properties as air/oxygen electrode materials.
Electrochim Acta 2012;68:198e201.
[18] Lee J, Kim S, Cao R, Choi N, Liu M, Lee K, et al. Metal-air
batteries with high energy density: Li-air versus Zn-air. Adv
Energy Mater 2011;1:34e50.
[19] Nikolova V, Iliev P, Petrov K, Vitanov T, Zhecheva E,
Stoyanova R, et al. Electrocatalysts for bifunctional oxygen/
air electrodes. J Power Sources 2008;185:727e33.
[20] Singh R, Mishra D, Anindita Sinha A, Singh A. Novel
electrocatalysts for generating oxygen from alkaline water
electrolysis. Electrochem Commun 2007;9:1369e73.
[21] Lu B, Cao D, Wang P, Wang G, Gao Y. Oxygen evolution
reaction on Ni-substituted Co
3
O
4
nanowire array electrodes.
Int J Hydrogen Energy 2011;36:72e8.
[22] Li Y, Hasin P, Wu Y. Ni
x
Co
3x
O
4
nanowire arrays for
electrocatalytic oxygen evolution. Adv Mater 2010;22:1926e9.
[23] Yue XL, Irvine JTS. (La, Sr)(Cr, Mn)O
3
/GDC cathode for high
temperature steam electrolysis and steam-carbon dioxide
co-electrolysis. Solid State Ionics 2012;225:131e5.
[24] Tao SW, Irvine JTS. A stable. Easily sintered proton-
conducting oxide electrolyte for moderate-temperature fuel
cells and electrolyzers. Adv Mater 2006;18:1581e4.
[25] Lee WH, Kim H. Oxidized iridium nanodendrites as catalysts
for oxygen evolution reactions. Catal Commun
2011;12:408e11.
[26] Garsuch A, Panchenko A, Querner C, Karpov A, Oesten R.
FeAgMo
2
O
8
-A novel oxygen evolution catalyst material for
alkaline metal-air batteries. Electrochem Commun
2010;12:1642e5.
[27] Ma L, Sui S, Zhai Y. Preparation and characterization of Ir/TiC
catalyst for oxygen evolution. J Power Sources
2008;177:470e7.
[28] Wang W, Zhao Q, Dong J, Li J. A novel silver oxides oxygen
evolving catalyst for water splitting. Int J Hydrogen Energy
2011;36:7374e80.
[29] Hamdani M, Singh R, Chartier P. Co
3
O
4
and co-based spinel
oxides bifunctional oxygen electrodes. Int J Electrochem Sci
2010;5:556e77.
[30] Rios E, Reyes H, Ortiz J, Gautier JL. Double channel electrode
ow cell application to the study of HO
2
-
production on
Mn
x
Co
3x
O
4
(0 x 1) spinel lms. Electrochim Acta
2005;50:2705e11.
[31] Xu SS, Li SS, Yao WT, Dong DH, Xie K. Direct electrolysis of
CO
2
using an oxygen-ion conducting solid oxide electrolyzer
based on La
0.75
Sr
0.25
Cr
0.5
Mn
0.5
O
3d
electrode. J Power Sources
2013;230:115e21.
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 8 ( 2 0 1 3 ) 1 4 9 4 3 e1 4 9 5 1 14951