Characterization and Stability of La0.7Sr0.3Co0.3Fe0.

7O3 Perovskite-type Oxide

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Characterization and Stability of La0.7Sr0.3Co0.3Fe0.7O3 Perovskite-type Oxide

LI Yan*, Luo Zhongyang**, Yu Chunjiang**, Wei Xinli*, Cen Kefa** *School of Chemical Engineering, Zhengzhou University, Zhengzhou, 450001, China
(E-mail: lliyan@zzu.edu.cn)

**State Key Laboratory of Clean Energy Utilization, Zhejiang University, Hangzhou, 310027, China
(E-mail: zyluo@cmee.zju.edu.cn) Abstract: Compositely doped oxide La0.7Sr0.3Co0.3Fe0.7O3 LSCF was synthesized using solid state reaction and citric acid-nitrate low temperature self-propagating combustion methods. The crystal structure and the particle size micrograph of LSCF powders synthesized by different methods were investigated with XRD and SEM. The experimental results show that the single perovskites phase of LSCF can be synthesized by both methods. The particle size of LSCF by citric acid-nitrate low temperature self-propagating combustion method was the smaller. Two types of cathodes wafers were fabricated with the two kinds of LSCF powders and Ce0.9Gd0.1O1.95 (GDC) at the mass rate of 6:4, respectively. The electrical conductivity of sintered samples was measured by four probe DC method from 100 -800 . The cathode with LSCF particle by citric acid-nitrate low temperature self-propagating combustion method has the higher electrical conductivity. The conduction mechanism for the samples is attributable to the adiabatic-hopping of p-type small polaron. In order to investigate the stability, the samples were put into the muffle furnace to heat up in air at 800 for 800h. To analyze the reason for reduced electrical conductivity, the crystal structure and the particle micrograph of the cathodes before and after exposure were investigated with XRD and SEM. The result shows that both cathodes have good stability, good compatibility with GDC. The sample micrographs do not change too much. The electrical conductivity of the two cathodes reduces a little after exposure. Keywords: Solid oxide fuel cell, La0.7Sr0.3Co0.3Fe0.7O3 synthesis method, Cathode, Electrical conductivity, Stability LSCF powder was synthesized using solid state reaction and citric acid-nitrate low temperature self-propagating combustion methods. Two kinds of cathodes wafers were fabricated with this two kinds of LSCF powders and Ce0.9Gd0.1O1.95 GDC at the mass ratio of 6:4. In order to study the stability, the samples were put into the muffle furnace and heated up in air at 800 for 800h. The effect of LSCF powder fabrication technique on LSCF power morphology, microstructure of the cermet cathode, particle size and electrical conductivity of cathode wafers was investigated. The change of the two kinds of cathodes wafers before and after exposure in air was analyzed and compared.

1 INTRODUCTION
La1-xSrxCo1-yFeyO3- peroskite-type complex oxide has good stability because of its large cation match location number. On one hand, this kind of material shows high oxide ion conductivity due to Variable Valence cation or doping Cations with different Valence, on the other hand, it shows high electronic conductivity because of the changed valence of transition metal ion. Currently, La1-xSrxCo1-yFeyO3material becomes representative in the application field of SOFC cathode material [1-3]. Teraoka studied ionic and electronic conductivity of La1-xSrxCo1-yFeyO3- through four probe and Oxygen Permeability technology, the result shows that the ionic conductivity increases with the increase of the Sr concentration or the decrease of Fe concentration [4]. Tai studied the impact of Sr concentration on crystal structure and properties of La1-xSrxCo1-yFeyO3 and found the single peroskite structure can be formed when x 0.4 [5,6]. According to current research, it is necessary to further study La0.7Sr0.3Co0.3Fe0.7O3 material because it is a kind of ideal cathode material. However, most of current studies about La1-xSrxCo1-yFeyO3- material concentrate on the impact of element proportion on material properties. The impact of different fabrication method and the long-time effect is seldom noticed. In this paper, compositely doped oxide La0.7Sr0.3Co0.3Fe0.7O3

2 EXPERIMENTAL PROCEDURE
2.1 Citric acid-nitrate low temperature self-propagating combustion method Stoichiometric amounts of La(NO3)3 6H2O, Sr(NO3)3, Co(NO3)3 6H2O and Fe(NO3)3 9H2O were mixed in distilled water, then 1.5 mol of citric acid was added to the mixture for each mol of metal ion and some ammonia was added to adjust PH 5. The mixture was heated to cause evaporation of the solvent. After spontaneous ignition, the resulted foam-shape ash was collected and calcined in air at 900 for 14 hours, then cooled to room temperature and was ball-milled for 1 hours at 180r/min, and put to muffle furnace to calcine in air

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International Conference on Power Engineering-2007, October 23-27, 2007, Hangzhou, China powders are shown in Fig.2. It is noticeable that both the two kind of LSCF powders form agglomerates. The particle size of LSCF made by citric acid-nitrate low temperature self-propagating combustion method was smaller. The average size is about 200nm except partly above 1 m because of the strong agglomeration. The LSCF powder made by solid state reaction method has bigger particle diameter which ranges between 100nm and 4-5 m and is obviously bigger than the size calculated through scherrer formula [7]. Possible reason for this kind of chelation is that high calcination temperature and long calcination time produce molten phenomenon when the crystal is forming. The specific surface areas of the LSCF powders were 0.5279m2/g and 0.1976m2/g measured by nitrogen adsorption according to the BET method with QUANTACHROME AUTOSORB-1 instrument. It coincides with SEM analysis that the specific surface area increases when the particle size decreases.

at 1100 for 24 hours again to form the ultimate power called b-LSCF. 2.2 Solid state reaction method Stoichiometric amounts of La2O3, SrCO3, Co3O4 and Fe2O3 were mixed and ball-milled for one hour at 180r/min, then calcined in air at 1100 for 24 hours at the increasing temperature rate of 120 /h. The resulted powder was ball-milled for one hour at 180r/min and calcined in air at 1200 for 24 hours again to form the ultimate power called m-LSCF. 2.3 Cathode slice fabrication and degradation test For all the cathodes in this study, LSCF powder was mixed with self-made GDC powder at the mass ratio of 6:4. This mixture with added binder was ball-milled for 24 hours to form a homogenous powder that was cold pressed under 30MPa into wafers ( 25mm1mm). The shaped wafers were put into the muffle furnace to be heated up to 400 at the increasing rate of 30 /h and kept for 2 hours, and continued to heat up to 800 at the increasing rate of 60 /h and kept for 2 hours, then continued to heat up to 1100 at the increasing rate of 30 /h and kept for 4 hours. Then the calcined powder was cooled to room temperature at the same decreasing temperature rate according to the increasing rate. The two kind cathodes wafers were called b-LSCF-slice and m-LSCF-slice according to different LSCF power, respectively. In order to investigate the stability, the samples were put into the muffle furnace to heat up in air at 800 for 800h, which were called b-LSCF-lose and m-LSCF-lose accordingly. 2.4 Measurement procedure The crystallization of the synthesized powders and fabricated cathodes wafers before and after exposure was examined by X-ray diffraction (XRD, D-max-rA) using Cu-K radiation. The microstructure and particle size were analyzed by Field Scanning Electron Microscopy (FSEM, SIRION). The electrical conductivity of the cathodes wafers before and after exposure was measured between 100 and 800 by four probe DC methods. The samples were cut into rectangle slice at the size of 3mm5mm using low-speed saw and connected with Pt wire and paste, then put into a reaction furnace to change the working temperature. S-type thermocouple was used to measure the temperature of the sample and Keithley 2182 was used to input the temperature to a computer. The resistance was measured with Model LR-700 AC Resistance Bridge.

Fig.1 Power X-ray diffraction patterns of LSCF by different synthesis methods

3 RESULTS AND DISCUSSION

3.1 Cathode powder characteristics Fig.1 shows the X-ray diffraction patterns of LSCF made by different methods. The result shows that the single perovskite phase of LSCF can be synthesized by both methods and all peaks are acute which demonstrates that all the samples have good crystal shape. The micrographs of LSCF

Fig.2 SEM photographs of LSCF powder by different

Characterization and Stability of La0.7Sr0.3Co0.3Fe0.7O3 Perovskite-type Oxide synthesis methods 3.2 Electrical conductivity before and after exposure The Arrhenius curve between ln T and 1000/T of the sintered cathodes wafers was shown in Fig.3. The figure shows that the electrical conductivity of all the samples changes with temperature in the same changing trend. The electrical conductivity of b-LSCF-slice is higher than that of m-LSCF-slice. After exposure, the electrical conductivity of both samples decreases. For all the samples, the plots of ln T versus 1000/T are linear and the electrical conductivity increases with temperature when temperature is lower than 600 . There is a peak at 600 or so, then the electrical conductivity decreases with further increased temperature. This result coincides with the study of Huang Duan-ping [8], but there is a lower electrical conductivity value due to the added GDC. For ABO3 perovskite-type LSCF, oxygen vacancies and quadrivalent cation form when La3+ is partly substituted by Sr2+, which can be demonstrated with Kroger-Vink symbols as Eq. (1) : [SrLa ]=[BB ]+2[Vo ]. (1) At low temperature, the charge compensation of the system is conducted through B4+. The behavior is consistent with small polaron conduction mechanism as predicted by Arrhenius type Eq. (2): (2) =(C/T)exp(-Ea/kT). Where: Ea is the activation energy, and k is the Boltzmann constant. The pre-exponential constant C includes the carrier concentration as well as other material-dependent parameters. T is adiabatic temperature. The electrical conductivity of the system increases mostly because of the increase of carrier concentration. At about 600 , it decreases with increasing temperature, which is the result of the electrons movement from local area state to collectivity movement [6].At the same time, oxygen vacancies begin to form in order to maintain charge neutrality, which mainly depends on ionic compensation as shown in Eq. (3): (3) 2BB +Oo Vo +2BB+1/2O2. The oxygen concentration keeps decreasing with increasing temperature, and the oxygen vacancies concentration decreases, which results in the decrease of the electrical conductivity of the system.

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The XRD patterns of the cathodes wafers before and after 800h-exposure in air at 800 are shown in Fig.4. No reaction product was detected, which reveals LSCF has good chemical compatibility with GDC, but the peak lowers after exposure.

Fig.4 X-ray diffraction patterns for cathodes wafers before and after 800h-exposure in air at 800 3.4 Microstructure before and after exposure The SEM photos of the cathodes wafers before and after 800h-exposure in air at 800 are shown in Fig.5. LSCF grains separate after ball-milling. The particles are uniformly dispersed and developed during calcining. b-lscf-slice has smaller particle diameter, more pores and higher electrical conductivity than that of m-lscf-slice. The micrographs of both the samples did not change too much, which demonstrates the samples have good stability at 800 in air. It is a common acknowledgement that thin origin powder, large specific surface area, enough porosity and high ionic and electronic conductivity are essential for high performance cathode. For a LSCF-GDC cathode, the LSCF grains are to achieve high ionic and electronic conductivity and good catalysis performance for O2, while the GDC grains serve as mechanical support for LSCF and make thermal expansion fit to electrolyte, so the characteristic and fabrication method of LSCF are of great importance. The different fabrication methods of LSCF make them have different microstructure. The microstructure of LSCF grain in b-lscf-slice meets all the requirements better, which makes it has higher electrical conductivity. In contrast, the larger LSCF grain in m-lscf-slice reduces the three-phase boundary length [9], which results in lower electrical conductivity.

Fig.3 Arrhenius plots of electrical conductivity of LSCF/GDC samples 3.3 XRD patterns before and after exposure

(a) citric acid-nitrate low temperature self-propagating combustion method, before exposure

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International Conference on Power Engineering-2007, October 23-27, 2007, Hangzhou, China (3) LSCF material has high electrical conductivity. The electrical conductivity of LSCF synthesized by citric acid-nitrate low temperature self-propagating combustion method is higher than that of the LSCF made by solid state reaction method. (4) The electrical conductivity of both the samples decreases after 800h-exposure in air at 800 , but in the same changing trend. (5) The micrographs of both the samples do not change too much and no reaction product is detected, which demonstrates the samples have good stability at 800 in air.

(b) solid state reaction method, before exposure

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(c) citric acid-nitrate low temperature self-propagating combustion method, after exposure

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(d) solid state reaction method, after exposure Fig.5 SEM photos for cathodes wafers before and after 800h-exposure in air at 800

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4 CONCLUSIONS
(1) LSCF can be well synthesized by both citric acid-nitrate low temperature self-propagating combustion and solid state reaction methods. Both the two kinds of LSCF powders have good chemical compatibility with GDC electrolyte. (2) Both the two kinds of LSCF powders form agglomerates. The LSCF made by citric acid-nitrate low temperature self-propagating combustion method has lower aggregation performance and less particle diameter than that of the LSCF made by solid state reaction method.

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