掺杂钛酸锶SOFC阳极材料的制备与电性能研究
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摘要
掺杂钛酸锶材料由于其具有混合离子-电子电导且对碳氢燃料有良好的催化性能而被认为具有作为新型SOFC阳极材料潜在的应用价值。本文对掺杂钛酸锶新型SOFC阳极材料的制备和电学性能进行了研究,探讨了其作为新型阳极材料的可行性。
对Y2O3掺杂钛酸锶Sr1-1.5xYxTiO_3(x=0.01、0.02、0.03、0.04、0.05)和La2O3掺杂钛酸锶Sr1-1.5xLaxTiO_3(x=0.1、0.2、0.3、0.4、0.5)的预合成和烧结工艺进行了研究。通过DSC-TG分析粉料的预合成制度;通过XRD分析了1100℃下预合成后粉料的晶体结构为典型的钙钛矿结构;根据DIL分析确定不同物质掺杂钛酸锶的最佳烧结温度,采用排水法测定了试样的烧结密度;1400℃烧结的Y_2O_3掺杂钛酸锶的试样密度达到理论密度的93%以上,1600℃烧结的La_2O_3掺杂钛酸锶试样的密度达到理论密度的94%以上。
对掺杂钛酸锶的电学性能进行了研究,Y2O3和La2O3掺杂钛酸锶的电导率均随掺杂量的增加而出现最大值,随测试温度的增加而降低,其中,1400℃烧结的Y_2O_3掺杂钛酸锶电导率高于1450℃下烧结的试样电导率,当钛酸锶中Y_2O_3的掺杂量为0.04mol时,800℃电导率达到最大为26.3 S/cm;1600℃下烧结La2O3掺杂钛酸锶的电导率高于Y_2O_3的电导率,且当钛酸锶中La_2O_3掺杂量为0.15mol时其电导率在800℃最高为103.5 S/cm。对掺杂钛酸锶材料和电解质YSZ在1400℃下共烧没有发生化学反应,表现出良好的化学相容性。
为优化阳极材料的电学性能,对Y_2O_3、Co_3O_4和La_2O_3、Co_3O_4复合掺杂钛酸锶材料的电学性能进行了尝试性研究,但是复合掺杂产生了缺陷缔合而不利于电导率的提高。
Doped SrTiO3 is considered to be the potential anode material for SOFC because of its mixed ionic-electronic conductivities and excellent catalysis to hydrocarbon fuels. In this paper, the preparation and electrical performance of SrTiO3 used for SOFC anode materials were investigated.
The calcinations process of Y2O3 doped SrTiO3 Sr1-1.5xYxTiO3 (x=0.01, 0.02, 0.03, 0.04, 0.05) and La2O3 doped SrTiO3 Sr1-1.5xLaxTiO3 (x=0.1, 0.2, 0.3, 0.4, 0.5) were investigated by DSC-TG. The structure of the 1100℃calcined powders was examined by X-ray diffraction (XRD). The optimal sintering temperature of SrTiO3 doped with different substances was investigated based on DIL analysis. Density of samples was measured by the Archimedes principle. The relative density of Y2O3 doped SrTiO3 samples is larger than 93 %, and La2O3 doped SrTiO3 is larger than 94 %.
Electrical performance of doped SrTiO3 was studied. The conductivity of doped SrTiO3 showed a peak as the increase of dopant content, and decreased with the increase of test temperature. Y2O3 doped SrTiO3 sintered at 1400℃is higher than that at 1450℃. The conductivity reached the maximal 26.3 S/cm at 800℃when the content of Y2O3 was 8mol%. The conductivity of La2O3 doped SrTiO3 sintered at 1600℃was 103.5 S/cm at 800℃when the content of La2O3 was 30mol%. There is no chemical reaction between doped SrTiO3 and YSZ sintered at 1400℃that showed good chemical compatibility.
Complex-doped SrTiO3 was studied in order to improve the electrical performance of the anode materials. But the association of defects in the complex-doped SrTiO3 have disadvantage to the improvement of electrical conductivity.
对Y2O3掺杂钛酸锶Sr1-1.5xYxTiO_3(x=0.01、0.02、0.03、0.04、0.05)和La2O3掺杂钛酸锶Sr1-1.5xLaxTiO_3(x=0.1、0.2、0.3、0.4、0.5)的预合成和烧结工艺进行了研究。通过DSC-TG分析粉料的预合成制度;通过XRD分析了1100℃下预合成后粉料的晶体结构为典型的钙钛矿结构;根据DIL分析确定不同物质掺杂钛酸锶的最佳烧结温度,采用排水法测定了试样的烧结密度;1400℃烧结的Y_2O_3掺杂钛酸锶的试样密度达到理论密度的93%以上,1600℃烧结的La_2O_3掺杂钛酸锶试样的密度达到理论密度的94%以上。
对掺杂钛酸锶的电学性能进行了研究,Y2O3和La2O3掺杂钛酸锶的电导率均随掺杂量的增加而出现最大值,随测试温度的增加而降低,其中,1400℃烧结的Y_2O_3掺杂钛酸锶电导率高于1450℃下烧结的试样电导率,当钛酸锶中Y_2O_3的掺杂量为0.04mol时,800℃电导率达到最大为26.3 S/cm;1600℃下烧结La2O3掺杂钛酸锶的电导率高于Y_2O_3的电导率,且当钛酸锶中La_2O_3掺杂量为0.15mol时其电导率在800℃最高为103.5 S/cm。对掺杂钛酸锶材料和电解质YSZ在1400℃下共烧没有发生化学反应,表现出良好的化学相容性。
为优化阳极材料的电学性能,对Y_2O_3、Co_3O_4和La_2O_3、Co_3O_4复合掺杂钛酸锶材料的电学性能进行了尝试性研究,但是复合掺杂产生了缺陷缔合而不利于电导率的提高。
Doped SrTiO3 is considered to be the potential anode material for SOFC because of its mixed ionic-electronic conductivities and excellent catalysis to hydrocarbon fuels. In this paper, the preparation and electrical performance of SrTiO3 used for SOFC anode materials were investigated.
The calcinations process of Y2O3 doped SrTiO3 Sr1-1.5xYxTiO3 (x=0.01, 0.02, 0.03, 0.04, 0.05) and La2O3 doped SrTiO3 Sr1-1.5xLaxTiO3 (x=0.1, 0.2, 0.3, 0.4, 0.5) were investigated by DSC-TG. The structure of the 1100℃calcined powders was examined by X-ray diffraction (XRD). The optimal sintering temperature of SrTiO3 doped with different substances was investigated based on DIL analysis. Density of samples was measured by the Archimedes principle. The relative density of Y2O3 doped SrTiO3 samples is larger than 93 %, and La2O3 doped SrTiO3 is larger than 94 %.
Electrical performance of doped SrTiO3 was studied. The conductivity of doped SrTiO3 showed a peak as the increase of dopant content, and decreased with the increase of test temperature. Y2O3 doped SrTiO3 sintered at 1400℃is higher than that at 1450℃. The conductivity reached the maximal 26.3 S/cm at 800℃when the content of Y2O3 was 8mol%. The conductivity of La2O3 doped SrTiO3 sintered at 1600℃was 103.5 S/cm at 800℃when the content of La2O3 was 30mol%. There is no chemical reaction between doped SrTiO3 and YSZ sintered at 1400℃that showed good chemical compatibility.
Complex-doped SrTiO3 was studied in order to improve the electrical performance of the anode materials. But the association of defects in the complex-doped SrTiO3 have disadvantage to the improvement of electrical conductivity.
引文
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[3] 韩敏芳,尹会燕,唐秀玲等,固体氧化物燃料电池发展及展望,真空电子技术,2005,4:23~26
[4] 张义煌,董永来,江义等,薄膜型中温固体氧化物燃料电池制备及性能考察,电化学,2000,6(1):78~83
[5] 孟光耀,付清溪,彭定坤,中温固态氧化物燃料电池,太阳能学报,2002,23(3):378~382
[6] 刘旭利,马俊峰,刘文化等,固体氧化物燃料电池的研究进展,硅酸盐通报,2001(1):24~29
[7] 程继贵,邓丽萍,孟光耀,固体氧化物燃料电池阳极材料制备及性能研究进展,兵器材料科学与工程,2002,25(6):45~49
[8] 赵兵,卢立柱,谢慧琴,中低温固体氧化物燃料电池(SOFC)电解质材料,稀土,1998,19(4):55~61
[9] 魏丽,陈诵英,王琴,中温固体氧化物燃料电池电解质材料的研究进展,稀有金属,2003,27(2):286~292
[10] Xinge Zhang, Satoshi Ohara, Radenka Maric, et al., Interface reactions in the NiO-SDC-LSGM system, Solid State Ionics, 2003, 133: 153~160
[11] 唐先敏,向梅芝,孙尧卿,固体氧化物燃料电池的材料研究进展,材料导报,1995,(1):28~32
[12] 于兴文,黄学杰,陈立泉,固体氧化物燃料电池的研究进展,电池,2002,32(2):110~112
[13] 刘莉,唐超群,CeO2基低温固体电解质材料的研究进展,电源技术,2001,25(6):428
[14] 梁广川,刘文西,陈玉如,等,Sm,Gd共同掺杂的CeO2基电解质性能研究,硅酸盐学报,2000,28(1):44~46
[15] Herle J V, Hortia, Kawada T, et al., Low temperature fabrication of (Y, Gd, Sm)-doped ceria electrolyte, Solid State Ionics, 1996, 86~88: 1225-1258
[16] Kuroda K, Hashimoto I, Adachi K, et al., characterization of solid fuel cell using doped lanthanum gallate, Solid State Ionics, 2000, 132(3-4): 199-208
[17] Ishihara T, Honda M, Nishiguchi H, et al., Intermediate temperature solid oxide fuel cell using LaGaO3 electrolyte II, Improvement of oxide ion conductivity and powerdensity by doping Fe for Ga site of LaGaO3, Journal of Electrochemical Society, 2000, 147(4): 1333~1337
[18] Misha Y, Mitsuysau H, Ohtaki M, et al., Solid oxide fuel cell with comoposite electrolyte consisting of samaria doped ceria and yttria stabilized electrolyte, Journal of Electrochemical Society, 1998, 145(3): 1004-1007
[19] Ma Gi L, Shimara T, Iwahara T, et al., ionic conduction and nonstoichiometry in BaxCe0.90Y0.10O3-δ, Solid state Ionics, 1998,110: 103~110
[20] 吕喆，刘江，黄喜强，等，SrCe0.9Gd0.1O3固体电解质燃料电池性能研究,高等学校化学学报,2001,22(4):630～633
[21] Zhu Bin, Bengt-Erik Mellander, Intermediate temperature fuel cells with electrolytes based on oxyacid salts, Journal of Power Sources, 1994, 52: 289~293
[22] Zhu Bin, Bengt-Erik Mellander, Proton conduction in salt-ceramic composite systems, Solid State Ionics, 1995, 77: 244~249
[23] Zhu Bin, Meng Guangyao, Mellander Bengt-Erik, Non-conventional fuel cell systems: new concepts and development, Journal of Power Sources, 1999, 79: 30~36
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