中温固体氧化物燃料电池的研制与电极过程的研究
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摘要
本文对经典柠檬酸法进行了改进，并采用改进的柠檬酸法合成出可以用于负载型La_(0.9)Sr_(0.1)Ga_(0.8)Mg_(0.2)O_(3-δ)(LSGM)薄膜制备的电解质超细粉料；系统考察了阳极基底电导率、微观孔结构等随LSGM掺入量不同而发生变化的规律及烧结方法、基底组成等对负载型LSGM薄膜质量的影响；采用分步烧结工艺制备出具有一定输出性能带SDC夹层的LSGM薄膜型中温固体氧化物燃料电池(SOFC)单电池。为了彻底避免高温下LSGM与NiO发生有害反应，首次采用浸渍阳极催化剂的方法，制备出高性能的阳极负载LSGM薄膜型(电解质薄膜厚度为15μm，LSM-YSZ作阴极)中温SOFC单电池，并用电化学、EDX等方法对电池开路电位偏低的原因、各种电池材料间的化学相容性等进行了研究。采用交流阻抗、极化、循环伏安等电化学方法对SSC-SDC、SSC-LSGM复合阴极的电化学性质进行了考察；系统地研究了Ag-SSC-SDC复合阴极的电化学性质随Ag粉种类、掺入量变化的规律。在此基础上，研制出20 wt％普通Ag-SSC-SDC高活性中温SOFC复合阴极。此外，本文还对BSCF电导率随SrO掺杂量、温度、环境氧分压变化的规律及其作为SOFC阴极材料的电化学活性、存在的问题等进行了研究；对Fe、Mg、Nd、Ga、Nd和Ga掺杂SrTiO_3的电导率随掺杂元素种类、温度、环境氧分压变化的规律及其作为中温SOFC抗积炭阳极材料的活性、存在问题可能的解决方案等进行了研究。
Traditional citric acid method (Pechini method) was modified and Mg0.2 O3-δ(LSGM) ultra-fine powder was synthesized by the improved citric acid method at relatively low temperature for the preparation of anode supported LSGM thin film. The effects of compositions of NiO-LSGM substrates on the electrical conductivity, the microstructure parameters of the reduced substrates were investigated. A LSGM thin film based SOFC single cell with an SDC interlayer prepared by step sintering procedures was fabricated and a relatively low output performance was achieved, hi order to prohibit the occurrence of the severe reaction between LSGM and NiO at high temperature, for the first time in the world, a SOFC with an impregnated anode, 15 um thick LSGM electrolyte and LSM-YSZ composite cathode was fabricated and tested, showing a high output performance (The maximum output power density reached to above 800 mW/cm2 at 800癈 when H2 was used as fuel and air as oxidant). The causes for the relatively low open circuit potent
ial and the chemical compatibility of the cell materials at high temperatures were also elucidated by EDX and electrochemical methods. The electrical conductivity of SSC-SDC, SSC-LSGM composite cathode and the dependence of the electrochemical properties of Ag-SSC-SDC composite cathode upon the kind of Ag powder, the ratio of the Ag powder, temperature and environmental oxygen partial pressure were systematically studied. Following these work, a high activity cathode of 20 wt% normal Ag-SSC-SDC was developed. The effects of SrO doping level, temperature and oxygen partial pressure on the electrochemical conductivity of BSCF, the electrochemical activity of BSCF as cathode in an SOFC and related problems were discussed. The electrical conductivities of Fe, Mg, Nb, Ga doped SrTiO3 and Nb, Ga co-doped SrTiO3 were measured at various temperatures and oxygen partial pressures and the activities of these doped SrTiO3 as carbon tolerant
anode materials, problems and possible routes to deal with these problems were also researched.
Traditional citric acid method (Pechini method) was modified and Mg0.2 O3-δ(LSGM) ultra-fine powder was synthesized by the improved citric acid method at relatively low temperature for the preparation of anode supported LSGM thin film. The effects of compositions of NiO-LSGM substrates on the electrical conductivity, the microstructure parameters of the reduced substrates were investigated. A LSGM thin film based SOFC single cell with an SDC interlayer prepared by step sintering procedures was fabricated and a relatively low output performance was achieved, hi order to prohibit the occurrence of the severe reaction between LSGM and NiO at high temperature, for the first time in the world, a SOFC with an impregnated anode, 15 um thick LSGM electrolyte and LSM-YSZ composite cathode was fabricated and tested, showing a high output performance (The maximum output power density reached to above 800 mW/cm2 at 800癈 when H2 was used as fuel and air as oxidant). The causes for the relatively low open circuit potent
ial and the chemical compatibility of the cell materials at high temperatures were also elucidated by EDX and electrochemical methods. The electrical conductivity of SSC-SDC, SSC-LSGM composite cathode and the dependence of the electrochemical properties of Ag-SSC-SDC composite cathode upon the kind of Ag powder, the ratio of the Ag powder, temperature and environmental oxygen partial pressure were systematically studied. Following these work, a high activity cathode of 20 wt% normal Ag-SSC-SDC was developed. The effects of SrO doping level, temperature and oxygen partial pressure on the electrochemical conductivity of BSCF, the electrochemical activity of BSCF as cathode in an SOFC and related problems were discussed. The electrical conductivities of Fe, Mg, Nb, Ga doped SrTiO3 and Nb, Ga co-doped SrTiO3 were measured at various temperatures and oxygen partial pressures and the activities of these doped SrTiO3 as carbon tolerant
anode materials, problems and possible routes to deal with these problems were also researched.
引文
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[8] Harumi Yokokawa, Natsuko Sakai, Teruhisa Horita and Katsuhiko Yamaji. Recent developments in solid oxide fuel cell materials. Fuel cells, 2001, 1(2). 117-131.
[9] Mark C. Williams. Status and market applications for the solid oxide fuel cell in the U.S. -A new direction. SOFC Ⅶ-Proceedings of the seventh international symposium. The electrochemical society, INC. 2001. 3-7.
[10] D. Stover, R. Henne, P. Otschik, H. Schichl. Recent developments of SOFC technology in Germany. SOFC Ⅶ-Proceedings of the seventh international symposium. The electrochemical society, INC. 2001.38-49.
[11] Gilles Lequeux. Status of the european SOFC programme. SOFC Ⅶ-Proceedings of the seventh international symposium. The electrochemical society, INC. 2001.14-27.
[12] T. Takayama and M. Suzuki. Curren status of SOFC R&D program at NEDO. SOFC Ⅶ-Proceedings of the seventh international symposium. The electrochemical society, INC. 2001.8-13.
[13] E. Ponthieu. Status of SOFC development in Europe. SOFC Ⅶ-Proceedings of the sixth international symposium. The electrochemical society, INC. 1999. 19-27.
[14] 李瑛，王林山．燃料电池．北京，冶金工业出版社，2000．227-235，258-266．
[15] 江义．固体氧化物燃料电池材料．新能源材料．天津大学出版社，2000．205-221
[16] Tatsumi Ishihara. Current status of intermediate temperature solid oxide fuel cell. 2001, 36(7). 483-485.
[17] 王零森．二氧化锆陶瓷(一)．陶瓷工程，1997，31(1)．40-44．
[18] 王零森．氧化锆陶瓷(二)．陶瓷工程，1997，31(2)．43-50．
[19] 王常珍．体电解质和化学传感器．冶金工业出版社，2000．
[20] H. Yokokawa. Phase diagrams and thermodynamic properties of zirconia based ceramics. Key engineering materials vols., 1998, 153-154. 37-74.
[21] Hideaki Inaba, Hiroaki Tagawa. Ceria-based solid electrolyte. Solid state ionics, 1996, 83. 1-16.
[22] Zhongliang Zhan, Ting-Lian Wen, Hengyong Tu, and Zhi-Yi Lu. AC impedance investigation of samarium doped ceria. Journal of the electrochemical society, 2001, 148(5). A427-A432.
[23] Mogens Mogensen, Nigel M. Sammes, Geoff. A Tompsett. Physical, chemical and electrochemical properties of pure and doped celia. Solid state ionics, 2000, 129. 63-94.
[24] Hideaki Inaba, Toshifumi Nakajima, Hroaki Tagawa. Sintering behaviors of ceriaa and gadolinia-doped ceria. Solid state ionics, 1998, 106. 263-268.
[25] Toshiyoki Mori, Takayasu Ikegami, and Hiroshi Yamamura. Application of a crystallographic index for improvement of the electrolytic properties of the CeO_2-Sm_2O_3 system. Journal of the electrochemical society, 1999, 146(12). 4380-4385.
[26] Tastsumi Ishihara, Hideaki Matsuda and Yusaku Takita. Doped LaGaO3 perovskite type oxide as a new oxide ionic conductor. J. Am. Chem. Soc., 1994, 116. 3801-3803.
[27] P.R. Slater, J.T.S. Irvine, T. Ishihara, Y. Takita. The Structure of the oxide ion conductor La_(0.9)Sr_(0.1)Ga_(0.8)Mg_(0.2)O_(2.83) by powder neutron diffraction. Solid State Ionics, 1998, 107. 319-323.
[28] Peng-nian, Huang and Anthony Petric. Superoxygen ion conductivity of lanthanum gallate doped with strontium and magnesium. J. Eleetrochem. Soc., 1996, 143(5). 1644-1648.
[29] Pengnan Huang,Alesh Horky and Anthony Petric. Interracial reaction between nickel oxide and lanthanum gallate during sintering and its effect on conductivity. J. Am. Ceram. Soc., 1999, 82(9). 2402-2406.
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