中温固体氧化物燃料电池阴极材料Pr2-xSrxCoO4+δ的制备及性能研究

doi:10.3724/SP.J.1077.2010.00738

摘要/Abstract

摘要：

采用固相反应法合成了中温固体氧化物燃料电池阴极材料Pr_2-xSr_xCoO_4+δ (x=0.8,1.0, 1.2). 通过XRD、SEM、热膨胀法、直流四探针法、交流阻抗谱法和循环伏安法对该体系材料的晶体结构、热膨胀系数、电导率和电化学性能进行了研究. 结果表明, 合成的粉体均形成了单相K₂NiF₄结构, Pr_0.8Sr_1.2CoO_4+δ与电解质材料Sm_0.2Ce_0.8O_1.9(SDC)在1100℃空气气氛下混合烧结, 未生成杂相. 材料的热膨胀系数随着Sr含量的增加而升高. 800℃时样品的电导率均大于100 S/cm. 随着Sr含量的增加, 极化电阻减小, Pr_0.8Sr_1.2CoO_4+δ在空气中的极化电阻最小, 700℃为0.29 Ω·cm².

关键词: 固体氧化物燃料电池, 阴极, 热膨胀系数, 电导率, 电化学性能

Abstract:

The samples of Pr_2-xSr_xCoO_4+δ(x=0.8, 1.0, 1.2) as cathode material for intermediate-temperature solid oxide fuel cell (IT-SOFC) were synthesized by solid-state reaction. Crystal structure, thermal expansion, electrical conductivity and electrochemical properties were investigated by XRD, SEM, dilatometry, DC four-probe method, AC impedance and cyclic voltammetry (CV) techniques, respectively. The XRD results showed all the samples obtained as a single K₂NiF₄-structural phase, there were no chemical reaction occurred between the Pr_0.08Sr_1.2CoO_4+δelectrode and the Sm_0.2Ce_0.8O_1.9 (SDC) electrolyte at 1100℃ in air. The thermal expansion coefficients (TECs) increased with Sr content increasing. The electrical conductivity of the specimens was over 100S/cm at 800℃. The polarization resistance decreased with the increasing of Sr content. Pr_0.8Sr_1.2O_4+δ had the optimum value of 0.29Ω·cm² at 700℃ in air.

Key words: SOFC, cathode, thermal expansion, electrical conductivity, electrochemical properties

中图分类号:

TM911

曹悦, 顾海涛, 陈涵, 郑益锋, 周明, 郭露村. 中温固体氧化物燃料电池阴极材料Pr_2-xSr_xCoO_4+δ的制备及性能研究[J]. 无机材料学报, 2010, 25(7): 738-742.

CAO Yue, GU Hai-Tao, CHEN Han, ZHENG Yi-Feng, ZHOU Ming, GUO Lu-Cun. Preparation and Characterization of Pr_2-xSr_xCoO_4+δ Cathode Materials for IT-SOFC[J]. Journal of Inorganic Materials, 2010, 25(7): 738-742.

参考文献

[1]Minh N Q. Ceramic fuel cells. J. Am. Ceram. Soc., 1993, 76(3): 563-588.
[2]Weber A, Ivers-Tiffée E. Materials and concepts for solid oxide fuel cells (SOFCs) in stationary and mobile applications. J. Power Sources, 2004, 127(1/2): 273-283.
[3]Molenda J, Swierczek K, Zajac W. Functional materials for the IT-SOFC. J. Power Sources, 2007, 173(2): 657-670.
[4]Dutta A, Mukhopadhyay J, Basu R N. Combustion synthesis and characterization of LSCF-based materials as cathode of intermediate temperature solid oxide fuel cells. J. Eur. Ceram. Soc., 2009, 29(10): 2003-2011.
[5]Sayer M, Odier P. Electrical properties and stoichiometry in La₂NiO₄. J. Solid State Chem., 1987, 67(1): 26-36.
[6]Flem G L, Demazeau G, Hagenmuller P. Relations between structure and physical properties in K₂NiF₄-type oxides. J. Solid State Chem., 1982, 44(1): 82-88.
[7]张雪黎, 罗来涛. A₂BO₄类钙钛矿型复合氧化物在催化领域的应用研究进展.工业催化, 2006, 14(3): 6-10.
[8]徐廷献, 樊丽莹, 徐明霞(XU Ting-Xian, et al). 类钙钛矿型陶瓷结构和性能的研究. 硅酸盐学报(Journal of the Chinese Ceramic Society), 2002, 30(2): 198-202.
[9]Daroukha M A, Vashooka V V, Ullmanna H, et al. Oxides of the AMO3 and A2MO4-type: structural stability, electrical conductivity and thermal expansion. Solid State Ionics, 2003, 158(1/2): 141-150.
[10]Nie H W, Wen T L, Wang S R, et al. Preparation, thermal expansion, chemical compatibility, electrical conductivity and polarization of A_2-αA'_αMO₄(A=Pr, Sm; A'=Sr; M=Mn, Ni; α=0.3,0.6) as a new cathode for SOFC. Solid State Ionics, 2006, 177(19-25): 1929-1932.
[11]Skinner S J, Kilner J A. Oxygen diffusion and surface exchange in La_2-xSr_xNiO_4+δ. Solid State Ionics, 2000, 135(1-4): 709-712.
[12]Boehm E, Bassat J M, Steil M C, et al. Oxygen transport properties of La₂Ni_1-xCu_xO_4+δ mixed conducting. Solid State Sci., 2003, 5(7): 973-981.
[13]Wang Y S, Nie H W, Wang S R, et al. A_2-xA_xBO₄-type oxides as cathode materials for IT-SOFCs(A=Pr, Sm; A=Sr; B=Fe, Co). Mater. Lett., 2006, 60(9/10): 1174-1178.
[14]Jin Chao, Liu Jiang. Preparation of Ba_1.2Sr_0.8CoO_4+δ K₂NiF₄-type structure oxide and cathodic behavioral of Ba_1.2Sr_0.8CoO_4+δ–GDC composite cathode for intermediate temperature solid oxide fuel cells. J. Alloys Compd., 2009, 474(1/2): 573-577.
[15]Gu Haitao, Chen Han, Gao Ling, et al. Effect of Co doping on the properties of Sr_0.8Ce_0.2MnO_3-δ cathode for intermediate-temperature solid-oxide fuel cells. Int. J. Hydrogen Energy, 2008, 33(17): 4681-4688.
[16]Huang Xiqiang, Zhang Fengmei, Lu Zhe, et al. Preparation and characteristics of Pr_1.6Sr_0.4NiO₄+YSZ as composite cathode of solid oxide fuel cells. J. Phys. Chem. Solids, 2009, 70(3/4): 665-668.
[17]Li Q, Zhao H, Huo L H, et al. Electrode properties of Sr doped La₂CuO₄ as new cathode material for intermediate-temperature SOFCs. Electrochem.Comm., 2007, 9(7): 1508-1512.
[18]Li S Y, Lu Z, Huang X Q, et al. Thermal, electrical and electrochemical properties of Nd-doped Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3-δ as a cathode material for SOFC. Solid State Ionics, 2008, 178(35/36): 1853-1858.