单气室固体氧化物燃料电池的材料、微堆结构与相关应用

doi:10.13208/j.electrochem.191142

摘要/Abstract

摘要：

单气室固体氧化物燃料电池（SC-SOFC）是一种整个电池处在单一气室中,阳极和阴极分别对混合气体中的燃料和氧气进行选择催化产生电动势的特殊结构燃料电池. SC-SOFC因其独特的原理和结构而具有无需密封、易于堆叠、可以快速启动和不易发生积碳等诸多优点,有很大的应用潜力. 作者在SC-SOFC的原理和特点的基础上,系统地总结了SC-SOFC所用材料、微堆结构设计、衰退机制及应用方面的研究进展;以提高SC-SOFC微堆的输出电压和功率为目的,改进预混气体环境下运行的微堆结构,采取星型布局的四电池微堆其输出功率提高到420 mW;随后,逐步改进供气方式,结合计算流体力学数值模拟研究,提出了单路多点供气和双路多点供气模式,成功地将单个SC-SOFC微堆模块的输出功率提升到8.178 W,进而开展了微堆模块外部串并联和与燃烧器的结合实验验证. 研究结果表明,SC-SOFC可以很便捷地连接成微堆模块并产生数瓦的输出功率,未来有望用于以供热为主型的热电联供系统. 作者还借助原位电阻和开路电压的原位同步测试,阐明了Ni在CH₄-O₂气氛中的反复氧化-还原循环是SC-SOFC发生不可逆衰退的主要机制,这一发现后来催生出氧化-还原法制备多孔金属的新技术.

关键词: 固体氧化物燃料电池, 单气室, 微堆, 选择催化

Abstract:

Single-chamber solid oxide fuel cell (SC-SOFC) is a special type of fuel cells, in which both an anode and a cathode are placed in one chamber. Its working principle relies on the selective catalytic activity of the electrodes towards fuel and oxidant in a gas mixture, leading to the generation of an electromotive force. Because of its unique principle and structure, SC-SOFC has many advantages such as sealing-free, easy stacking, quick start-up and no carbon deposition, thus, it possesses large potential in application. Herein, the principles and characteristics of SC-SOFC are introduced. Furthermore, the SC-SOFC materials, micro-stack design, degeneration mechanisms and potential applications in recent years are reviewed systematically. In order to improve the output voltage and power of SC-SOFC micro-stack, the structure of micro-stack running in pre-mixed gas environment is modified, and the output power of four-cell micro-stack with star-type is increased to 420 mW. Then, the gas supply mode of SC-SOFC micro-stack is also improved step by step combined with the numerical simulation of computational fluid dynamics, and a single-channel/multi-point gas supply mode and a double-channel/multi-point gas supply mode are proposed. The output power of a single SC-SOFC micro-stack module is as high as 8.178 W. In addition, either external series or parallel connection of the micro-stack module, and the experimental verification with the burners are carried out. The results show that SC-SOFC can be easily connected into micro-stack module which produce several watts of output power, and are expected to be used in the combined heat-power system with heat supply prior in the future. By means of the simultaneous measurements of in situ resistance and open circuit voltage, it is also clarified that the repeated oxidation-reduction cycle of Ni at CH₄-O₂ atmosphere is the primary mechanism for the irreversible decay in SC-SOFC. This discovery later has promoted a new technology for the preparation of porous metals by oxidation-reduction method.

Key words: solid oxide fuel cell, single-chamber, micro-stack, selective catalytic activity

中图分类号:

TM911
O646

吕喆, 魏波, 王志红, 田彦婷. 单气室固体氧化物燃料电池的材料、微堆结构与相关应用[J]. 电化学（中英文）, 2020, 26(2): 230-242.

Lv Zhe, WEI Bo, WANG Zhi-hong, TIAN Yan-ting. Materials, Micro-Stacks and Related Applications of Single-Chamber Solid Oxide Fuel Cells[J]. Journal of Electrochemistry, 2020, 26(2): 230-242.

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链接本文: https://electrochem.xmu.edu.cn/CN/10.13208/j.electrochem.191142

https://electrochem.xmu.edu.cn/CN/Y2020/V26/I2/230

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参考文献 76

[1]	Wachsman E D, Marlowe C A, Lee K T . Role of solid oxide fuel cells in a balanced energy strategy[J]. Energy Environmental Science, 2012,5(2):5498-5509.
[2]	Gao Z, Mogni L V, Miller E C , et al. A perspective on low-temperature solid oxide fuel cells[J]. Energy & Environmental Science, 2016,9(5):1602-1644.
[3]	Kilner J A, Burriel M . Materials for intermediate-temperature solid-oxide fuel cells[J]. Annual Review of Materials Research, 2014,44:365-393.
[4]	Irvine J T S, Neagu D, Verbraeken M C , et al. Evolution of the electrochemical interface in high-temperature fuel cells and electrolysers[J]. Nature Energy, 2016,1(1):15014.
[5]	Yano M, Tomita A, Sano M , et al. Recent advances in single-chamber solid oxide fuel cells: A review[J]. Solid State Ionics, 2007,177:3351-3359.
[6]	Wang K( 王康), Shao Z P( 邵宗平 ). The single chamber solid oxide fuel cell[J]. Progress in Chemistry( 化学进展), 2007,19(2/3):267-275.
[7]	Kuhn M, Napporn T W . Single-chamber solid oxide fuel cell technology—From its origins to today’s state of the art[J]. Energies, 2010,3(1):57-134.
[8]	Hibino T, Hashimoto A, Inoue T , et al. A low-operating-temperature solid oxide fuel cell in hydrocarbon-air mixtures[J]. Science, 2000,288(5473):2031-2033.
[9]	Shao Z P, Haile S M, Ahn J, Barnett S A . et al. A thermally self-sustained micro solid-oxide fuel-cell stack with high power density[J]. Nature, 2005,435(7043):795-798.
[10]	Eyraud C, Enoir L, Gery M . Fuel cells utilizing the electrochemical properties of absorbates[J]. Comptes Rendus, 1961,252:1599-1603.
[11]	Gool W V . The possible use of surface migration in fuel cells and herogenrous catalysis[J]. Phillips Research Re-ports, 1965,20:81-93.
[12]	Louis G A, Lee J M, Maricle D L , et al. Solid electrolyte electrochemical cell[P]. US Patent 4248941, 1981.
[13]	Dyer C K . A novel thin-film electrochemical device for energy conversion CuO[J]. Nature, 1990,343(6258):547-548.
[14]	Hibino T, Wang S, Kakimoto S , et al. Single chamber solid oxide fuel cell constructed from an yttria-stabilized zirconia electrolyte[J]. Electrochemical and Solid-State Letters, 1999,2(7):317-319.
[15]	Hibino T, Wang S Q, Kakimoto S , et al. One-chamber solid oxide fuel cell constructed from a YSZ electrolyte with a Ni anode and LSM cathode[J]. Solid State Ionics, 2000,127(1/2):89-98.
[16]	Shao Z P, Haile S M . A high-performance cathode for the next generation of solid-oxide fuel cells[J]. Nature, 2004,431:170-173.
[17]	Hibino T, Iwahara H . Simplification of solid oxide fuel cell system using partial oxidation of methane[J]. Chemistry Letters, 1993,22(7):1131-1134.
[18]	Hibino T, Ushiki K, Kuwahara Y . New concept for simplifying SOFC system[J]. Solid State Ionics, 1996,91(1/2):69-74.
[19]	Riess I, Vanderput P J, Schoonman J . Solid oxide fuel-cells operating on uniform mixtures of fuel and air[J]. Solid State Ionics, 1995,82(1/2):1-4.
[20]	Hibino T, Hashimoto A, Inoue T , et al. A solid oxide fuel cell using an exothermic reaction as the heat source[J]. Journal of The Electrochemical Society, 2001,148(6):A544-A549.
[21]	Bay L, Horita T, Sakai N , et al. Hydrogen solubility in prdoped and un-doped YSZ for a one chamber fuel cell[J]. Solid State Ionics, 1998,113(S1):363-367.
[22]	Mordarski G, Suski L, Kolacz J , et al. Electrode open circuit potentials and oxidation process at Au and Pt electrodes/solid oxide electrolyte interfaces in common methane plus air gas mixture[J]. Polish Journal of Chemistry, 2005,79(6):1063-1077.
[23]	Asano K, Hibino T, Iwahara H . A novel solid oxide fuel cell system using the partial oxidation of methane[J]. Journal of The Electrochemical Society, 1995,142(10):3241-3245.
[24]	Hibino T, Hashimoto A, Yano M , et al. High performance anodes for SOFC operating in methane-air mixture at reduced temperatures[J]. Journal of The Electrochemical Society, 2002,149(2):A133-A136.
[25]	Zhang C M, Sun L L, Ran R , et al. Activation of a single-chamber solid oxide fuel cell by a simple catalyst-assisted in-situ process[J]. Electrochemistry Communications, 2009,11(8):1563-1566.
[26]	Zhang C M, Lin Y, Ran R , et al. Improving single-chamber performance of an anode-supported SOFC by impregnating anode with active nickel catalyst[J]. Intermational Journal of Hydrogen Energy, 2010,35(15):8171-8176.
[27]	Tomita A, Hirabayashi D, Hibino T , et al. Single-chamber SOFC with a Ce_0.9Gd_0.1O_1.95 electrolyte film for low-temperature operation[J]. Electrochemical and Solid State Letters, 2005,8(1):A63-A65.
[28]	Jacques-Bedard X, Napporn T W, Roberge R , et al. Coplanar electrodes design for a single-chamber SOFC— Assessment of the operating parameters[J]. Journal of The Electrochemical Society, 2007,154(3):B305-B309.
[29]	Wang Z H, Lü Z, Chen K F , et al. Redox tolerance of thin and thick Ni/YSZ anodes of electrolyte-supported single-chamber solid oxide fuel cells under methane oxidation conditions[J]. Fuel Cells, 2013,13(6):1109-1115.
[30]	Zhu X B, Lü Z, Wei B , et al. Fabrication and evaluation of a Ni/La_0.75Sr_0.25Cr_0.5Fe_0.5O₃-_δ co-impregnated yttria-stabili-zed zirconia anode for single-chamber solid oxide fuel cell[J]. International Journal of Hydrogen Energy, 2010,35(13):6897-6904.
[31]	Hibino T, Hashimoto A, Inoue T , et al. Single-chamber solid oxide fuel cells at intermediate temperatures with various hydrocarbon-air mixtures[J]. Journal of The Electrochemical Society, 2000,147(8):2888-2892.
[32]	Lü Z( 吕喆), Wei B( 魏波), Tian Y T( 田彦婷 ), et al. Key materials and micro-stacks of single chamber solid oxide fuel cells[J]. Progress in Chemistry( 化学进展), 2011,23(2/3):183-196.
[33]	Steele B C H . Appraisal of Ce₁-_yGd_yO₂-_y_/2 electrolytes for IT-SOFC operation at 500 ^oC [J]. Solid State Ionics, 2000,129(1/4):95-110.
[34]	Wei B, Lü Z, Huang X Q , et al. Enhanced performance of a single-chamber solid oxide fuel cell with an SDC-impregnated cathode[J]. Journal of Power Sources, 2007,167(1):58-63.
[35]	Liu M L, Lü Z, Wei B , et al. Anode-supported micro-SOFC stacks operated under single-chamber conditions[J]. Journal of The Electrochemical Society 2007,154(6):B588-B592.
[36]	Suzuki T, Jasinski P, Anderson H U , et al. Single chamber electrolyte supported SOFC module[J]. Electrochemical and Solid State Letters, 2004,7(11):A391-A393.
[37]	Jacques-Bedard X, Napporn T W, Roberge R , et al. Performance and ageing of an anode-supported SOFC operated in single-chamber conditions[J]. Journal of Power Sources, 2006,153(1):108-113. doi: 10.1016/j.jpowsour.2005.03.138 URL
[38]	Napporn T W, Jacques-Bedard X, Morin F , et al. Operating conditions of a single-chamber SOFC[J]. Journal of The Electrochemical Society, 2004,151(12):A2088-A2094.
[39]	Shao Z P, Zhang C M, Wang W , et al. Electric power and synjournal gas co-generation from methane with zero waste gas emission[J]. Angewandte Chemie International Edition, 2011,50(8):1792-1797.
[40]	Gaudillere C, Olivier L, Vernoux P , et al. Alternative perovskite materials as a cathode component for intermediate temperature single-chamber solid oxide fuel cell[J]. Journal of Power Sources 2010,195(15):4758-4764.
[41]	Morel B, Roberge R, Savoie S , et al. Catalytic activity and performance of LSM cathode materials in single chamber SOFC[J]. Applied Catalysis A - General, 2007,323:181-187.
[42]	Liu M L, Lü Z, Wei B , et al. Study on impedance spectra of La_0.7Sr_0.3MnO₃ and Sm_0.2Ce_0.8O_1.9-impregnated La_0.7Sr_0.3-MnO₃ cathode in single chamber fuel cell condition[J]. Electrochimica Acta, 2009,54(20):4726-4730.
[43]	Suzuki T, Jasinski P, Anderson H U , et al. Role of composite cathodes in single chamber SOFC[J]. Journal of The Electrochemical Society 2004,151(10):A1678-A1682.
[44]	Shao Z P, Haile S M . A high-performance cathode for the next generation of solid-oxide fuel cells[J]. Nature, 2004,431(7005):170-173.
[45]	Zhang Y, Gao X C, Sunarso J , et al. Significantly improving the durability of single-chamber solid oxide fuel cells: A highly active CO₂-resistant perovskite cathode[J]. ACS Applied Energy Materials, 2018,1(3):1337-1343.
[46]	Ai G( 艾刚), Lü Z( 吕喆), Wei B( 魏波 ), et al. Performance of anode supported single chamber solid oxide fuel cells[J]. Chinese Journal of Catalysis( 催化学报), 2006,27(10):885-889.
[47]	Liu M L, Lü Z, Wei B , et al. Effect of the cell distance on the cathode in single chamber SOFC short stack[J]. Journal of The Electrochemical Society, 2009,156(10):B1253-B1256. doi: 10.1149/1.3196245 URL
[48]	Liu M L, Qi X, Lü Z , et al. Effect of flow geometry on anode-supported single chamber SOFC arrayed as V-shape[J]. International Journal of Hydrogen Energy, 2013,38(4):1976-1982.
[49]	Liu M L, Lü Z, Wei B , et al. Effects of the single chamber SOFC stack configuration on the performance of the single cells[J]. Solid State Ionics, 2010,181(19/20):939-942.
[50]	Liu M L, Lü Z, Wei B , et al. Performance of an annular solid-oxide fuel cell micro-stack array operating in single-chamber conditions[J]. Journal of Power Sources, 2010,195:4247-4251.
[51]	Liu M L, Lü Z, Wei B , et al. A novel cell-array design for single chamber SOFC microstack[J]. Fuel Cells, 2010,9(5):717-721. doi: 10.1002/fuce.v9:5 URL
[52]	Wei B, Lü Z, Huang X Q , et al. A novel design of single-chamber SOFC micro-stack operated in methane-oxygen mixture[J]. Electrochemistry Communications, 2009,11(2):347-350. doi: 10.1016/j.elecom.2008.11.037 URL
[53]	Tian Y T, Lü Z, Liu M L , et al. Effects of gas supply method on the performance of the single-chamber SOFC micro-stack and the single cells[J]. Journal of Solid State Electrochemistry, 2013,17(1):269-275. doi: 10.1007/s10008-012-1865-6 URL
[54]	Tian Y T, Lü Z, Wang Z H , et al. Enhanced performance of a single-chamber solid oxide fuel cell with dual gas supply method[J]. Ionics, 2019,25(3):1281-1289.
[55]	Tian Y T, Lü Z, Wei B , et al. A non-sealed solid oxide fuel cell micro-stack with two gas channels[J]. International Journal of Hydrogen Energy, 2011,36(12):7251-7256.
[56]	Tian Y T, Lü Z, Zhang Y H , et al. Study of a single-cham-ber solid oxide fuel cell micro-stack with V-shaped congener-electrode-facing configuration[J]. Fuel Cells, 2012,12(1):4-10.
[57]	Tian Y T, Lü Z, Wei B , et al. Evaluation of a non-sealed solid oxide fuel cell stack with cells embedded in plane configuration[J]. Fuel Cells, 2012,12(4):523-529.
[58]	Horiuchi M, Suganuma S, Watanabe M . Electrochemical power generation directly from combustion flame of gases, liquids, and solids[J]. Journal of The Electrochemical Society, 2004,151(9):A1402-A1405.
[59]	Zhu X B, Lü Z, Wei B , et al. A direct flame solid oxide fuel cell for potential combined heat and power generation[J]. International Journal of Hydrogen Energy, 2012,37(10):8621-8629.
[60]	Zhu X B, Lü Z, Wei B , et al. Direct flame SOFC with LSCM/Ni co-impregnated yttria-stabilized zircona anodes operated on liquefied petroleum gas flame[J]. Journal of The Electrochemicl Society, 2010,157(12):B1838-B1843.
[61]	Hibino T, Kuwahara Y, Wang S . Effect of electrode and electrolyte modification on the performance of one-cham-ber solid oxide fuel cell[J]. Journal of The Electrochemical Society, 1999,146(8):2821-2826.
[62]	Buergler B E, Grundy A N, Gauckler L J . Thermodynamic equilibrium of single-chamber SOFC relevant methane-air mixtures[J]. Journal of The Electrochemical Society, 2006,153(7):A1378-A1385.
[63]	Buergler B E, Siegrist M E, Gauckler L J . Single chamber solid oxide fuel cells with integrated current-collectors[J]. Solid State Ionics, 2005,176(19/22):1717-1722.
[64]	Gubner A, Landes H, Metzger J, et al. Investigation into the degradation of cermet anode of a solid oxide fuel cell[C]// Fifth International Symposium on Solid Oxide Fuel Cells (SOFC-V), The Electrochemical Society, Inc. Jülich Germany, 1997: 844-850.
[65]	Zhang X L, Hayward D O, Mingos D M P . Further studies on oscillations over nickel wires during the partia oxidation of methane[J]. Catalysis Letters, 2003,86(4):235-243.
[66]	Zhang X L, Mingos D M P, Hayward D O . Rate oscillations during partial oxidation of methane over chromel-alumel thermocouples[J]. Catalysis Letters, 2001,72(3/4):147-152.
[67]	Zhang X L, Lee C S M, Hayward D O , et al. Oscillatory behaviour observed in the rate of oxidation of methane over metal catalysts[J]. Catalysis Today, 2005,105(2):283-294.
[68]	Wang Z H, Lü Z, Wei B , et al. Redox of Ni/YSZ anodes and oscillatory behavior in single-chamber SOFC under methane oxidation conditions[J]. Electrochimica Acta, 2011,56(19):6688-6695.
[69]	Morales M, Pérez-Falcón J M, Moure A , et al. Performance and degradation of La_0.8Sr_0.2Ga_0.85Mg_0.15O₃-_δ electro-lyte-supported cells in single-chamber configuration[J]. International Journal of Hydrogen Energy, 2014,39(10):5451-5459.
[70]	Morel B, Roberge R, Savoie S , et al. Temperature and performance variations along single chamber solid oxide fuel cells[J]. Journal of Power Sources, 2009,186:89-95.
[71]	Stefan I C, Jacobson C P, Visco S J , et al. Single chamber fuel cells: Flow geometry, rate, and composition considerations[J]. Electrochemical and Solid State Letters, 2004,7(7):A198-A200.
[72]	Tian Y T( 田彦婷 ). Influence mechanism of gas flow distribution and gas component on single chamber fuel cell micro stack[D]. Harbin Institute of Technology( 哈尔滨工业大学), 2013: 18-39.
[73]	Yano M, Nagaoa M, Okamoto K , et al. A single-chamber SOFC stack operating in engine exhaust[J]. Electrochemical and Solid State Letters, 2008,11(3):B29-B33.
[74]	Wang Z H, Yan Y M, Liu M T , et al. Rapid porosity formation of silver under SOFC conditions in methane-oxygen mixed gas[J]. International Journal of Hydrogen Energy, 2016,41(47):22344-22353.
[75]	Wang Z H, Yan Y M, Chen Y F , et al. 3D-hierarchical porous nickel sculptured by a simple redox process and its application in high-performance supercapacitors[J]. Jounral of Material Chemistry A, 2017,5(39):20709-20719.
[76]	Cao F H, Wang Z H, Wang Y Z , et al. In situ fabrication of cellular architecture on silver metals using methane/oxygen gas mixture and its application for energy storage[J]. Electrochimica Acta, 2018,280:25-32.

Fuel	Molecular formula	Explosive limit/vol%
Hydrogen	H₂	4 ~ 75
Methane	CH₄	5 ~ 15
Ethane	C₂H₆	3 ~ 15.5
Propane	C₃H₈	2.2 ~ 9.5
Butane	C₄H₁₀	1.9 ~ 8.5
Carbon monoxide	CO	12.5 ~ 74
Ethanol	C₂H₅OH	3.4 ~ 19