Solid State Ionics 177 (2006) 3211 3216 www.elsevier.

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Intermediate temperature solid oxide fuel cell using (La,Sr)(Co,Fe)O3-based cathodes

Wi-Heon Kim a , Hwa-Seob Song b , Jooho Moon b,, Hae-Won Lee c
c

Samsung Electro-Mechanics Co., Ltd, Suwon, Kyunggi-Do, 442-743, Korea Department of Materials Science and Engineering, Yonsei University, Seoul 120-749, Korea Nano-Materials Research Center, Korea Institute of Science and Technology Seoul 136-791, Korea
b

Received 6 May 2006; received in revised form 26 July 2006; accepted 31 July 2006

Abstract Anode-supported SOFCs involving LSCF (La0.6Sr0.4Co0.2Fe0.8O3)-based cathodes are fabricated utilizing GDC interlayer on 8YSZ electrolyte for intermediate temperatures. The GDC interlayer between the LSCF cathode and YSZ electrolyte is used to prevent formation of insulating phases such as SrZrO3 or La2Zr2O7. The cell performance with the GDC interlayer was ten times better than the one without GDC at operating temperature of 750 C. However, the observed power density (370 mW/cm2) was lower than the value reported in the literature. This can be attributed to an imperfect GDC interlayer in the present study. The GDC interlayer was porous and non-uniform, so that adverse interfacial reactions could not be completely prevented. The chemical incompatibility at the interface was evaluated by SEM and EPMA, which explains the dependence of cell performance on sintering temperatures of the GDC interlayer. 2006 Elsevier B.V. All rights reserved.
Keywords: SOFCs; GDC; Interlayer; LSCF

1. Introduction Solid oxide fuel cells (SOFCs) have been one of the promising energy sources in the future. Reducing their operating temperature is a primary hurdle to commercialize SOFCs. In this regard, most recent studies have been focused on decreasing the operating temperature to 550 C750 C in order to lower the cost and to extend the lifetime of SOFCs. However, decreasing the operating temperature gives rise to lower cell performance due to less active electrode and poor conductive electrolyte. For anode-supported SOFC to be operated below 750 C, the key issue to improve the electrochemical performance is to reduce cathodic polarization resistance, which is attributed to the largest contribution of the total resistances, and to minimize ohmic resistance resulting from electrolyte [1]. These mainly depend on electrocatalytic activity of the cathodes

Corresponding author. Tel.: +82 2 2123 2855; fax: +82 2 365 5882. E-mail address: jmoon@yonsei.ac.kr (J. Moon). 0167-2738/$ - see front matter 2006 Elsevier B.V. All rights reserved. doi:10.1016/j.ssi.2006.07.049

and ionic conductivity and thickness of the electrolyte. The electrode should also be thermally and chemically compatible with the underlying electrolyte, otherwise non-catalytic insulting phases may form at the interface, increasing the polarization resistance. Mixed ionicelectronic conductor LSCF is an attractive material as a cathode for intermediate temperature SOFCs. Compared with conventional cathodes based on LSM, the performance of SOFCs with LSCF cathode is better due to higher catalytic activity as well as good ionic and electronic conductivities. However, it is reported that the insulating SrZrO3 or La2Zr2O7 phase between LSCF cathode and yttriastabilized zirconia (YSZ) electrolyte can be formed at the temperature range needed for LSCF cathode sintering and in turn lower the electrochemical performance [24]. In many studies, the GDC or SDC have been used as an interlayer between LSCF cathode and YSZ electrolyte to prevent undesirable interfacial chemical reactions [4,5,13]. The interlayer film should be not only dense but also have no thermal chemical interactions with the cathode and electrolyte. In this

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study, we have focused on the GDC interlayer formed by dip coating. Chemical reactions behavior between the LSCF cathode and YSZ with/without GDC interlayer was investigated by XRD and elemental analysis. It is demonstrated that microstructural control of the GDC interlayer plays an important role to improve the cell performance. 2. Experimental methods 2.1. Powder preparation The LSCF cathode powders were prepared by the Pechini method [6,7]. The nitrate salts of La, Sr, Co, and Fe were dissolved in water in molar ratio of 3:2:1:4 (La0.6Sr0.4Co0.2 Fe0.8O3). Then, ethylene glycol and citric acid were added to bind the metal cations. After a polymerization reaction at 100 C, the polymer gel was charred at 400 C to remove organics and nitrates and then calcined at either 800 C (denoted as LSCF800) or 1000 C (denoted as LSCF1000) for 4 h to develop crystalline perovskite phase. BET analysis, X-ray diffraction (XRD), and scanning electron microscopy (SEM) were used to characterize the materials. 2.2. Cell fabrication Disk-shaped anode-supports with thickness 1.0 mm were prepared by pressing NiOYSZ composite granules made by

Fig. 2. Anode supported single cell performance data at 750 C as a function of sintering temperature and LSCF starting powder (H2: 250 cm3/min, Air: 250 cm3/min).

liquid condensation process [8]. The YSZ suspension was prepared by mixing 8 mol% Y2O3-stabilized ZrO2 powder (Tosoh, TZ8Y) with organic additives. The YSZ suspension was applied onto the anode substrate using dip-coating and then cofired with the anode at 1400 C for 4 h to achieve thin and dense electrolyte film (thickness 10 m). The mean pore diameter and porosity of NiYSZ anode-supports after reduction were 0.59 m and 41%, respectively [8]. The GDC (Ce0.8Gd0.2O2, Rhodia) interlayer was applied if necessary on top of the YSZ electrolyte by dip-coating followed by sintering at temperatures of 1250 C1400 C. The LSCF cathode paste prepared by mixing the powder with ethylcellulose and terpineol was screen-printed onto the GDC interlayer and sintered at 1000 C and 1100 C. The area of the cathode layer was 1.5 cm2 and its thickness was about 1520 m. 2.3. Characterization of microstructure and chemical reaction The cell microstructure was investigated using scanning electron microscopy (ESEM, FEG XL 30, FEI). X-ray diffraction (XRD) and electron probe micro analyzer (EPMA, EPMA1600, SHIMADZU) were used to analyze chemical reactions between LSCF and YSZ at varying temperatures (9001200 C) and at the interfaces between GDC and YSZ with sintering temperature (12501400 C). 2.4. Evaluation of the cell performance The cell performance was measured from 550 C to 750 C at 100 C interval using a fuel gas consisting of humidified H2 at the anode chamber and air at the cathode chamber. The current voltage characteristic of the cell was measured with increasing current load by 50 mA. AC impedance spectroscopy (Solartron SI 1260/SI 1287) was used to measure the polarization resistance of the electrochemical cells at the operating temperatures. The impedance measurements were performed at decreasing frequency from 100 kHz to 0.1 Hz, with an amplitude of 20 mV.

Fig. 1. SEM photographs of LSCF calcined at (a) 800 C (LSCF800, specific surface area = 7.3 m2/g) and (b) 1000 C (LSCF1000, specific surface area = 1.7 m2/g).

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3. Result and discussions 3.1. Effects of LSCF starting powder and its firing temperature on cell performance Calcination temperature of the Pechini method-derived powders has an influence on microstructure of the resulting cathode. The polarization resistance of the cathode and the cell perfor-

Fig. 4. X-ray diffraction patterns for LSCF cathodeYSZ electrolyte composites sintered at the varying temperatures: (a) 900, (b) 1000, (c) 1100, and (d) 1200 C.

mance are strongly dependent on microstructure of the cathode such as phase contiguity and porosity [912]. Fig. 1 shows SEM photographs of the LSCF powders calcined at 800 C and 1000 C. The specific surface areas of LSCF800 and LSCF1000 were 7.3 and 1.6 m2/g, respectively. XRD analysis revealed that both the synthesized LSCF800 and LSCF1000 are highly crystalline perovskite phase without any impurity or secondary phases. The electrochemical performance of the cells fabricated with LSCF800 and LSCF1000 was shown in Fig. 2. The cathodes were sintered at either 1000 C or 1100 C on the GDC interlayer sintered at 1390 C. The maximum power density was observed for the cell made with LSCF1000 sintered at 1000 C (denoted as LSCF10001000), exhibiting 340 mW/ cm2 when measured at 750 C. The cell prepared with smaller LSCF particles, i.e., LSCF800, fired at 1000 C (LSCF800 1000) showed a little less power density 272 mW/cm2, probably due to reduced electrochemical reactive sites by excess sintering. When sintered at 1100 C, lower power densities were observed regardless of the starting powder characteristics. Although the performance of all the cells tested varied to some extent depending on the sintering temperature and LSCF

Fig. 3. Influences of the GDC interlayer on the cell characteristics: (a) cell performance, (b) polarization resistance, and (c) ohmic resistance data measured at 750 C. The cathodes were fabricated with LSCF800 sintered at 1100 C.

Fig. 5. The cell performance for the samples with GDC interlayer sintered at the varying temperatures. The same cathodes of LSCF800 fired at 1100 C were used.

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starting powders, however, this variation was not so clear as described in a recent report regarding LSCF(La0.6Sr0.4Co0.2Fe0.8O3)-based SOFCs in which the power was in the range of 540 mW/cm2 at 0.7 V [13]. Even the cell made from commercial LSCF powder (Rhodia) exhibited the power density of 310 mW/cm2. These observations indicate that our poor cell performance is mainly attributed to the GDC interlayer, not to the cathode itself. 3.2. LSCF cathode electrochemical performance with GDC interlayer It has been reported that the introduction of GDC interlayer prevents formation of poor conducting phases like Sr-zirconate or La-zirconate. The power density for the cell with GDC interlayer was ten times higher than the cell without GDC, as shown in Fig. 3(a). Lower power density could be attributed to increased polarization resistance as shown in Fig. 3(b), which likely results from the formation of secondary phases at the electrode/electrolyte interface. The X-ray diffraction analyses for LSCFYSZ composites reacted between 900 C and 1200 C were performed to confirm the chemical stability between LSCF and YSZ. Fig. 4 showed the appearance of the secondary phases such as SrZrO3 and La2Zr2O7. Even at 900 C, SrZrO3 was detected and La2Zr2O7 starts to form at 1100 C. This result indicates that the GDC interlayer should be sufficiently dense and uniform, otherwise the chemical incompatibility between the GDC and YSZ significantly deteriorates the cell performance as observed in Fig. 3(b).

Ohmic resistance of the cell is expected to decrease by introducing a higher ionic conducting thin GDC interlayer (2 3 m) even if the total electrolyte thickness slightly increases. Regardless of the presence of GDC, however, the ohmic resistances were similar for both cells in the range of operating temperatures (550 C750 C) as presented in Fig. 3(c). This result possibly indicates that the additional contribution of our 23 m GDC interlayer is very small to enhance the ionic conductivity of the electrolyte. The electrochemical performance of the cells with GDC interlayer sintered at the varying temperatures (12501400 C) was compared. The LSCF800 cathode was applied on the fired GDC interlayer, followed by sintering at 1000 C (i.e., LSCF8001000). As shown in Fig. 5, the power density increased with increasing GDC sintering temperature, reaching a maximum at 370 mW/cm2 when the interlayer was fired at 1350 C, while further increase in sintering temperature deteriorates the cell performance. The variation in the cell power on the GDC firing temperature should be understood in terms of its microstructure and interfacial chemical reactivity. 3.3. Analysis of microstructure and chemical reaction at interface Fig. 6 shows cross-sectional microstructures of the cells with GDC sintered at different temperatures. The GDC layers became denser and thinner with increasing sintering temperature. The interlayer exhibited relatively porous structure with the thickness of 34 m when fired at below 1300 C, while

Fig. 6. SEM photographs of cross-section of anode-support single cell with GDC interlayer sintered at (a) 1250 C, (b) 1300 C, (c) 1350 C, and (d) 1390 C.

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nearly fully dense layer with thickness 12 m was observed at 1350 C. The spatial distributions of La, Sr, Ce, and Zr elements were determined by EPMA mapping over LSCF/GDC/YSZ interfaces to evaluate their chemical reaction behavior as a function of the GDC sintering temperature. As shown in Fig. 7, it is clear for the cells with GDC fired at 1250 C and 1300 C that both the La and Sr species diffuse through porous GDC layer to react with YSZ, forming electrochemically inactive La- or Sr-zirconia phases. In contrast, the cell fired at 1350 C maintains well-defined phase boundaries of the Ce and Zr in which the La distribution is limited to the upper region, while the Sr diffuses down to some extent. Further increase in the sintering temperature could form a uniform pore-free interlayer by sufficient densification. But it is not perfectly dense because the layer is too thin to accommodate significant volumetric shrinkage induced by excess densification when fired at too high temperature. The EPMA results combined with SEM microstructural analysis are in good agreement with the cell performance data. The maximum power density was observed for the cell with GDC sintered at 1350 C in which the adverse interfacial reactions are minimized. It should be noted that the position of the Zr species is elevated into the GDC interlayer region for the cells fired at above 1300 C. This indicates that when it was sintered at 1390 C, YSZGDC solid solution is formed, which in turn lowers cell performance by increasing ohmic resistance as

shown in Fig. 5. YSZGDC solid solution is known to have a lower conductivity than YSZ and GDC [2,14]. The presence of such a less ionically conductive YSZGDC solid solution together with a SrZrO3 insulting phase at the interfaces prevents our cell with LSCF/GDC-based cathode from exhibiting high cell performance. In this regard, it is especially important to obtain uniform and dense ceria interlayer at reasonably low temperature in order to use YSZ electrolyte for SOFCs operated at intermediate temperatures. 4. Conclusions We have investigated the influence of GDC interlayer on the cell performance for LSCF-based cathode on YSZ electrolyte in anode-supported configuration. The GDC interlayer played an important role as a diffusion barrier to prevent chemical reaction at the LSCF/YSZ interface. There was an optimum sintering temperature for the GDC interlayer in order not only to develop a sufficient barrier against the La and Sr migration from LSCF cathode but also to prevent formation of a solid solution with the underlying YSZ electrolyte. However, our GDC interlayer is considered as an imperfect barrier, even optimized in our experiments. SEM analysis and elemental distribution mapping confirm the presence of insulting phase and less ionic conductive YSZGDC solid solution. This explains relatively less cell performance of our cells compared to the one with the same

Fig. 7. EPMA mapping data of Sr, La, Zr and Ce elements obtained at the cross-sections of LSCF/GDC/YSZ interface in which the GDC interlayer was fired at the varying temperatures: (a) 1250 C, (b) 1300 C, (c) 1350 C, and (d) 1390 C. The scanned area was 63.5 m in width and 7 m in height.

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material system reported by others. The cell with GDC interlayer sintered at 1350 C had the maximum power density of 370 mW/cm2 at 750 C. Acknowledgement This work was supported by the Core technology Development Program for Fuel Cell of Ministry of Science and Technology and Korea Institute of Science and Technology Evaluation and Planning. It was also partially supported by the National Research Laboratory (NRL) Program of Korea Science and Engineering Foundation. References
[1] T.J. Amstrong, J.G. Rich, J. Electrochem. Soc. 153 (2006) A515. [2] A. Tsoga, A. Gupta, A. Naoumidis, P. Nikolopoulos, Acta Mater. 48 (2000) 4709.