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Boosting the oxygen reduction reaction

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mechanisms in IT-SOFC cathodes by catalytic

Cite this: J. Mater. Chem. A, 2015, 3,
16440 functionalization
Open Access Article. Published on 14 July 2015. Downloaded on 08/03/2016 18:23:24.

Received 10th July 2015 L. Navarrete, C. Sols and J. M. Serra*

Accepted 14th July 2015

DOI: 10.1039/c5ta05187h

www.rsc.org/MaterialsA

A robust LSM-GDC composite was used as a backbone electrode for suitable catalyst is decisive for an ecient SOFC cathode
the inltration of dierent catalysts, dispersed as oxide nanoparticles development. In this work, Pr, Sm, Ce, Zr, Ba and Co oxides are
after ring. Catalyst candidates were screened using symmetric cells brought onto the cathode and act as oxygen reduction catalysts
supported on the GDC electrolyte. Among the tested catalysts, due to their redox character and particular adsorption proper-
praseodymium inltration exhibited an outstanding and highly stable ties. In order to preserve the nanoscale size of the catalysts and
promotion eect of the oxygen reduction reaction. Impedance good dispersion,8 the inltration was performed on sintered
spectroscopy modelling provided insight into the nature of the distinct and well-consolidated LSM-GDC electrodes, instead of incor-
mechanisms limiting the cathode performance. The Pr-promotion in porating them into the LSM-GDC cathode inks prior to elec-
cathodes resulted in a vefold rise in the power density peak when trode ring.9,10 Dierent 2 M solutions (ethanolwater) with
tested on a fully assembled anode-supported fuel cell. adjusted surface tension were prepared with the dierent Co,
Ba, Ce, Pr, Sm and Zr precursors. The solution was dropped
onto the electrode, and inltration was carried out by
The reduction of the operation temperature of conventional capillarity.
SOFCs (Solid Oxide Fuel Cells) is very challenging but will be Symmetrical cells were prepared by using cathodes based on
very benecial to avoid the use of expensive building materials LSM-GDC composite backbones. A 50/50 % wt ratio was selected
and to enlarge the stack lifetime. LSM (La0.8Sr0.2MnO3
d) is still since it has been reported as the optimum for SOFC LSM-based
the material of choice due to its stability, electronic conductivity cathode purposes.11 GDC powder was synthesized by a co-
and compatibility with dierent materials such as yttria stabi- precipitation method, whereas LSM powder was purchased
lized zirconia (YSZ), doped ceria or perovskites. However, the from Fuel Cell Materials (USA). Screen printing inks made of
optimal operation of this cathode is reached at high tempera- LSM-GDC composite cathodes were prepared by three roll
tures (above 800  C).1 In order to reduce the operation milling LSM powder, GDC and a 6wt% ethylcelluloseterpineol
temperature, it is necessary to enlarge the three phase boundary solution in a 1 : 1 : 2 weight ratio.
(TPB) length, since LSM is an electronic conductor and the TPB This ink was applied on both sides of fully dense GDC
is limited to the electrodeelectrolyte region exposed to the gas.2 electrolytes. GDC electrolyte powder was provided by Treibacher
For this purpose, YSZ is industrially preferred at high temper- Industrie AG. The nal thickness of the electrolytes was z650
ature. GDC (Ce0.8Gd0.2O2
d) is a superior ionic conductor at mm and the disc diameter was 15 mm. Porous electrodes (9 mm
intermediate temperatures (<700  C), compatible with LSM and of diameter) were obtained aer calcining screen-printed layers
mixed with LSM can favour the presence of percolative path- at 1150  C for 2 h. A top screen-printed gold mesh was further
ways for both electrons and ions.35 This strategy will increase applied on the LSM-GDC electrode in order to ensure proper
the TPB to the whole electrode thickness and improve the current collection. Field Emission Scanning Electron Micros-
cathode performance at lower temperatures. However, the copy (FESEM) images of the symmetrical cells cross-section
performance of these composite cathodes is limited by surface aer electrochemical impedance spectroscopy (EIS) testing are
related processes, such as oxygen dissociation and adsorption shown in Fig. 1. FESEM images reveal that the electrode
O2(g) / 2Oad and Oad + e
/ O
ad.3,6,7 Thus, the use of a porosity appears to be adequate for gas diusion. Furthermore,
the whole electrode surface was covered (Fig. 1) with dierent
Instituto de Teconologa Qumica, Avda/ Los Naranjos s/n, 46022, Valencia, Spain. inltrated oxide catalysts, as inferred from XRD analysis
E-mail: [email protected]; Fax: +34 963877809; Tel: +34 963879448 (ESI Fig. S1), and the particle sizes range from 20 to 40 nm. The
Electronic supplementary information (ESI) available. See DOI: inltrated particles are spherical, except for Pr which presents a
10.1039/c5ta05187h

16440 | J. Mater. Chem. A, 2015, 3, 1644016444 This journal is The Royal Society of Chemistry 2015
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Communication Journal of Materials Chemistry A

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Fig. 1 From left to right; back SEM backscattering electrons of the

LSM-GDC backbone, Co backbone inltrated. Inltrated oxide SEM Fig. 2 Top; Arrhenius plot of the Rp obtained from the impedance
magnication; Pr, Zr, Co, Ce, Ba and Sm electrodes in order to ensure measurements for the symmetrical cells in air and bottom; polarization
proper current collection. resistance of LSM_GDC inltrated by Pr in the stability test.

needle-like morphology. The nanocatalyst size and morphology Table 1 Ea (eV) and degradation of the samples (U cm
2 h
1)
are retained aer the EIS test (ESI Fig. S2 and S7) and no Inltrated Ea (eV) Degradation rate 700  C (U cm
2 h
1)
coarsening is visible, which is an important factor in the
stability of the electrode operation. Blank 1.18 5.87  10
4
The electrochemical performance of the dierent promoted Ce 1.14 2.00  10
3
electrodes was studied by means of EIS on the corresponding Co 1.79 7.68  10
3
Pr 1.86 1.95  10
4 (0100 h)
inltrated symmetrical cells, which was compared with that of 1.20
5.29  10
6 (100270 h)
the LSM-GDC pristine electrode. As can be inferred from Fig. 2, Zr 1.20
3.42  10
4
every nanocatalyst enhances the cell performance of the pristine Sm 1.22 1.41  10
3
sample, except Co and Ba. Pr exhibits exceptional promotion Ba 1.14 1.38  10
2
behaviour, i.e., the electrode polarization resistance (Rp)
diminishes by two orders of magnitude with regard to that of
the pristine electrode. Other metal oxides show benecial reected in the electrical conductivity behaviour.1416 It seems
eects, namely, Ce, Zr and Sm inltration leads to 10, 5 and 2 that the variation of Ea in the Rp coincides with this phase
times smaller Rp values, respectively. The derived activation transition.
energy (Ea) for all samples (Table 1) is very similar [1.141.22 The stability of the inltrated cathodes was tested at 700  C
eV], except for Co, which exhibits signicantly higher Ea. for 1200 minutes, and the degradation rate is listed in Table 1. A
Besides, the Pr electrode shows a two-fold Arrhenius behaviour: very slight change in the Rp value is obtained for all samples,
a higher Ea value was obtained at high temperatures (700550 which corroborates the stability of the inltrated catalyst in the

C); and at low temperature (550450  C) an Ea value within the measured time. Exceptionally, Zr improves the cell performance
quoted range observed for most inltrated electrodes was with time, i.e. Rp decreases, which is assigned to transient
obtained. Assuming that the backbone is identical for all activation or equilibration of the catalyst. A longer stability test
samples, the changes in Rp are uniquely ascribed to the catalytic was performed for the Pr electrode and it is also shown in Table
promotion. The particular Ea observed for the Pr electrode at 1. Two dierent behaviours can be distinguished (Fig. 2
higher temperatures evidences a change in its rate limiting step. bottom). First, there is an initial degradation or equilibration,
Due to the high catalytic activity, the nature of the limiting step but aer 100 h of operation it disappears, as can be deduced
is presumably not related to the surface oxygen reduction from the almost constant Rp up to 275 h. In general, as
process. In addition, the controlled phase transition of this concluded from the degradation rate values, all the catalysts
oxide has been widely investigated.12,13 Pr oxide undergoes a show a rst equilibration (activation and/or degradation) period
phase transition from the ordered PrO1.833 at room temperature until they reach their nal state under the operation conditions,
to disordered PrO1.83 at increasing temperatures, which is aer which Rp remains constant. Furthermore, the

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Table 2 Fitting results at t1 30 min and t2 after 1200 min for the pristine and inltrated samples

Inltration oxide t RHF (U cm2) RMF (U cm2) RLF (U cm2) fHF (Hz) fMF (Hz) fLF (Hz)

Blank 1 0.91 1.07 8.40  103 742

2 0.90 1.08 8.61  103 740
Ce 1 0.36 0.12 3.23  104 1814
2 0.41 0.16 2.82  104 1307
Co 1 0.53 1.05 1.44  105 266
2 0.56 1.37 1.31  105 185
4.45  10
3 3.84  104
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Pr 1 0.05 2
2 0.07 5.58  10
3 3.07  104 2
Zr 1 0.41 0.31 2.61  104 1050
2 0.40 0.28 2.21  104 1011
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Sm 1 0.75 0.35 9.69  103 1623

2 0.70 0.46 9.64  103 1230
Ba 1 0.43 1.43 3.38  10
1 1.78  105 6494 17
2 0.60 1.54 7.80  10
1 2.21  105 5857 15

reproducibility of the results obtained was assessed by thanks to the catalytic promotion. However, Ba and Co-inl-
measuring three dierent cells inltrated with Pr, obtaining trated electrodes present higher MF contributions than that of
practically the same electrochemical results (ESI Fig. S3). the blank electrode which is directly attributed to the inhibition
In order to discern the dierent contributions of the resis- of surface related processes.
tance and the associated processes aected by the inltration, In addition, the stability of the dierent contributions was
the EIS measurements were tted to a double R||CPE equivalent checked (Table 2). The MF resistance increases with operation
circuit, except for Ba that required a three R||CPE circuit (Table time (t2 1200 min), except for Zr that diminishes. Moreover,
2). The pristine (blank) electrode shows two contributions, i.e., the frequency range associated with these surface processes is
the highest one at medium frequencies (MF, 0.77 kHz), which shied towards lower values whereas the HF range remains
limits the performance, and another one at high frequencies more or less unaltered for all samples. Finally, aer 1200 min,
(HF, 8220 kHz). MF contribution has been associated with the the dominant mechanism is still associated with HF processes,
coupled dissociative adsorption, transfer of species at TPB and for Pr, Ce, Zr and Sm, which agrees with the absence of catalytic
surface diusion processes.6,17,18 MF contributions are dimin- surface deterioration (catalyst coarsening) revealed by SEM
ished through the inltration with Pr, Ce, Zr and Sm catalysts, (Fig. S2).
in this order from the highest to the lowest reached Rp magni- To shed further light into the nature of the limiting steps in
tude. This eect is unambiguously assigned to the enhance- the oxygen reduction reaction (ORR), the best electrode (Pr
ment of the aforementioned surface related processes. On the inltrated) and the blank sample were tested at dierent pO2.
other hand, HF processes become limited in the electrode The blank sample presents three arc contributions at 600  C,
performance as the MF processes are progressively ameliorated HF, MF and LF, while the Pr sample has only two contributions,
HF and MLF (mediumlow frequency, 3001500 Hz). Each

Fig. 3 Fitting results of the polarization resistances for high (HF),

medium (MF), mediumlow (MLF) and low frequencies (LF) at 600  C Fig. 4 iV and iP curves for LSM-GDC/YSZ/Ni-YSZ and LSM-GDC +
for dierent pO2 and m values for the dierent frequencies. Pr/YSZ/Ni-YSZ.

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Table 3 Fitting results for the EIS spectra recorded at the OCV in a fully assembled fuel cell at 700  C

LSM-GDC/YSZ/Ni-YSZ LSM-GDC + Pr/YSZ/Ni-YSZ

Frequency range R (U cm2) C (F cm
2) f (Hz) R (U cm2) C (F cm
2) f (Hz)

HF 0.17 2.24  10
5 4.31  104 0.07 2.89  10
4 7.59  103
MF 2.57 3.10  10
5 2005 0.47 8.75  10
4 384
LF 0.57 1.09  10
3 256 0.07 3.75  10
1 6
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contribution can be related to the oxygen partial pressure by the where dissociation and oxygen adsorption processes are
equation R f PO2
mi and m claries the limiting step in the improved. This reduction of the dierent contributions is
Open Access Article. Published on 14 July 2015. Downloaded on 08/03/2016 18:23:24.

ORR:19,20 Fig. 3 depicts the modelled resistances for the dierent responsible for the enhancement of the power density reached
contributions. for the inltrated SOFC.
The non-inltrated electrode shows a pO2 independent (m
0) HF contribution, which can be assigned to the ionic transport
of the composite. The limiting processes associated with MF Conclusions
and LF slightly increases when decreasing the pO2 with m 0.12
Dierent inltrations in a robust LSM-GDC backbone electrode
and 3/8, respectively. The value of 3/8 is related to the partial
were performed, some catalysts such as Sm, Zr, Ce and Pr
reduction of the atomic oxygen (Oad + e
/ Oad
). However, the
improve the electrode performance by the reduction of the
m value 0.12 observed for MF processes origins from the
resistance at medium frequency, associated with surface
combination of two dierent mechanisms, the transport of the
processes. In contrast, Co and Ba catalysts worsen the cell
partially reduced atomic oxygen to the TPB (Oad
/ OTPB
) m
performance by increasing the resistance at medium frequen-
1/4, and the total reduction of oxygen (OTPB
+ e
/ OTPB2
)
cies in the temperature operation range.
with m 0.
The stability of the operation with time for dierent acti-
The Pr inltration decreases mainly the resistance at LM
vated cathodes was systematically studied. At rst, there is a
frequencies and slightly the HF associated resistance, which in
slight increase in the polarization resistance with time until
this case limits cathode performance. This HF contribution is
reaching a constant value. The Zr catalyst is a particular case,
also pO2 independent as it corresponds to the limiting ionic
since the polarization resistance decreases with time. The
conductivity. The slight decrease of the resistance can be
modelling results as a function of pO2 revealed that the rate-
assigned to Pr oxide properties that favour the surface diusion
limiting mechanism in the ORR is the surface transport of
of oxygen species to be transported in contrast to the blank
oxygen species towards the TPB.
sample. Furthermore, LF processes can be assigned to the
Finally, the best cathode was tested in a fully assembled
transport of partially reduced atomic oxygen to the TPB (m 1/
anode-supported fuel cell achieving a 5-fold improvement of the
4).20,21
power density. These results demonstrate the applicability of
Finally, to conrm the results obtained by using symmetrical
the inltration for the cathode performance with the resulting
cells, the best cathode and the blank were tested as a fully
improvement of the power density in the fully assembled fuel
assembled fuel cell. For this purpose, an anode-supported cell
cell.
based on the Ni-YSZ anode and 8 mm-thick YSZ electrolyte was
used (Fig. 4). The maximum power density obtained at 700  C,
by using air as oxidant feed and wet hydrogen as fuel, is ve Acknowledgements
times higher for the Pr-inltrated cathode, reaching a peak
value of 567 W cm
2 at 700  C (Fig. 4). This work was nancially supported by Spanish Government;
As both samples were identical, except for the inltration, an ENE2011-24761 and SEV-2012-0267. Electron Microscopy
EIS measurement was performed in complete fuel cell mode Service of the UPV is also acknowledged and anode supported
near the OCV at 700  C. Table 3 shows the results of the tting cells were kindly supplied by Forschungszentrum J
ulich.
with the equivalent circuit mentioned above (three R||CPE
elements). All resistances decrease with the Pr inltration; all
processes increase the capacitance and change the character-
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