DOI : 10.1002/celc.

201402017
NickelCopper/Gadolinium-Doped Ceria (CGO) Composite
Electrocatalyst as a Protective Layer for a Solid-Oxide Fuel
Cell Anode Fed with Ethanol
Massimiliano Lo Faro,*
[a]
Rafael M. Reis,
[b]
Guilherme G. A. Saglietti,
[b]
Andre G. Sato,
[b]
Edson
A. Ticianelli,
[b]
Sabrina C. Zignani,
[a, b]
and Antonio S. Aric
[a]
1. Introduction
A major worldwide challenge is the development and wide-
scale use of sustainable energy sources to reduce the effects
of global warming and overcome problems related to the
finite nature of fossil fuel reserves. Promising energy conver-
sion processes, including fuel cells, are being developed to
solve these problems. The performance of such energy devices
depends crucially on the properties of their components and
materials.
State-of-the-art solid-oxide fuel cells (SOFCs) suffer from the
direct utilisation of fuels other than H
2
and reformed methane.
The occurrence of carbon deposits on the anode with conse-
quent electrocatalyst poisoning in the absence of proper pre-
reforming steps is a well-known drawback.
[1]
To address this
problem in the short and medium term, a possible solution is
to apply a protective layer to the anode to mitigate carbon
deposition and anode poisoning by undesired contaminants.
SOFCs are conveniently used for distributed energy genera-
tion; these devices can be directly fed with biofuels.
For remote electrical energy generation, in terms of energy
density, it is useful if fuels are in a liquid form, such as alcohols.
Ethanol is characterised by a high volumetric energy density
(6100 Whl
1
) and low environmental impact.
[2]
It can be ob-
tained from the fermentation of agriculture products.
[3]
To preliminarily assess the feasibility of a SOFC to work with
bio-fuels, conditions simulating operation with practical bio-
fuel streams should be investigated. In particular, bio-ethanol
typically contains a significant percentage of water;
[4]
more-
over, bio-fuels are generally rich in CO
2
.
[5]
The approach used herein was to compare the behaviour of
a conventional anode-supported cell (ASC) in the presence and
absence of a protective layer based on a nickelcopper gadoli-
nium-doped ceria (NiCu/CGO) composite. This material has
been already investigated in SOFCs, but in the bulk form due
to its ability to oxidise organic fuels and resilience against
forming carbon deposits.
[6]
These properties derive from the
excellent synergy of nickel providing electrocatalytic activity
and copper ensuring resilience to cooking. Copper breaks the
assemblies of nickel atoms, which activate carbon deposition.
Doped ceria produces an extension of the ionic domain into
the electronic conducting electrocatalytic layer and promotes
oxidation. However, such electrocatalytic systems perform
more poorly than a conventional nickelY
2
O
3
-stabilized ZrO
2
(Ni/YSZ) anode in the presence of syngas (H
2
+CO) and it is
mechanically less robust. Another drawback is due to the pro-
pensity of NiO/doped-ceria systems forming a solid solution.
[7]
Such effects generally cause a loss in activity for the electro-
chemical reaction mainly due to the loss of surface area and
decrease in the electronic and ionic conductivity.
[7a, 8]
This effect
is generally faster in the presence of a large concentration of
dopants in CeO
2
.
[9]
However, the occurrence of an interaction
between nickel and copper and the presence of a moderate
concentration of dopant in CeO
2
(Ce
0.9
Gd
0.1
O
2
) can mitigate
nickel inclusion into the fluorite-type lattice of CeO
2
. The risks
of poor conductivity may be addressed by the utilisation of
A nickelcopper alloy is prepared by using the oxalate method
and subsequent in situ reduction. The bimetallic alloy is mixed
with gadolinium-doped ceria (CGO) to obtain a composite ma-
terial with mixed electronicionic conductivity. The catalytic
and electrocatalytic properties of the composite material for
ethanol conversion are described. Different conditions to simu-
late bio-ethanol feed operation are selected. Electrochemical
tests are performed by utilizing the NiCu/CGO cermet as
a barrier layer in a conventional anode-supported solid-oxide
fuel cell (AS-SOFC). A comparative study between the modified
cell and a conventional AS-SOFC without the protective layer is
made. A maximum power density of 277 mWcm
2
@0.63 V is
recorded in the presence of a mixture of ethanolwater for
a cell containing the protective anodic layer compared with
231 mWcm
2
@0.64 V for a bare cell under the same condi-
tions. This corresponds to a 20% increase in performance.
[a] Dr. M. Lo Faro, Dr. S. C. Zignani, Dr. A. S. Aric
CNR-ITAE, Via Salita S. Lucia sopra Contesse 5
98126 Messina (Italy)
E-mail : lofaro@itae.cnr.it
[b] Dr. R. M. Reis, Dr. G. G. A. Saglietti, Dr. A. G. Sato, Prof. E. A. Ticianelli,
Dr. S. C. Zignani
Institution USP-IQSC, Av. Trab. So-carlense
400 CEP 13560-970 So Carlos, SP (Brazil)
Supporting Information for this article is available on the WWW under
http://dx.doi.org/10.1002/celc.201402017.
This manuscript is part of a Special Section devoted to the GEI 2013.
2014 Wiley-VCH Verlag GmbH&Co. KGaA, Weinheim ChemElectroChem 2014, 1, 1395 1402 1395
CHEMELECTROCHEM
ARTICLES
a thin film as a protective layer characterised by low
series resistance.
The studies performed herein thus focus on the
utilisation of such an electrocatalytic system as a bar-
rier layer against carbon formation on the conven-
tional Ni/YSZ anode under operation in the presence
of ethanol. Accordingly, the basic idea is to use such
a composite as a thin protective layer for a thick con-
ventional SOFC anode.
2. Results and Discussion
2.1. Physico-chemical Analysis of the NiCu/CGO
Electrocatalyst
The crystal structure and morphology of the as-calcined NiCu
electrocatalyst were investigated (Figure 1). The main phase
after calcination was a mixed oxide of nickel and copper. Crys-
tallisation mainly occurs in the cubic phase (similar to
Ni
0.8
Cu
0.2
O JCPDS no. 25-1049). However, the simultaneous
presence of NiCu oxide in a tetragonal phase (NiCuO
2
, JCPDS
no. 6-720) cannot be ruled out. Peak positions, in particular, re-
flect the occurrence of the Ni
x
Cu
1x
O cubic phase, whereas
peak intensities indicate a good match with the tetragonal
NiCuO
2
phase. However, the different relative intensities of the
experimentally recorded diffraction peaks for the equimolar
NiCu oxide and the cubic Ni
0.8
Cu
0.2
O phase in the literature
may also be related to the different Ni/Cu ratio. No phase sep-
aration into NiO and CuO was observed by XRD. However,
such a result may be the consequence of large peak broaden-
ing caused by the fine particles. A crystallite size of about 4
5 nm was derived from the broadening of the XRD peaks.
The morphologies of calcined NiCu electrocatalyst and
composite NiCu/CGO electrocatalyst after ball-milling are
shown in the Figure 2. Fine particles with a typical particle size
of about 510 nm were present in both materials. Large aggre-
gates of NiCu nanoparticles were observed in the sample
milled for 20 h. Only a low amount of NiCu phase is properly
dispersed on the support (Figure 2b).
X-ray fluorescence (XRF) analysis (not shown) indicated that
the final composition of the electrocatalyst was Ni/Cu/CGO
25:25:50 (w/w/w).
2.2. Ex Situ Catalytic Test for the NiCu/CGO Composite
Catalytic experiments were performed for 10 h to investigate
the reliability of the NiCu/CGO electrocatalyst for ethanol re-
forming under autothermal conditions. This procedure pro-
vides an ex situ screening analysis of the catalytic properties
under conditions close to those occurring during SOFC opera-
tion.
[10]
Pre-treatment of the electrocatalysts at 8008C in the
presence of H
2
, similar to the SOFC conditioning procedure,
was performed to activate the electrocatalyst. The ex situ cata-
lytic tests, in addition to serving as a screening method, allow
insights into the reaction process.
Figure 3 shows the outlet gas composition from ethanol au-
tothermal reforming (ATR) at the NiCu/CGO composite, as de-
termined by gas chromatography (GC). The outlet gas was pre-
ventatively dried before GC analysis. The experiment demon-
strates that this electrocatalyst operates with good stability
under the reaction stream. However, it gives rise to a significant
difference in the composition of outlet gas relative to the ther-
modynamic equilibrium, especially concerning CO
2
and CO.
The calculated equilibrium composition for the external etha-
nol autothermal reformer at 8008C is 40 mol % H
2
O, 40 mol %
H
2
, 10 mol % CO
2
, and 10 mol % CO with traces of CH
4
and
others sub-products. Thus, in the equilibrium composition, the
ratio of H
2
/CO is 4:1, whereas the experimentally obtained
value is about 6:1. On the contrary, the equilibrium value of
H
2
/CO
2
is 4:1, whereas the experimental value is about 3:1.
Figure 1. X-ray diffraction (XRD) spectrum of the as-calcined NiCu electro-
catalyst.
Figure 2. Transmission electron microscopy (TEM) micrographs of the as-calcined NiCu
catalyst (a) and ball-milled NiCu/CGO catalyst (b).
Figure 3. Reaction yield for the main products of the ethanol ATR process at
8008C for 10 h in the presence of the NiCu/CGO electrocatalyst.
2014 Wiley-VCH Verlag GmbH&Co. KGaA, Weinheim ChemElectroChem 2014, 1, 1395 1402 1396
CHEMELECTROCHEM
ARTICLES www.chemelectrochem.org
From these considerations, it is derived that part of
CO is oxidised to CO
2
in comparison to the expected
equilibrium composition. This effect is ascribed to ox-
idative properties of the composite electrocatalyst es-
pecially due to the presence of CGO. Such character-
istics should mitigate carbon deposition phenomena
in the anodic fuel cell compartment.
To obtain information on the thickness and cohe-
sion between the various layers and interfaces of the
multiple component SOFC, scanning electron micros-
copy (SEM) analysis was performed on the cell cross
section (Figure 4). The bare cell is shown in Figure 4a.
The three layers consist of the anode support
(150 mm, bottom), the full density thin electrolyte
(10 mm, middle) and the cathode layer (4050 mm, top). Thin
functional layers are present at the electrodeelectrolyte inter-
faces (not shown in detail). Figure 4b shows the interface be-
tween the supporting anode and pre-layer in the modified cell.
The pre-layer thickness was about 5 mm. The pre-layer appears
to be slightly less porous than the supported anode; this is es-
sentially due to different particle sizes and relative contents of
metal and ceramic phases in these layers (Ni/YSZ supporting
anode 70: 30 wt %, NiCu/CGO pre-layer 50:50 wt %). No de-
lamination effects between the protective layer and the sup-
port were observed. This indicates that the thermal expansion
of the composite layers is similar. The thermal expansion coeffi-
cient of Y
0.08
Zr
0.92
O
2
is similar to Ce
0.9
Gd
0.1
O
2
(11.610
6
vs.
14.410
6
K
1
in the temperature range of 2009808C).
[11]
Figure 5 shows the XRD spectrum collected in grazing angle
mode of the pre-layer modified cell after sintering at 10008C
(Figure 5a) and subsequent reduction at 8008C in H
2
(Fig-
ure 5b). After the firing step in air (Figure 5a), X-ray reflections
related to the fluorite phase of CGO (CeO
2
JCPDS card no. 4-
593) and to the cubic structure of Ni
x
Cu
1x
O (similar to
Ni
0.8
Cu
0.2
O, JCPDS no. 25-1049) were present. It is observed
that further crystallisation of the NiCu oxide occurs after the
thermal treatment of the protective layer at 10008C. In this
case, there is a good match with the Ni
0.8
Cu
0.2
O cubic phase
from the literature, but shifts for the peak positions, which re-
flect that a different composition (Ni/Cu=50:50 at %) is ob-
served. According to the XRD spectrum, there is a significant
interaction between the nickel and copper metals in the layer
deposited on the SOFC anode and a growth of the particles
with a single cubic phase compared with the as-calcined mate-
rial. The crystallite size in the Ni
x
Cu
1x
O layer after cell manu-
facturing, as determined by the Scherrer equation, was approx-
imately 35 nm. After reduction in hydrogen, an equimolar
NiCu metal alloy is obtained together with CGO.
2.3. Electrochemical Studies
Polarisation and electrochemical-impedance spectroscopy (EIS)
were initially recorded in the presence of H
2
feed under open-
circuit voltage (OCV) and at 0.8 V. The latter operating condi-
tions correspond to about 70% electrical efficiency, which is
generally of practical interest for SOFCs. Figure 6a shows the
EIS spectra collected under OCV (1.17 V for both cells) for the
two types of cells investigated. These impedance spectra have
been fitted by using the equivalent circuit model with series
RQ elements.
[12]
Complete fitting results are reported in the
Supporting Information. In the following discussion, the most
relevant parameters, such as series and polarisation resistances,
are described. A comparison of the two spectra clearly evi-
denced an increase in the total resistance (R
t
), obtained from
the intercept at low frequency, in the case of the protective
layer coated on the anode; this was ascribed mainly to the
larger semicircle at low frequency. No large change in the
series resistance at high frequency was observed as a conse-
quence of the additional layer. Figure 6b shows the EIS behav-
iour at 0.8 V for the two cells. In this case, a slight increase in
the series resistance (R
s
), as determined from the intercept at
high frequency, was registered in the case of the modified cell.
The value of R
s
recorded in the case of the bare cell was
0.21 Wcm
2
, whereas it was 0.26 Wcm
2
in the case of the cell
Figure 4. SEM images of the complete bare cell (a) and the interface between the anode
and pre-layer in the modified cell (b). Scale bars: 100 mm (a) and 20 mm (b).
Figure 5. XRD spectrum of the pre-layer anode coating in grazing angle con-
figuration: a) after calcination at 10008C and b) after subsequent reduction
in H
2
at 8008C.
2014 Wiley-VCH Verlag GmbH&Co. KGaA, Weinheim ChemElectroChem 2014, 1, 1395 1402 1397
CHEMELECTROCHEM
ARTICLES www.chemelectrochem.org
modified with the pre-layer. A slight re-oxidation of the pre-
layer may have occurred under these conditions. Such an
effect may be positive in terms of tolerance to carbon deposi-
tion. A slightly oxidised electrocatalyst phase can reduce the
anode propensity to promote carbon fibre growth, which
occurs for a pure metallic electrocatalyst. A remarkable differ-
ence in the EIS profile for the two cells was observed and as-
cribed to the semicircle at very low frequencies related to
mass transport constraints. This effect occurs at low frequency
in the Nyquist plot for the cell covered by the protective layer
(Figure 6b). The performance of the SOFCs was evaluated by
measuring the currentvoltage (IV) characteristics and calcu-
lating the currentpower curves (IP), as shown in Figure 6c.
It can be seen that, in the presence of H
2
feed, both cells
showed the same OCV (1.17 V), whereas the modified cell per-
formance was lower than that of the bare cell. Significant diffu-
sion constraints were recorded for the modified cell at a current
density higher than 700 mAcm
2
. However, at a cell voltage of
0.8 V, the difference in performance between the two cells is
very small.
A comparison of the behaviour of both cells in the presence
of diluted ethanol (1:3 in water) is shown in Figure 7. A signifi-
cant decrease in the OCV down to 1 V was evident for both
cells. Slight noise in the recorded curves was possibly due to
the use of the isocratic pump for feeding ethanol. As shown in
Figure 7, the modified cell had a slightly higher open-circuit
potential (0.97 V instead of 0.92 V recorded for the bare cell).
Accordingly, the polarisation resistance (R
p
=R
t
R
s
) for the
spectra collected at OCV (Figure 7a) was affected by the differ-
ent direct current (DC) voltage conditions, whereas the series
resistance (R
s
) was similar (0.23 Wcm
2
) for these cells. Similar al-
ternating current (AC)impedance profiles between the two
cells were observed at 0.8 V (Figure 7b). In this case, the DC
voltage is the same for the cells under investigation. Interest-
ingly, the value of R
s
, which is generally affected by electronic
percolation in the anode, was similar in the presence of diluted
ethanol for the two cells. The R
s
value of the bare cell in-
creased a slightly from 0.21 Wcm
2
in hydrogen to 0.23 Wcm
2
in diluted ethanol due to the less-reducing environment,
whereas R
s
in the modified cell decreased from 0.26 Wcm
2
in
hydrogen to 0.23 Wcm
2
in diluted ethanol. It was likely that, in
the case of Ni/YSZ exposed to the mixture of ethanol/water,
there was a partial re-oxidation of Ni on the surface, whereas,
in the case of NiCu/CGO exposed to the same solution of eth-
anol, a slight formation of carbon deposits may have increased
the conductivity of the protective layer.
Figure 6. Comparison of the electrochemical experiments performed in the
presence of H
2
at 8008C for modified and bare cells: a) EIS spectrum at OCV,
b) EIS spectrum at 0.8 V, and c) currentvoltage and currentpower curves.
Figure 7. Comparison of the electrochemical experiments performed in the
presence of diluted ethanol (1:3 in water) at 8008C for modified and bare
cells: a) EIS spectrum at OCV, b) EIS spectrum at 0.8 V, and c) currentvoltage
and currentpower curves.
2014 Wiley-VCH Verlag GmbH&Co. KGaA, Weinheim ChemElectroChem 2014, 1, 1395 1402 1398
CHEMELECTROCHEM
ARTICLES www.chemelectrochem.org
Figure 7c shows a comparison of polarisation and power
density curves for the cells presently investigated. In case of
the cell containing a protective layer, the maximum per-
formance obtained was 275 mWcm
2
at 0.62 V, which was
about 19% more than the maximum performance achieved for
the bare cell. The performance obtained at 0.8 V was slightly
better for the cell with the protective layer. This result associat-
ed with the better OCV reveals a positive effect of the NiCu/
CGO layer on the performance of the SOFC fed with a mixture
of ethanol/water at 0.8 V, which corresponds to suitable electri-
cal efficiency.
The electrochemical behaviour in the presence of a pure
stream of ethanol at the anode is shown in Figure 8. It should
be noted that, in this case, the OCV of the bare cell was signifi-
cantly higher (1.10 V) than that of the modified cell (0.97 V).
The impedance spectra collected under OCV (Figure 8a) are
thus strongly affected by the different OCV values. EIS spectra
at 0.8 V (same DC voltage for the two cells) have similar R
s
values for both cells (Figure 8b). At low frequency, the modi-
fied cell appeared to be more stable. The polarisation curves in
Figure 8c show a performance only slightly higher for the bare
cell, even if it is characterised by a large fluctuation. Overall
performances were better in the presence of pure ethanol
than those for the mixture of ethanol/water. This indicates
that, under the specific SOFC operation conditions, the electro-
chemical process in Equation (1):
C
2
H
5
OH 6 O
2
!2 CO
2
12 e

3 H
2
O 1
is occurring faster than the ethanol reforming process and sub-
sequent electrochemical reactions given in Equations (2)(4):
C
2
H
5
OH H
2
O !2 CO 4 H
2
2
4 H
2
4 O
2
!4 H
2
O 8 e

3
2 CO 2 O
2
!2 CO
2
4 e

4
Furthermore, a cracking mechanism cannot be excluded,
possibly as a consequence of the segregation of nickel clusters
on the electrocatalyst surface.
However, because water is formed at the anode during the
direct ethanol oxidation process, some dilution of ethanol by
the water reaction product may occur with time. Thus, during
prolonged operation, an equilibrium is established between
the ethanol feed stream and water reaction products at the
surface of the anode electrocatalyst. This situation resembles
SOFC operation with a mixture of ethanol/water.
In a third set of experiments, the cell modified with the pro-
tective layer was fed with a stream of reformed ethanol pro-
duced by an external catalytic processor operating under
steam reforming conditions of ethanol at 4008C. Figure 9a
shows an outline of the overall plant, including the chemical
processor connected to a SOFC bench. As reported in the Ex-
perimental Section, the composition of the stream at the inlet
of the SOFC cell was as follows: 42 mol % H
2
O, 23 mol % H
2
,
14 mol % CO
2
, 1 mol % CO, 20 mol % of CH
4
, and traces of acet-
aldehyde. Figure 9b shows the polarisation behaviour in the
presence of a stream of reformed ethanol. It should be noted
that the OCV was not affected by the presence of excess CO
2
(1.03 V), whereas the performance obtained in the presence of
reformed ethanol (275 mWcm
2
) was lower than that obtained
by feeding the SOFC with ethanol (335 mWcm
2
). As above
discussed, reformed ethanol, in addition to syngas, contained
CO
2
, water and traces of hydrocarbons. This may explain the
decrease in performance. Accordingly, it is not convenient to
utilise a pre-reformer if a proper protective layer for the SOFC
anode is used. A decrease in the performance was observed
by adding further CO
2
to the stream of reformed ethanol (Fig-
ure 8b). CO
2
causes a further dilution of the stream and shifts
the equilibrium at the electrocatalyst surface towards reactant
species. This determines the performance reduction and con-
firms that an excess of reaction products plays a negative role
on the SOFC performances. Nevertheless, the possibility of
using a biofuel rich in CO
2
directly fed into the SOFC modified
with a pre-layer at the anode represents a clear simplification
of the system and may allow the wide diffusion of this
technology.
Figure 8. Comparison of the electrochemical experiments performed in the
presence of pure ethanol at 8008C for modified and bare cells: a) EIS spec-
trum at OCV, b) EIS spectrum at 0.8 V, and c) currentvoltage and current
power curves.
2014 Wiley-VCH Verlag GmbH&Co. KGaA, Weinheim ChemElectroChem 2014, 1, 1395 1402 1399
CHEMELECTROCHEM
ARTICLES www.chemelectrochem.org
A SEM study of the SOFC protective layer after several hours
( 50 h) operation in ethanol showed a highly porous mor-
phology (Figure 10a). A modest formation of carbon
deposits with an average diameter of 45 nm was ob-
served only at high magnification (Figure 10b). This
confirms the positive role of copper in mitigating the
occurrence of carbon deposits. A small formation of
carbon fibres may, under some circumstances, im-
prove electronic percolation in the protective layer.
The performance of the SOFC equipped with the
protective layer can be improved by enhancing elec-
tron percolation through an optimisation of the rela-
tive content between NiCu and CGO. However,
a compromise appears to be necessary between con-
ductivity and resilience to carbon deposition. The
latter may be influenced by the ceria content in the
pre-layer.
Table 1 shows a comparison of the results achieved with the
present electrocatalysts and promoters reported in the litera-
ture for conventional nickel-based cells. It can be observed
that the NiCu/CGO electrocatalyst, in the presence of an or-
ganic fuel at a similar performance level, allows an electrical ef-
ficiency to be achieved which is higher than that reported in
the literature. This is obtained without significant modification
of the cell architecture. Such an approach could be useful for
SOFC developers who prefer to avoid significant modification
to the cell architecture.
3. Conclusions
The crystal structure, morphology and electrochemical proper-
ties of a NiCu alloy/gadolinium-doped ceria (CGO) composite
used as a protective layer in a conventional solid-oxide fuel
cell (anode-supported cell) were studied in relation to the uti-
lisation of ethanol as a fuel.
A nickelcopper alloy with nanosized particles and a cubic
crystallographic phase was obtained. A ball-milling procedure
was used to obtain the composite NiCu/CGO electrocatalyst.
The electrochemical performance achieved in the presence
of pure, diluted and reformed ethanol fuels demonstrated that
the protective layer played a positive role in the presence of
ethanol, especially when water was present in the anodic
stream, and reached a maximum power density of about 20%
higher than that of the bare cell. However, the electrocatalytic
activity could be further enhanced by improving the dispersion
between NiCu and CGO. The present experiments have dem-
onstrated that the utilisation of a protective layer represents
Figure 9. a) Schematic diagram of the microplant for the steam reforming of
ethanol used in conjunction with the SOFC bench. b) A comparison of elec-
trochemical polarisations performed at 8008C for the modified cell fed with
reformed ethanol and CO
2
.
Figure 10. Surface morphology of the modified cell after electrochemical operation in
ethanol : a) low and b) high magnification (carbon fibre deposits with a diameter of
45 nm were detected). Scale bars: 1 mm (a) and 200 nm (b).
Table 1. A brief summary of modified SOFCs reported to date.
[a]
Catalyst Preparation Deposition Type of cell Performance in H
2
Performance in C-based fuel Ref.
NiCu/
CGO
oxalate
method
spray coat-
ing
Ni/YSZ//YSZ/YDC//LSFCO 0.355 Wcm
2
@0.62 V
(8008C)
0.334 Wcm
2
@0.62 V in pure ethanol
(8008C)
Figures 6c
and 8c
SDC impregnation dip-coat-
ing
Ni/YSZ//YSZ//LSM 0.450 Wcm
2
@0.55 V
(7008C)
0.280 Wcm
2
@0.48 V in 25% CH
4
+75%
air (7008C)
[13]
CuCeO
2
citric method tape cast-
ing
CuCeO
2
/NiCeO
2
/NiScSZ//
ScSZ//PCM
0.600 W cm
2
@0.45 V
(8008C)
0.350 W cm
2
@0.53 V in ethanol/water
(2:1) (8008C)
[14]
[a] YSZ=yttrium-stabilised zirconia (Y
0.08
Zr
0.92
O
2
), YDC=yttrium-doped ceria (Y
0.10
Ce
0.90
O
2
), LSFCO=La
0.6
Sr
0.4
Fe
0.8
Co
0.2
O
3
, LSM=La
0.85
Sr
0.15
MnO
3
, ScSZ=scan-
dia-stabilized zirconia, PCM=(Pr
0.7
Ca
0.3
)
0.9
MnO
3
.
2014 Wiley-VCH Verlag GmbH&Co. KGaA, Weinheim ChemElectroChem 2014, 1, 1395 1402 1400
CHEMELECTROCHEM
ARTICLES www.chemelectrochem.org
a clear simplification of the SOFC system because no external
reforming step appeared to be strictly necessary in the case of
the pre-layer modified anode.
The protective layer could also efficiently operate when an
excess of CO
2
was present in the anodic stream, as occurs fre-
quently with biofuels.
Experimental Section
The NiCu electrocatalyst was prepared by using the method
shown in the block diagram in Figure 11. Nickel(II) nitrate hexahy-
drate (CAS 244074; Sigma Aldrich) and copper(II) nitrate hemi(pen-
tahydrate) (CAS 467855; Sigma Aldrich) were used as precursors.
Reagent grade sodium borohydride was added to the solution of
oxalate complex to promote chemical reduction at low tempera-
ture and to form the NiCu alloy. This step allowed atomic mixing
between Ni and Cu to be achieved at the nanoparticle level before
the calcination step; thus avoiding the occurrence of separate
oxide phases during thermal treatment.
Due to the different crystallographic properties of NiO (cubic,
JCPDS no. 4-835) and CuO (monoclinic, JCPDS no. 5-661), it was
not a simple task to obtain a solid solution of these oxides at an
equimolar ratio. We observed that no phase separation for the
mixed oxides occurred if the solution of oxalate complex was treat-
ed with NaBH
4
.
All reagents shown in the block diagram in Figure 11 were pure
grade chemicals. H
2
C
2
O
4
and NaBH
4
were used in excess of 50 wt %
relative to the stoichiometric value calculated to form a bimetallic
alloy.
XRF analysis for the calcined powders was performed with Bruker
equipment (mod. S4 Explorer) to investigate the exact composition
of the as-prepared NiCu electrocatalyst. The as-calcined powder
was studied by XRD analysis [XPERT Philips diffractometer with Cu
Ka radiation (l=0.15418 nm)] in the range 208 2q908.
The as-calcined NiCu powders were milled together with CGO
(Ce
0.9
Gd
0.1
O
2
Praxair, 38.92 m
2
g
1
) in a planetary mill (Firtsch Pul-
verisette) for 20 h to obtain the final electrocatalyst. The final ratio
between the metallic and ceramic materials was 50:50 (w/w). The
crystallite sizes of the NiCu and NiCu/CGO electrocatalysts were
measured by TEM (FEI CM12-EDX instrument operating at 120 kV
and equipped with a LaB
6
filament).
An ex situ test concerning the ATR of ethanol was performed by
using an external chemical processor, the setup of which was de-
scribed in detail in previous work.
[15]
The selected oxygen to
carbon (O/C, excluding oxygen in the formula for ethanol) and
steam to carbon (S/C) ratios were 0.5 and 2.5, respectively;
[16]
whereas a gas space velocity (GHSV) of 120000 h
1
was fixed.
Reaction streams were analysed by GC (Varian Micro GC instru-
ment) equipped with a thermal conductivity detector (TCD) and
a four-column system [molecular sieves of different sizes (MS 5 ),
Poraplot Q and C-PSIL columns] . Before chromatographic analysis,
water contained in the reaction stream was eliminated by a trap.
SOFC performances were investigated for operation with pure eth-
anol, a mixture of ethanol/water, reformed ethanol and a stream of
reformed ethanol enriched with CO
2
. The effect of coating the ex-
ternal anode surface with a protective layer was studied. The bare
SOFC consisted of a state-of-the-art ASC. Button cells of 2 cm
2
were prepared. The manufacturing procedure for the bare SOFC
was reported previously.
[17]
The cell consisted of a Ni/YSZ (75 mol % NiO) supporting anode,
a fluorite-type YSZ/YDC electrolyte bilayer, and LSFCO cathode.
The modified cell differed from the bare cell by the addition of
a pre-layer (protective layer) of about 5 mm at the anode side
(5 mgcm
2
). This layer was deposited by spray coating on the
anode of the ASC and subsequently it was fired in static air at
10008C for 2 h.
The pre-layer was investigated by grazing angle X-ray diffraction to
reduce the reflection intensity from the substrate. The various
layers were analysed by SEM.
Afterwards, the modified cell and the bare cell were investigated
electrochemically at 8008C in a fuel cell test station, including an
Autolab PGSTAT30 Metrohm potentiostatgalvanostat and a fre-
quency-response analyser (EIS) equipped with a 20A booster. The
EIS measurements were performed in the frequency range from
10 mHz to 1 MHz with an applied AC voltage amplitude of 0.010 V
root mean square (rms). Data fitting was performed by using the
equivalent electric circuit model implemented in the AUTOLAB
METROHM software.
A pre-treatment of 20 h in presence of H
2
at 8008C was adopted
to allow complete reduction of the anode. During the conditioning
procedure, the feed stream of H
2
was initially diluted (10% in Ar).
Pure H
2
was used to complete the conditioning process.
The electrochemical experiments were performed by feeding hy-
drogen, pure and diluted ethanol (1:3 in water), and reformed eth-
anol into the anode compartment, whereas the cathode was under
static air. The fuel flow rate was set to a value corresponding to an
equivalent Faradic current of 1 Acm
2
. The liquid fuels were fed by
using an isocratic pump and subsequently mixed with an argon
carrier. The experiments with reformed ethanol were performed in
the presence of a chemical processor operating at 4008C under
steam reforming of ethanol (1:3 in water). In another experiment,
Figure 11. The NiCu catalyst preparation procedure.
2014 Wiley-VCH Verlag GmbH&Co. KGaA, Weinheim ChemElectroChem 2014, 1, 1395 1402 1401
CHEMELECTROCHEM
ARTICLES www.chemelectrochem.org
CO
2
was fed together with reformed ethanol. The catalyst used in
the external ethanol reformer was RhFe/CaAl
2
O
3
. This is a bench-
mark catalyst for this process.
The conversion of ethanol in the external reformer was close to
100%; the main reaction products of the reforming process provid-
ing the stream fed to the SOFC were 42 mol % H
2
O, 23 mol % H
2
,
14 mol % CO
2
, 1 mol % CO, 20 mol % of CH
4
, and traces of acet-
aldehyde.
Acknowledgements
The present work was carried out, in part, in the framework of
the Research Program promoted by the Brazilian Conselho Na-
cional de Desenvolvimento Cientfico e Tecnolgico entitled
Cincia sem Fronteiras processo no. 402180/2012-7. S.C.Z.
thanks CNPq for a post-doctoral fellowship awarded under the
reference number CNPq Proc. 238319/2012-1. We also acknowl-
edge the Italian Ministry of Research and Education for financial
support of the BIOITSOFC project within the program PROGRAM-
MI DI RICERCA SCIENTIFICA DI RILEVANTE INTERESSE NAZIONALE-
PRIN PROGRAMMA DI RICERCAAnno 20102011prot. 2010
KHLKFC.
Keywords: copper electrochemistry ethanol fuel cells
nickel
[1] a) S. L. Douvartzides, F. A. Coutelieris, A. K. Demin, P. E. Tsiakaras, AIChE J.
2003, 49, 248257; b) N. Laosiripojana, S. Assabumrungrat, J. Power
Sources 2007, 163, 943951; c) T. Iida, M. Kawano, T. Matsui, R. Kikuchi,
K. Eguchi, J. Electrochem. Soc. 2007, 154, B234B241; d) H. Timmer-
mann, W. Sawady, D. Campbell, A. Weber, R. Reimert, E. Ivers-Tiffee, J.
Electrochem. Soc. 2008, 155, B356B359; e) M. S. Batista, R. K. S. Santos,
E. M. Assaf, J. M. Assaf, E. A. Ticianelli, J. Power Sources 2003, 124, 99
103.
[2] a) S. L. Douvartzides, F. A. Coutelieris, A. K. Demin, P. E. Tsiakaras, Int. J.
Hydrogen Energy 2004, 29, 375379; b) M. Cimenti, J. M. Hill, J. Power
Sources 2009, 186, 377384; c) L. Hernndez, V. Kafarov, Int. J. Hydrogen
Energy 2009, 34, 70417050.
[3] a) J. Szczodrak, J. Fiedurek, Biomass Bioenergy 1996, 10, 367375;
b) M. H. Nguyen, R. G. H. Prince, Biomass Bioenergy 1996, 10, 361365.
[4] I. de Carvalho Macedo, Biomass Bioenergy 1998, 14, 7781.
[5] M. A. Sanderson, F. Agblevor, M. Collins, D. K. Johnson, Biomass Bioener-
gy 1996, 11, 365370.
[6] a) D. La Rosa, A. Sin, M. Lo Faro, G. Monforte, V. Antonucci, A. S. Aric, J.
Power Sources 2009, 193, 160164; b) D. La Rosa, M. Lo Faro, G. Mon-
forte, V. Antonucci, A. S. Aric, J. Appl. Electrochem. 2009, 39, 477483.
[7] a) W. Shan, M. Luo, P. Ying, W. Shen, C. Li, Appl. Catal. A 2003, 246, 19;
b) W. Zhang, L. T. Kuhn, P. S. Jrgensen, B. R. Sudireddy, J. J. Bentzen, C.
Bernuy-Lopez, S. Veltz, T. Ramos, J. Power Sources 2014, 258, 297304;
c) F. Ye, T. Mori, D. R. Ou, J. Zou, J. Drennan, S. Nakayama, M. Miyayama,
Solid State Ionics 2010, 181, 646652.
[8] G. Wrobel, M. P. Sohier, A. DHuysser, J. P. Bonnelle, J. P. Marcq, Appl.
Catal. A 1993, 101, 7393.
[9] D. R. Ou, T. Mori, F. Ye, M. Takahashi, J. Zou, J. Drennan, Acta Mater.
2006, 54, 37373746.
[10] M. Lo Faro, V. Antonucci, P. L. Antonucci, A. S. Aric, Fuel 2012, 102,
554559.
[11] A. Heel, A. Vital, P. Holtappels, T. Graule, J. Electroceram. 2009, 22, 40
46.
[12] J. R. Macdonald, W. B. Johnson in Impedance Spectroscopy, Wiley, Hobo-
ken, 2005, pp. 126.
[13] S. P. Yoon, J. Han, S. W. Nam, T.-H. Lim, S.-A. Hong, J. Power Sources
2004, 136, 3036.
[14] X.-F. Ye, S. R. Wang, Q. Hu, Z. R. Wang, T. L. Wen, Z. Y. Wen, Electrochem.
Commun. 2009, 11, 823826.
[15] M. Lo Faro, D. La Rosa, P. Frontera, P. Antonucci, V. Antonucci, A. Aric,
Catal. Lett. 2010, 136, 5764.
[16] M. Lo Faro, V. Modafferi, P. Frontera, P. Antonucci, A. S. Aric, Fuel Pro-
cess. Technol. 2013, 113, 2833.
[17] D. Montinaro, V. Sglavo, M. Bertoldi, T. Zandonella, A. Aric, M. Lo Faro,
V. Antonucci, Solid State Ionics 2006, 177, 20932097.
Received: February 18, 2014
Revised: April 1, 2014
Published online on May 23, 2014
2014 Wiley-VCH Verlag GmbH&Co. KGaA, Weinheim ChemElectroChem 2014, 1, 1395 1402 1402
CHEMELECTROCHEM
ARTICLES www.chemelectrochem.org