Solid State Ionics 275 (2015) 106109

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Solid State Ionics

journal homepage: www.elsevier.com/locate/ssi

Ce(Mn,Fe)O2(La,Sr)(Fe,Mn)O3 composite as an active cathode for

electrochemical reduction of CO2 in proton conducting solid oxide cells
Tae Ho Shin a,,1,2, Jae-ha Myung a,1, Khan M. Naeem a,b, Cristian Savaniu a, John T.S. Irvine a,
a
b

School of Chemistry, University of St Andrews, St Andrews, Scotland, United Kingdom

Centre of Advanced Materials and Energy Studies (CAMES), University Brunei Darussalam, Brunei

a r t i c l e

i n f o

Article history:
Received 12 December 2014
Received in revised form 24 February 2015
Accepted 11 March 2015
Available online 29 March 2015
Keywords:
Solid oxide electrolyser
Composite cathode
CO2 reduction
Proton conductor
Ceria

a b s t r a c t
A solid oxide electrolysis cell concept for reducing CO2 to CO was studied using a proton conducting
mixed oxide BaCe0.7Zr0.1Y0.1Yb0.06Zn0.04O3 (BCZYYZ) as an electrolyte. The oxide composite mixture:
Ce0.6Mn0.3Fe0.1O2La0.6Sr0.4Fe0.9Mn0.1O3 (12.587.5 wt.%) was examined as enhancing catalyst electrode for
CO2 reduction and proton oxidation reaction on the cathode side for avoiding coke formation. Here we demonstrate the successful electrochemical reduction of CO2 in proton conducting SOECs. During electrochemical
reduction of CO2 at 700 C, current densities as high as 0.5 A/cm2 and 1 A/cm2 at 1.3 V and 2.2 V respectively,
were withdrawn even though the cell employed a 400 m thick BCZYYZ electrolyte support.
2015 The Authors. Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/by-nc-nd/4.0/).

1. Introduction
Development of new energy sources such as solar and wind, giving a
rich and diverse energy supply based upon renewable and environmentally friendly sources, has emphasized the need for new methods of
energy storage. Recently, there has been an increased focus on hydrogen as an alternative energy mediator of conversion and storage because of high gravimetric energy density and zero carbon emission
[15]. However, the utilisation of hydrogen has been limited due to
the practical engineering and economic limitations with respect to its
generation and distribution [6]. On the other hand hydrocarbon fuels
and carbon monoxide match the existing energy infrastructure well because of their similarity to current fossil fuels; they would be effective
energy carriers in a period of transition toward zero carbon emission
[79]. The synthetic hydrocarbon fuels from CO2/H2O with renewable
electricity have therefore been proposed as an alternative method to
transport new energy sources from where they are available to its
point of use within a carbon neutral cycle [1013]. In addition, using
electrochemical reaction for recycling or reuse of CO2 from new energy
sources would therefore be a feasible alternative to advanced capture
and utilisation of CO2.
Corresponding authors at: School of Chemistry, University of St Andrews, St Andrews,
Fife, Scotland KY16 9ST, United Kingdom.
E-mail addresses: ths@st-andrews.ac.uk, ceramist95@gmail.com (T.H. Shin),
jtsi@st-andrews.ac.uk (J.T.S. Irvine).
1
These authors contributed equally to this work as rst author.
2
This author's afliation has been changed to Korea Institute of Ceramic Engineering
Technology (KICET).

A proton conducting solid oxide electrolyser has recently been

applied for electrolysis of water combined with electrochemical conversion of CO2 [1316]. Using a proton conducting oxide as electrolyte in
CO2 condition, it is possible to produce hydrogen from steam while
simultaneously reducing CO2 to generate hydrocarbon such as methane
as illustrated in Fig. 1. Xie et al. have demonstrated the successful in-situ
electrochemical conversion of H2O/CO2 into methane at 650 C from 1
to 2% of CO2 in previous work [13]. At the cathode side, if CO2 is fed
then reverse water gas shift reaction (WGSR) would take place following the overall cathode reaction.

CO2 4H 4e CO 2H2 O

If the partial pressure of CH4 at equilibrium is low, however, most

the CO2 would be converted into CO. In the case of the proton
conducting solid oxide cell, the electrochemical reaction would be
mainly dominated by the cathode reaction. Thus, the cathode should require good properties in terms of electrical conductivity as well as catalytic activity for hydrocarbon formation. Furthermore, carbon tolerance
would be one of the important issues because carbon deposition is likely
to occur at the cathode side during CO2 reduction. In the present work,
the mixed oxide composite with Ce(Mn, Fe)O2(La,Sr)(Fe,Mn)O3
(CMFLSFM) was employed as a catalyst coating layer on the cathode
side in proton conducting solid oxide cells to facilitate catalysis and
electrochemical electrode reaction with pure CO2 gas. The CMFLSFM
composite oxide previously showed outstanding catalytic activity for
fuel oxidation without carbon coking in the hydrocarbon-type solid
oxide fuel cells as an oxide anode [17,18]. Compare to the typical

http://dx.doi.org/10.1016/j.ssi.2015.03.015
0167-2738/ 2015 The Authors. Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).

T.H. Shin et al. / Solid State Ionics 275 (2015) 106109

(a)
CO2 Electrode

Protonic
Electrolyte

CO2

Steam Electrode

H 2O / H 2

107

(b) Single cathode: LSCF+GDC

CO2

BCZYYZ

LSCF + GDC
400 m
Ni-Fe (9:1)

3% H2O / H2

H+

(c) Double cathode: LSCF+GDC | CMF+LSFM

H 2+CO
+ CO 2
e-

H 2O, O 2

e-

CO2

BCZYYZ

CMF+LSFM
LSCF + GDC
400 m
Ni-Fe (9:1)

3% H2O / H2

Fig. 1. a) Schematic diagram of CO2 reduction in proton conductor. b) Cell conguration using single cathode layer, LSCF + GDC and c) double cathode layers, LSCF + GDC|CMF + LSFM.

cathode materials, (La,Sr)(Fe,Co)O3Gd doped ceria (GDC) cathode in

proton conducting electrolyser, CMFLSFM has an improved catalytic
activity for CO2 electro-conversion with a smaller overpotential loss.

Germany) with frequency ranged from 0.1 Hz to 100 kHz with amplitude of 10 mV.
3. Results and discussion

2. Experimental
Ce0.6Mn0.3Fe0.1O2 and La0.6Sr0.4Fe0.9Mn0.1O3 mixed oxides were
prepared using the conventional solid-state reaction method
described in detail previously [18]. The powders were mixed
under acetone in an agate mortar to form a composite oxide anode
consisting of 12.5 wt.% Ce(Mn, Fe)O2 and 87.5 wt.% La(Sr)Fe(Mn)O3.
BaCe0.7Zr0.1Y0.1Yb0.06Zn0.04O3 (BCZYYZ) powder was synthesized
by a modied glycine-nitrate combustion method. Ba(NO3)2 (98.0%,
Sigma-Aldrich Co. LLC, UK), Ce(NO3)36H2O(99.0%, Sigma-Aldrich Co.
LLC, UK), ZrO(NO3)2H2O, Y(NO3)36H2O (99.0%, Sigma-Aldrich Co.
LLC, UK), and Zn(NO3)26H2O(98.0%, Sigma-Aldrich Co. LLC, UK) were
added in the corresponding ratios into distilled water containing an
appropriate amount of citric acid (4:1 to metal ions) in a beaker under
stirring until a transparent and homogeneous solution was obtained.
The solution was evaporated on the hotplate and resulting powder
was calcined at 1000 C for crystallisation. The BCZYYZ electrolyte support was prepared by dry-pressing powder into a circular green body
followed by a high-temperature sintering in air at 1450 C for 6 h and
mechanical polishing until 2 cm diameter and 400 m thickness electrolyte supports were obtained. The faces of the BCZYYZ electrolyte disk
were coated with the corresponding electrode powder by screenprinting, and then electrodes were sintered at 1100 C for 30 min. To
compare with conventional La0.6Sr0.4Fe0.8Co0.2O3 (LSCF)Gd doped
ceria (GDC) commercial cathode, the CMFLSFM coating layer (b 5 m
thickness) was just added on top of the same LSCFGDC cathode in another single cell, NiFe|BCZYYZ|LSCFGDC|CMF-LSF. NiFe (9:1) alloy
powder was used for anode, coated using screen printing. To minimize
changing the geometric factor from adding CMFLSFM layer by screen
printing, coating layer was prepared as thin (b5 m) as possible. A
gold spot electrode prepared using commercial Au paste was used
as the reference electrode and was placed on the cathode side. We
connected gold lead wire to the reference electrode.
To evaluate electrochemical properties, IV curves and impedance
were measured with four silver leads with silver mesh as the electrode
current collector. In order to perform electrochemical testing in fuel cell
mode, humidied H2 was supplied into the NiFe electrode while the
cathode side was exposed to air as an oxidant gas. After fuel cell mode
test, 3 vol.% H2O/H2 and 100% CO2 were supplied into the anode
and cathode while external loading was also applied to perform the
electrochemical test for CO2 reduction. AC impedance spectroscopy
was recorded using an IM6 Electrochemical Workstation (Zahner,

Fig. 2 shows the microstructure of the CMFLSFM catalyst layer on

top of the LSCFGDC cathode layer together with the BCZYYZ electrolyte
support after electrochemical measurement. The adherence of the
electrolyte, cathode and functional catalyst layers is very good and no
delamination is observed even after the cell test. In addition, there
was no evidence for carbon deposition in cathode side during CO2 reduction. It is well known that a coke deposited resulted from CO2/CO
gas utilisation would appear as lament-like structures, leading to
catalyst deactivation. The absence of these structures suggests carbon
tolerance of the CMFLSFM in CO2 atmosphere, expected from previous
reports on the CMFLSFM composite SOFC anode [17].
To verify the inuence of CMFLSFM upon the catalytic activity of
the LSCFGDC cathode layer, electrochemical tests were performed on
cells comprising Ni:Fe anode, BCZYYZ electrolyte (400 m thick) and
LSCFGDC cathode with and without the added CMFLSFM functional
layer. Fig. 3 shows the currentpower density (IP) and currentvoltage
(IV) curves of the cell using the LSCFGDC cathode and CMFLSFM/
LSCFGDC dual cathode cell congurations. The open circuit voltage
(OCV) in humidied H2 fuel were close to the value predicted by the
Nernst equation, 1.061, 1.088, and 1.112 V at 800, 700, and 600 C,
respectively, for the cells having LSCFGDC cathode. On the other
hand, the OCV of the cell with added CMF-LSFM catalyst layer on the
LSCFGDC cathode was slightly lower than that of the cell using
only LSCFGDC cathode, 1.02, 1.066 and 1.102 V at 800, 700, and
600 C, respectively. According to previous literature for BaCeO3 proton
conductor, partial oxygen conduction would clearly occur at high temperature (N 700 C) and high oxygen partial pressure [19]. However,
the BCZYYZ electrolyte supporting cells were exposed to both high
oxygen condition (oxidant electrode) and lower oxygen condition
(fuel electrode) in real fuel cell operation mode. Thus, OCV value
would be more realistic information to check partial oxygen conduction
in proton electrolyte during operation rather than theoretical proton
transport number. Obviously, all of OCV values are over 1 V, which
is closed to theoretical value within whole temperature range
(600800 C) and OCV of ca. 1.1 V was particularly recorded at
600 C as shown in Fig. 3. It was observed that the introduction of
the CMFLSFM functional layer on the cathode side almost doubled
the maximum power density value (MPD) as can be seen from
Fig. 3(a) and (b), suggesting that not only catalytic surface activity
would be improved by CMFLSFM, but also the charge transfer is facilitated in the CMFLSFM catalytic functional layer because of its mixed

108

T.H. Shin et al. / Solid State Ionics 275 (2015) 106109

(a)

(b)
BCZYYZ

5m

Cathode CMF+LSFM

Anode

LSCF+GDC
100 m

Fig. 2. SEM images of a cell using double cathode: LSCF + GDC|CMF + LSFM, on BCZYYZ electrolyte support after electrochemical test, a) cross section, and b) high magnication.

ionicelectronic conduction properties. ASR values determined from

the IV curves are 2.80 and 2.06 cm2 for the cell using only LSCF
GDC cathode and additional CMFLSFM layer at 700 C, respectively.
Impedance spectroscopy data were obtained during the fuel cell tests
and helped shedding more light on this last point. Fig. 4 shows the
typical impedance plots for NiFe|BCZYYZ|LSCFGDC compared to the
NiFe|BCZYYZ|LSCFGDC|CMFLSF cell conguration at 700 C, under
OCV conditions. The intercept with the real axis at high frequencies represents the cell's ohmic resistance (Rs), whereas the difference between

(a)

Cell Voltage (V)

Anode
Cathode
3% H2O / 97% H2
Air

1.112V
1.066 V
1.051 V

800 C
o
700 C
o
600 C

0.8

0.15

-2

1.0

0.20
O.C.V

Power Density (/ W cm )

1.2

0.10

0.6
0.4

0.05
0.2
0.0
0.0

0.2

0.4

0.6

0.00

the high and lower frequency responses (semicircles) with the real axis
presents the sum of the polarisation resistance (Rp). The CMFLSFM
containing cell presented a lower polarisation resistance value than
that of only LSCFGDC cathode cell, in agreement with the ASR values
extracted from the IV curves shown in Fig. 3, since ohmic resistance
of the CMFLSFM containing cell was slightly larger due to its lower
electrical conductivity. However, ohmic resistances (Rs 2.2 cm2
at 700 C) would be almost dominated by electrolyte conductivity
and consequently Rs values were very closed to theoretical value
( 2.2 cm2), considering conductivity of the BCZYYZ at 700 C
( 0.018 1 cm1 at 700 C, R ohmic = thickness/(area)). In any
case, it is reasonable to assume that the lower value obtained for the
electrochemical reaction resistance by adding the catalyst layer, CMF
LSFM, was due to the improved catalytic activity of CMFLSFM material
that makes it suitable for proton conducting fuel cells.
Furthermore, in order to verify the electrochemical reduction of CO2,
we replaced the air feeding the cathode side of the electrochemical cell
with pure CO2 gas, monitoring the cell performance. Fig. 5(a) shows the
electrochemical performance in CO2 for NiFe|BCZYYZ|LSCFGDC
cell compared to the cell where CMFLSFM was added (Ni
Fe|BCZYYZ|LSCFGDC|CMFLSFM), at 700 C. As in the previous case,
the current density was signicantly improved by introducing CMF
LSFM as 0.5 A/cm2 were achieved at 1.3 V in this case compared to
0.18 A/cm2 measured with the LSCFGDC cathode only. This conrms
that CMFLSFM catalyst layer has also positive effects for the CO2 reduction reaction in a proton conducting electrolysing cell; thus, the
cell with the CMFLSFM active layer exhibits a much smaller
polarisation resistance value than that of only LSCFGDC cathode

-2

Current Density (/A cm )

(b)
Anode
Cathode
3% H2O / 97% H2
Air

0.8

-1.2

0.2

0.6
0.4

0.1
0.2

0.3

-0.9

Anode
Cathode
3% H 2O / 97% H 2
Air

LSCF+GDC
Additional CMF+LSFM

@ 700 C

5 Hz

-0.6

''

800 C
o
700 C
o
600 C

Resistance of cell

-2

1.101V
1.055 V
1.02 V

Z im/Ohm.cm

Cell Voltage (V)

1.0

-1.5

0.4
O.C.V

Power Density (/ W cm )

1.2

100 Hz
5 K Hz

-0.3

0.0

0.0
0.0

0.5

1.0

0.0

-2

2.0

2.5

3.0
'

Z im/Ohm.cm

3.5

4.0

Current Density (/A cm )

Fig. 3. IV curves and corresponding power density curve for a) the cell using single cathode,
NiFe|BCZYYZ|LSCFGDC, and b) double cathode, NiFe|BCZYYZ|LSCFGDC|CMFLSFM.

Fig. 4. Impedance spectra of the cells: using single cathode, NiFe|BCZYYZ|LSCFGDC, and
double cathode, NiFe|BCZYYZ|LSCFGDC|CMFLSFM under open current condition at
700 C.

T.H. Shin et al. / Solid State Ionics 275 (2015) 106109

-2.5

(a) -3.0

109

CO2 Reduction

@700 C

CO2 Reduction
-2.0

-2.5

Cell Voltage

-2.0
-1.5

Cell Voltage

LSCF+GDC
Additional CMF+LSFM
1.3 V
Anode
Cathode
3% H2O / 97% H2 100% CO2

-1.0

@600 C

-1.0

-0.5
Anode
3% H2O / 97% H2

-0.5
o

0.0

@700 C

0.5 A/cm

@800 C

1.3 V

-1.5

Cathode
100% CO2

0.0

0.0
0.00

0.25

0.50

0.75

1.00

0.5

1.0

Current Density / A cm

1.5
-2

-2

Current Density / A cm

Fig. 6. IV curves of CO2 reduction in proton conductor cells double cathode, Ni

Fe|BCZYYZ|LSCFGDC|CMFLSFM under open current condition as function of operation
temperature.

(b) -4
Resistance of cell
Anode
3% H2O / 97% H2

-3

LSCF+GDC
Additional CMF+LSFM

@ 700 C
-2

1 Hz

''

Z im/Ohm.cm

Cathode
100% CO2

-1

1 K Hz

0
2

5
'

10

Z im/Ohm.cm

Fig. 5. IV curves of CO2 reduction in proton conductor cells: using single cathode, Ni
Fe|BCZYYZ|LSCFGDC, and double cathode, NiFe|BCZYYZ|LSCFGDC|CMFLSFM under
open current condition at 700 C.

cell as shown in Fig. 5(b), in agreement with the value obtained from
the IV curves. We previously reported the analysis of the gas composition during electrochemical testing of similar cells, showing a
mixture of syngas and CH4 (1.2%), with a CO concentration of 61%
(produced at the rate of 3.25 ml/min cm 2 ) and the corresponding
CO2 conversion of around 65% [13]. Here, the exhaust gases are expected to have similar composition to the one reported in the previous study
because the current and voltage values (1.3 V, 0.25 A/cm2 at 600 C in
Fig. 6) are very similar to the ones obtained before, were strong evidence of CO2 reduction and methane production was demonstrated.
However, detailed analysis of gas products during the transient period
is now under study, and the results will be reported in a future report.
Fig. 6 summarises the IV curve for the electrochemical reduction of
CO2 in the CMFLSFM added (NiFe|BCZYYZ|LSCFGDC|CMFLSFM),
proton solid oxide cells, with 3% H2O/H2 fuel and 100% CO2 on anode
and cathode sides, respectively, at different temperatures. The absolute
open circuit voltages were around 0.157 V at 700 C coming from the
pre-reduced electrode in small oxygen partial pressure of pure CO2 gas.
The superior performance obtained with the CMFLSFM active cathode
layer is very encouraging for further development and utilisation of
these cells in a different design and at a larger scale.
4. Conclusions
In this work, a proton-conducting solid oxide cell with the conguration, NiFe|BCZYYZ|LSCFGDC|CMFLSFM, was demonstrated for the

efcient electro-conversion of H2O/CO2, demonstrating that the electrochemical performance was improved by CMFLSFM addition to the
cathode as a catalyst layer. The IV curves in the SOFC and CO2 reduction
modes exhibited higher current density when the CMFLSFM catalyst
layer was present, accompanied by a signicant decrease in polarisation
resistance of the cell. During CO2 reduction at 700 C, current density
values as high as 0.5 A/cm2 and 1 A/cm2 were obtained at 1.3 V and
2.2 V respectively, even with relatively thick BCZYYZ electrolyte
supports (ca. 400 m). Furthermore, no carbon deposition was evident
after the CO2 reduction of test when pure CO2 was used at the air
electrode side. Therefore, the electrochemical reduction of CO2 in proton conducting solid oxide electrolyser using a CMFLSFM catalyst
layer would be an attractive option for cycling CO2 since reasonably
high current density was achieved.
Acknowledgements
We thank EPSRC (EP/I022570/1, EP/K015540/1, EP/I038950/1) and
the Royal Society (WRMA 2012/R2) (Wolfson Research Merit award)
for support. We thank also the In-house Program (2E24842) of the
Korea Institute of Science and Technology (KIST), Republic of Korea
for support.
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