CONTRIBUTION TO SPECIAL ISSUE

Ag modified LSCF as cathode material for protonic conducting SOFCs

G.-H. Zhou, X.-Z. Fu, J.-L. Luo*, K. T. Chuang and A. R. Sanger
BaCe0?7Zr0?1Y0?2O32d (BCZY) electrolyte and La0?6Sr0?4Co0?2Fe0?8O32d (LSCF) cathode perovskite materials were synthesised using the citratenitrate combustion method. NiOBCZY anode supported thin film sold oxide fuel cells (SOFCs) was fabricated using spin coating and cosintering process. LSCF exhibited good chemical stability in H2O containing atmosphere and chemical compatibility with BCZY proton conducting material. The electrochemical performance of the AgLSCF composite cathode was dependent on the Ag content. The thin film proton conducting SOFC displayed highest maximum power density of 563 mW cm22 at 700uC for 10 wt-%Ag(LSCFzBCZY) composite cathode.
Keywords: Cathode catalyst, Thin film electrolyte, Solid oxide fuel cells, AgLSCF composite

This paper is part of a special issue on Solar Energy

Introduction
Lowering the operating temperature is one of the critical means to improve commercialisation of sold oxide fuel cell (SOFC) technology.1 Although proton conducting SOFCs can operate at lower temperature when compared to traditional Y2O3 stabilised ZrO2 (YSZ) oxide ion conducting SOFCs,2,3 the performances to date of proton conducting SOFCs still are lower than those of optimised oxide ion conducting SOFCs. These phenomena might be ascribed to high electrode polarisation and electrolyte resistance at reduced operating temperature.4 The electrolyte (ionic) resistance can be reduced dramatically using a thin lm electrolyte on an electrode support structure.5 However, the improvement of performance is still limited, mainly as a consequence of large cathode polarisation at low temperature. Thus, development of improved cathodes is of great importance for low to intermediate temperature SOFCs. An ideal cathode catalyst for protonic SOFCs should have the following characteristics: high electronic, protonic and oxide ionic conductivity; high electrocatalytic activity for oxygen reduction; chemically stable in oxidizing humid atmospheres at intermediate temperatures; and chemically and thermally compatible with other components of the fuel cells. However, it is almost impossible for one material to satisfy all these requirements as cathode materials. Researchers have been devoting their energy to improve cathode performance based on cathode materials commonly used in oxide ion conducting SOFCs. Protonic conductivity is introduced by adding proton conducting materials, which are often the same materials used as an electrolyte, to the cathode oxide.68 Noble metals such as
Department of Chemical and Materials Engineering, University of Alberta, Edmonton, AB T6G 2G6, Canada *Corresponding author, email Jingli.Luo@ualberta.ca

Ag, Pt and Pd are used in admixtures with the oxide cathodes to improve the cathode performance. The introduction of precious metals into oxide cathodes may increase the electronic conductivity and the electrocatalytic activity for the oxygen reduction reaction due to the high electronic conductivity of precious metals and the synergetic effect of precious metals and oxide electrodes.912 La0?6Sr0?4Co0?2Fe0?8O32d (LSCF) perovskite oxide is a promising cathode material for SOFCs operated at intermediate temperature.13 The performance of Ni YSZ|Ce0?9Gd0?1O1?95|LSCF cell was investigated in the temperature range of 550650uC.9 Peak power densities of 140 and 80 mW cm22 were observed at 650 and 600uC respectively. The addition of Pd to the LSCF cathode was found to decrease the overall cell resistance by 15% at 650uC and by 40% at 550uC.9 However, the cell performance deteriorated fast with the addition of Pd,10 and the price of Pd noble metal is very expensive. Ag is the least expensive among the noble metal family and has good catalytic activity and high electrical conductivity, which make it an excellent candidate as cathode material for SOFCs. The performance of AgLa0?6Sr0?4Co0?8Fe0?2O3Ce0?8Gd0?2O1?9 (GDC) cathode on a GDC electrolyte was studied using the ac impedance method at steady state with various dc bias currents; the addition of Ag into the LSCFGDC composite electrode improved the catalytic activity for oxygen reduction.11 The peak power density for the Ni (ZrO2)0?89(Sc2O3)0?1(CeO2)0?01(ScSZ)|ScSZ|GDC|LSCF single tubular cell without Ag loading at 550uC was 110 mW cm22 and signicantly increased to 490 mW cm22 with Ag impregnation.12 Herein, we investigated Ag modied LSCFz BaCe0?7Zr0?1Y0?2O32d (BCZY) composite as cathode catalyst for proton conducting SOFCs. BCZY was chosen as the electrolyte because it is more stable than BaCe0?85Y0?15O32d (BCY) against adverse reactions with CO2 and H2O containing atmospheres.6

2012 W. S. Maney & Son Ltd. Received 27 March 2012; accepted 26 July 2012 DOI 10.1179/106678512X13457972694584

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Experimental
Both the BCZY electrolyte and the LSCF cathode materials were prepared using the citratenitrate combustion method. The starting materials included Ba(NO3)2 (Alfa Aesar, 99z%), Ce(NO3)3.6H2O (Alfa Aesar, 99?5%), Y(NO3)3.6H2O (Alfa Aesar, 99?9%) and ZrO(NO3)2.xH2O (Aldrich, 99%) as metal precursors. The water content of zirconium (IV) oxynitrate hydrate was determined using thermogravimetric analysis. Stoichiometric amounts of metal nitrate were dissolved in deionised water. Citric acid (Alfa Aesar, 99?5z%) and NH4NO3 (Aldrich, 99?5z%) were added as chelating agent and oxidant at a molar ratio of citric acid/total metal ions/NH4NO3 of 1?5 : 1 : 3. When a clear solution was obtained, ammonium hydroxide (Acros, 2830%NH3 in water) was added dropwise to adjust the pH to ,8. The nal clear solution was heated on a hot plate to evaporate solvent until brown foam was formed and ignited. The as combusted powder was then calcined between 1000 and 1500uC for 10 h to get the desired perovskite phase. The as prepared powders were characterised using X-ray diffraction (XRD) at room temperature under ambient conditions with the Rigaku Ultima IV powder diffractometer with Co Ka radiation ). The scanning rate of the spectra was (l51?789 A 2hu min21. The commercially available software Jade was used to identify phases for the samples. The anode supported BCZY half cells were fabricated using a suspension spin coating method. Powders consisting of green nickel oxide (Novamet), BCZY and graphite powder (Aldrich, ,20 mm) as pore former with weight ratio 65 : 35 : 20 were thoroughly mixed in isopropanol in a high energy ball milling machine at 350 rev min21 for 1 h. The mixture was dried and pressed uniaxially into pellets followed by ring at 1100uC for 5 h to form porous substrates. BCZY electrolyte thin lm was deposited on the substrates with a spin coating method. The at substrates polished with sandpaper were xed in a spin coating machine (Cookson electronics equipment specialty coating system). A thin layer of stable suspension was spin coated onto the substrate and then dried, followed by evaporating and burning out part of the solvent with a heater. The thickness of the electrolyte could be controlled with the number of spin coating times. The suspension used for spin coating was obtained by mixing 20 wt-%BCZY powders and 80 wt-% organic vehicle in an ultrasonic machine for 30 min. The electrolyte coated anode substrate was then co-red at 1400uC for 5 h to form a dense electrolyte thin lm. The slurry of the cathode material made with the prepared powder mixture [BCZY/(LSCFzAg)550 : 50] and commercially available vehicle ink (Fuel Cell Materials) was brush painted onto the BCZY surface of the anode supported bilayer pellet followed by ring at 900uC for 0?5 h. Ag paste as the current collector was applied to cathode side and red at 800uC for 0?5 h to prepare the membrane electrode assembly. The membrane electrode assembly was placed between two co-axial alumina tubes to form the anode and cathode compartments. Ceramic sealant (Ceramabond 503, Aremco) was applied on the outer tubes to seal the gas compartments. The internal diameter of the outer alumina tubes was 8 mm, and the surface area of cathode was

1 X-ray diffraction patterns of LSCF powder calcined for 2 h at a 700uC, b 750uC and c 800uC

0?32 cm2. The cell was then heated in a Thermolyne F79300 tubular furnace to cure the sealant, and the temperature was adjusted to the selected operating temperature. Gold current collector wires (two probes) with spiral wound ends ran through the length of the inner tube. Electrode performance was investigated for the single cell conguration with an electrochemical workstation based on a Solartron 1287 potentiostat and a Solartron 1255 frequency response analyser. The tests were conducted using a four electrode set-up from 550 to 700uC at 50uC intervals. Air and 3 vol.-%H2O/H2 gas were fed to the cathode and the anode respectively, at 20 lb in22 pressure with the owrate of 100 mL min21. Potentiodynamic mode was used for performing currentpotential measurements. Potentiostatic mode was used to monitor the current stability at the set potential of 0?75 V. Impedance measurements were conducted under open circuit voltage (OCV) conditions. The frequency was varied from 0?01 Hz to 1 MHz with signal amplitude of 10 mV. The microstructure and morphology of particles and sintered products were determined with a Zeiss scanning electron microscope. The cross-section was obtained by fracturing the sample. A conducting carbon tape was used to ensure the electron conductivity. A thin layer of gold was sputtered onto the samples because the perovskite ceramics were non-conductive at room temperature.

Results and discussion

Characterisation of LSCF
As shown in Fig. 1, a single perovskite phase structure of LSCF powder was obtained using the citratenitrate combustion method at 700, 750, and 800uC for 2 h. No peaks attributed to impurities were detected using XRD technique. To determine the compatibility between the LSCF and the BCZY electrolyte, a mixture of LSCF and BCZY powers with weight ratio of 50 : 50 was red at 1000 and 1100uC for 10 h. There was no signicant amount of impurity from the mixture of BCZY and LSCF at 1000uC. As shown in Fig. 2, the XRD patterns of the mixture after the calcination at 1000uC can be indexed well based on a physical mixture of LSCF and

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4 Image (SEM) of cross-sectional area of anode supported single cell 2 X-ray diffraction patterns of BCZY, LSCF and mixed powder of LSCF and BCZY at weight ratio of 50 : 50 after calcination at 1000 and 1100uC

BCZY materials. However, when the temperature was increased to 1100uC, a small peak of unidentied phase was detected in the XRD pattern. Thus, the ring temperature of cathode with BCZY proton conducting electrolyte should not go higher than 1100uC to avoid any reaction between the cathode and the electrolyte layers. In a proton conducting SOFC, water is produced at the cathode side when protons are transported through the electrolyte and react with oxygen species at the cathode side. Therefore, the cathode material must be stable under a humid atmosphere. Figure 3 shows the XRD patterns of the as prepared LSCF and LSCF after exposure to 15 vol.-%H2Oair at 700uC for 20 h. No new phases were detected in the XRD patterns, which showed that the LSCF was stable against reaction in a humid atmosphere.

Characterisation of anode supported single cells

To prepare the Ag modied LSCF cathode, the ring temperature was limited by the melting temperature of Ag (961uC) to prevent agglomeration of the Ag species, which can block the transport path for gaseous oxygen.

Thus, the temperature was lower than commonly used ring temperatures of electrodes, typically between 1000 and 1200uC. While a low temperature may result in poor attachment between cathode and electrolyte, a low temperature also may alleviate complications arising from chemical incompatibility between the electrode and the electrolyte layers. The thickness of the dense electrolyte was ,40 mm (Fig. 4). Figure 5 is the cross-sectional scanning electron microscopy images of the cathode with different Ag contents red at 900uC after single cell tests. The cathode layer was well attached to the electrolyte layer. However, the cathode layer was not strongly attached to the electrolyte layer for the case without Ag addition. The cathode layer without Ag addition was easily removed from the electrolyte by scraping, whereas the Ag added cathode layer was not easily removed. The low melting point of Ag facilitated the adhesion properties of the cathode, and the ceramic impeded grain growth of Ag to some extent. The cathode grains were very ne due to the low sintering temperature, and the cathode was porous.

Electrochemical performance of single cells

The oxygen reduction reaction on cathodes of oxide ion conducting SOFCs has been extensively studied. It is well known that mixed ionicelectronic conductor can extend the electrochemically active sites to the cathode surface of triple phase boundary. When using a mixed oxide ionic electronic conductor on a protonic SOFC, the reaction sites are limited. In order to extend the reaction sites, a potential cathode must have protonic, oxide ionic and electronic conductivity. A cathode material conducting protons, oxide ions and electrons can extend reduction reaction sites from the electrolyte/cathode interface to the entire cathode surface. Unfortunately, a single phase protonic, oxide ionic and electronic conductor has not been developed. The idea of a composite cathode with a mixed ionicelectronic conductor and a protonic conductor may tailor the properties of a potential cathode for protonic SOFCs. The performance of a composite cathode may be further improved with the addition of Ag, which is a good electronic conductor. Figure 6 compares the maximum power densities of anode supported single cells with different Ag contents. The performance improved with an increase in Ag content in the cathode at a low amount up to 10 wt-%Ag, which

3 X-ray diffraction patterns of LSCF before and after being exposed to 15 vol.-%H2O/air at 700uC for 20 h

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a 10 wt-%Ag; b 20 wt-%Ag; c 40 wt-%Ag; d 50 wt-%Ag 5 Morphologies (SEM) of cross-sectional areas of Ag(LSCFzBCZY) cathode

might be ascribed to the decrease in ohmic resistance and catalytic activity enhancement. However, the performance decreased with further increase in Ag content. This trend becomes prominent at elevated temperatures. This might be because too much Ag and low LSCF catalytic materials in the cathode could decrease the oxygen reduction reaction.

Figure 7 is the electrochemical impedance spectroscopy of thin lm single cells with different amounts of Ag tested at 600uC under OCV conditions. Both the ohmic resistance and the polarisation resistance of the button cell decreased with 10 wt-%Ag, indicating that the addition of Ag increased the electronic conductivity and electrocatalytic activity of the cathode. Although ohmic resistances were usually mainly related to the electrolyte, here, the cathode layer with the BCZY/

6 Peak power densities for single cells as function of Ag content in cathode catalyst

7 Electrochemical impedance spectroscopy of single cell with different Ag content in cathode at 600uC under OCV condition

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8 IV and power density curves of single cell at 600uC with different Ag content in cathode

(LSCFzAg) ratio of 1 : 1 might also contribute the ohmic resistance in the thin lm electrolyte fuel cell. Interestingly, as shown in Fig. 7, for the single cells with Ag content .10 wt-%, both the ohmic and the polarisation resistance increased with an increase in Ag content in accordance with the performances compared in Fig. 8. Figure 9 shows the IV curves of a typical cell with 10 wt-%Ag cathode materials operating on H2 fuel at temperatures between 550 and 700uC. The OCVs were 1?16, 1?13, 1?10 and 1?06 V at 550, 600, 650 and 700uC respectively. This indicated that the electrolyte was dense enough to prevent gas crossover. The linear correlation between the voltage and applied current suggests that concentration polarisation did not take place, even at high current density. This further proves that the composite cathode was porous enough for the gaseous oxygen passing through, and the addition of 10 wt-%Ag did not cause agglomeration problems at the cathode. The maximum power densities at 550, 600, 650

and 700uC were 245, 360, 472 and 563 mW cm22 respectively. The impedance spectra of the cell with 10 wt-%Ag at various temperatures under OCV conditions were collected as Nyquist plots as shown in Fig. 10a. Ohmic

9 IV and power density curves of NizBCZY|BCZY|10 wt-%Ag(LSCFzBCZY) single cells with H2 as fuel at various temperatures

10 a impedance spectra of single cells with 10 wt-%Ag tested under OCV and b calculated resistance of cell as function of temperature

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stability test under cell operating condition was conducted at a constant applied potential of 0?75 V at 700uC, and the current density as a function of time is shown in Fig. 11. The current densities were relatively stable, and there was no substantial degradation in the cell performance within 3 days of operation, indicating that the composite cathode was a stable candidate material for application in protonic SOFCs at 700uC and lower temperatures.

Conclusions
Cathode material LSCF was prepared using a citrate nitrate combustion method. LSCF was stable against an H2O containing atmosphere and chemically compatible with proton conducting electrolyte material of BCZY at temperatures up to 1000uC. The mixed composite cathode with 10 wt-% Ag demonstrated enhanced catalytic activity toward oxygen reduction reaction compared to a LSCFzBCZY cathode without Ag. A long term durability test showed the composite cathode was stable.

11 Long term stability of NizBCZY|BCZY|10 wt-%Ag (LSCFzBCZY) single cell at constant output voltage of 0?75 V at 700uC

resistance Rohm is indicated by the intercept at high frequency with the real axis, while polarisation resistance Rp is given by the intercept of the impedance plot between high frequency and low frequency with the real axis and is related to the electrochemical reactions at both cathode/electrolyte and anode/electrolyte interfaces. The resistances decreased dramatically with increase in temperature. Figure 10b shows the calculated resistances (Rohm, Rp and Rtotal) obtained from electrochemical impedance spectroscopy in Fig. 10a. A very low area specic polarisation resistance of 0?07 V cm2 was obtained at 700uC, which resulted in the high performance. Rohm increased from 0?40 V cm2 at 700uC to 0?71 V cm2 at 550uC, while Rp increased from 0?07 V cm2 at 700uC to 1?04 V cm2 at 550uC. When the temperature decreased from 700 to 550uC, Rohm almost doubled, while Rp increased by 14 times, which conrmed that polarisation resistance was the predominant factor in the total cell resistance for the cell performance. It is critical to evaluate the long term durability of the single cell with a 10 wt-%Ag(LSCFzBCZY) composite cathode. One potential problem with Ag modied SOFC is that an operating temperature close to its melting point may cause agglomeration of Ag and thus deterioration of the cell performance with time. The

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