直接碳固体氧化物燃料电池

doi:10.13208/j.electrochem.191148

摘要/Abstract

摘要：

碳是重要的能量载体. 直接碳固体氧化物燃料电池（DC-SOFC）是一种直接使用固体碳为燃料的能量转换装置,通过电化学反应,DC-SOFC可将碳所蕴含的化学能直接而连续地转换成电能,转换效率高,产生的CO₂浓度高,易于捕集和后续处理. 本文系统地介绍DC-SOFC的结构组成、工作原理、研究现状和发展趋势,重点介绍了作者课题组在DC-SOFC研究方面的成果和进展,包括单电池和电池组的研制、采用生物质碳和煤炭为燃料时的性能和DC-SOFC在气电联产中的应用探索.

关键词: 直接碳固体氧化物燃料电池, 电化学氧化, Boudouard反应, 生物质碳, 煤炭, 气电联产

Abstract:

Carbon is richly reserved in coal, biomasses, and many other nature resources. It is usually used as an energy source through oxygen oxidation reaction. The oxidation is generally realized through combustion which causes serious air pollution. Besides, the conversion efficiency of generating electricity through the combustion process is limited by Carnot efficiency. A direct carbon solid oxide fuel cell (DC-SOFC) is a solid oxide fuel cell (SOFC) directly operated with solid carbon as the fuel. It can convert the chemical energy of carbon into electricity with high efficiency. The concentration of produced CO₂ from a DC-SOFC is so high that enables easy capture and segregation of CO₂. Here we systematically introduce the configuration, reaction process, research and development status, and prospects of DC-SOFC. Especially, we give a comprehensive review concerning research progress in DC-SOFC, including development and fabrication of single cells and stacks, DC-SOFC operating with biomass char and coal as the fuel, and gas-electricity cogeneration using DC-SOFC.

Key words: direct carbon solid oxide fuel cell, electrochemical oxidation, Boudouard reaction, biomass char, coal, gas-electricity cogeneration

中图分类号:

O646
TM912

刘江, 颜晓敏. 直接碳固体氧化物燃料电池[J]. 电化学（中英文）, 2020, 26(2): 175-189.

LIU Jiang, YAN Xiao-min. Direct Carbon Solid Oxide Fuel Cells[J]. Journal of Electrochemistry, 2020, 26(2): 175-189.

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链接本文: https://electrochem.xmu.edu.cn/CN/10.13208/j.electrochem.191148

https://electrochem.xmu.edu.cn/CN/Y2020/V26/I2/175

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参考文献 70

[1]	Birol F . World Energy Outlook 2018. IEA (International Energy Agency)[EB/OL]. Paris, 2018. .
[2]	Chen S( 陈硕), Chen T( 陈婷 ). Air pollution and public health: Evidence from sulfur dioxide emission of coal-fired power station in China[J]. Economic Research Journal( 经济研究), 2014,49(8):158-169.
[3]	Zou C N( 邹才能), Zhao Q( 赵群), Zhang G S( 张国生 ), et al. Energy revolution: From a fossil energy era to a new energy era[J]. Natural Gas Industry( 天然气工业), 2016,36(1):1-10.
[4]	Dicks A L . The role of carbon in fuel cells[J]. Journal of Power Sources, 2006,156(2):128-141.
[5]	Carlson E J . Program on technology innovation: systems assessment of direct carbon fuel cells technology. EPRI report[R]. Palo Alto: EPRI 2006. CA 1013362.
[6]	Cao D X, Sun Y, Wang G L . Direct carbon fuel cell: fundamentals and recent developments[J]. Journal of Power Sources, 2007,167(2):250-257.
[7]	Rady A C, Giddey S, Badwal S P S , et al. Review of fuels for direct carbon fuel cells[J]. Energy & Fuels, 2012,26(3):1471-1488.
[8]	Giddey S, Badwal S P S, Kulkarni A , et al. A comprehensive review of direct carbon fuel cell technology[J]. Progress in Energy and Combustion Science, 2012,38(3):360-399.
[9]	Gür T M . Critical review of carbon conversion in “carbon fuel cells”[J]. Chemical Reviews, 2013,113(8):6179-6206.
[10]	Cao T Y, Huang K, Shi Y X . Recent advances in high-temperature carbon-air fuel cells[J]. Energy & Environmental Science, 2017,10(2):460-490.
[11]	Zhong Y J, Su C, Cai R , et al. Process investigation of a solid carbon-fueled solid oxide fuel cell integrated with a CO₂ permeating membrane and a sintering-resistant reverse Boudouard reaction catalyst[J]. Energy & Fuels, 2016,30(3):1841-1848.
[12]	Kacprzak A, Kobylecki R, Bis Z . Influence of temperature and composition of NaOH-KOH and NaOH-LiOH electrolytes on the performance of a direct carbon fuel cell[J]. Journal of Power Sources, 2013,239:409-414.
[13]	Guo L, Calo J M, Kearney C , et al. The anodic reaction zone and performance of different carbonaceous fuels in a batch molten hydroxide direct carbon fuel cell[J]. Applied Energy, 2014,129:32-38.
[14]	Zecevic S, Patton E M, Parhami P . Carbon-air fuel cell without a reforming process[J]. Carbon, 2004,42(10):1983-1993.
[15]	Cooper J F, Selman R . Electrochemical oxidation of carbon for electric power generation: a review[J]. ECS Tran-sactions, 2009,19(14):15-25.
[16]	Jia L J, Tian Y, Liu Q H , et al. A direct carbon fuel cell with(molten carbonate)/(doped ceria) composite electrolyte[J]. Journal of Power Sources, 2010,195(17):5581-5586.
[17]	Elleuch A, Yu J S, Boussetta A , et al. Electrochemical oxidation of graphite in an intermediate temperature direct carbon fuel cell based on two-phases electrolyte[J]. International Journal of Hydrogen Energy, 2013,38(20):8514-8523.
[18]	Liu J, Zhou M Y, Zhang Y P , et al. Electrochemical oxidation of carbon at high temperature: principles and applications[J]. Energy & Fuels, 2018,32(4):4107-4117.
[19]	Nabae Y, Pointon K D, Irvine J T S . Electrochemical oxidation of solid carbon in hybrid DCFC with solid oxide and molten carbonate binary electrolyte[J]. Energy & Environmental Science, 2008,1(1):148-155.
[20]	Jayakumar A, Küngas R, Roy S , et al. A direct carbon fuel cell with a molten antimony anode[J]. Energy & Environmental Science, 2011,4(10):4133-4137.
[21]	Xu X Y, Zhou W, Liang F L , et al. A comparative study of different carbon fuels in an electrolyte-supported hybrid direct carbon fuel cell[J]. Applied Energy, 2013,108:402-409.
[22]	Hao W B, He X J, Mi Y L . Achieving high performance in intermediate temperature direct carbon fuel cells with renewable carbon as a fuel source[J]. Applied Energy, 2014,135:174-181.
[23]	Elleuch A, Halouani K, Li Y D . Investigation of chemical and electrochemical reactions mechanisms in a direct carbon fuel cell using olive wood charcoal as sustainable fuel[J]. Journal of Power Sources, 2015,281:350-361.
[24]	Yu J S, Zhao Y C, Li Y D . Utilization of corn cob biochar in a direct carbon fuel cell[J]. Journal of Power Sources, 2014,270:312-317.
[25]	Jain S L, Lakeman J B, Pointon K D , et al. Electrochemical performance of a hybrid direct carbon fuel cell powered by pyrolysed MDF[J]. Energy & Environmental Science, 2009,2(6):687-693.
[26]	Jiang C R, Ma J J, Bonaccorso A D , et al. Demonstration of high power, direct conversion of waste-derived carbon in a hybrid direct carbon fuel cell[J]. Energy & Environmental Science, 2012,5(5):6973-6980.
[27]	Ahn S Y, Eom S Y, Rhie Y H , et al. Utilization of wood biomass char in a direct carbon fuel cell(DCFC) system[J]. Applied Energy, 2013,105:207-216.
[28]	Li S W, Lee A C, Mitchell R E , et al. Direct carbon conversion in a helium fluidized bed fuel cell[J]. Solid State Ionics, 2008,179(27/32):1549-1552.
[29]	Wu Y Z, Su C, Zhang C M , et al. A new carbon fuel cell with high power output by integrating with in situ catalytic reverse Boudouard reaction[J]. Electrochemistry Communications, 2009,11(6):1265-1268.
[30]	Nakagawa N, Ishida M . Performance of an internal direct oxidation carbon fuel cell and its evaluation by graphic exergy analysis[J]. Industrial & Engineering Chemistry Research. 1988,27(7):1181-1185.
[31]	Tang Y B, Liu J . Effect of anode and Boudouard reaction catalysts on the performance of direct carbon solid oxide fuel cells[J]. International Journal of Hydrogen Energy, 2010,35(20):11188-11193.
[32]	Xie Y M, Tang Y B, Liu J . A verification of the reaction mechanism of direct carbon solid oxide fuel cells[J]. Journal of Solid State Electrochemistry, 2013,17(1):121-127.
[33]	Cai W Z, Liu J, Xie Y M , et al. An investigation on the kinetics of direct carbon solid oxide fuel cells[J]. Journal of Solid State Electrochemistry, 2016,20(8):2207-2216.
[34]	Xu H R, Chen B, Liu J , et al. Modeling of direct carbon solid oxide fuel cell for CO and electricity cogeneration[J]. Applied Energy, 2016,178:353-362. doi: 10.1016/j.apenergy.2016.06.064 URL
[35]	Gür T M, Huggins R A . Direct electrochemical conversion of carbon to electrical energy in a high temperature fuel cell[J]. Journal of The Electrochemistry Society, 1992,139(10):L95-L97. doi: 10.1149/1.2069025 URL
[36]	Tang Y B, Liu J, Sui J . A novel direct carbon solid oxide fuel cell[J]. ECS Transactions, 2009,25(2):1109-1114.
[37]	Tang Y B, Liu J . Fueling solid oxide fuel cells with activated carbon[J]. Acta Physico - Chimica Sinica, 2010,26(5):1191-1194.
[38]	Liu J( 刘江), Tang Y B( 唐玉宝), Sui J( 隋静 ). A direct carbon solid oxide fuel cell: Chinese Patent, ZL200910192848.8[P]. December 28, 2011.
[39]	Cai W Z, Liu J, Yu F Y , et al. A high performance direct carbon solid oxide fuel cell fueled by Ca-loaded activated carbon[J]. International Journal of Hydrogen Energy, 2017,42(33):21167-21176.
[40]	Xie Y M, Tang Y B, Liu J . An Al₂O₃-doped YSZ electrolyte-supporting solid oxide fuel cells fabricated by dip-coating and its direct operation on carbon fuel[J]. ECS Transactions, 2013,57(1):3039-3048.
[41]	Zhang L, Xiao J, Xie Y M , et al. Behavior of strontium- and magnesium-doped gallate electrolyte in direct carbon solid oxide fuel cells[J]. Journal of Alloys and Compounds, 2014,608:272-277.
[42]	Bai Y H, Liu Y, Tang Y B , et al. Direct carbon solid oxide fuel cell - a potential high performance battery[J]. International Journal of Hydrogen Energy, 2011,36(15):9189-9194.
[43]	Yu F Y, Zhang Y P, Yu L , et al. All-solid-state direct carbon fuel cells with thin yttrium-stabilized-zirconia electrolyte supported on nickel and iron bimetal-based anodes[J]. International Journal of Hydrogen Energy, 2016,41(21):9048-9058.
[44]	Xiao J, Han D, Yu F Y , et al. Characterization of symmetrical SrFe_0.75Mo_0.25O₃-_δ electrodes in direct carbon solid oxide fuel cells[J]. Journal of Alloys and Compounds, 2016,688:939-945.
[45]	Liu J( 刘江 ). Cone-shaped anode-supported solid oxide fuel cell/stack: Chinese Patent, ZL200510101483.3[P]. November 7, 2007.
[46]	Timurkutluk B, Timurkutluk C, Mat M D , et al. A review on cell/stack designs for high performance solid oxide fuel cells[J]. Renewable and Sustainable Energy Reviews, 2016,56:1101-1121.
[47]	Sui J, Liu J . An electrolyte-supported SOFC stack fabricated by slip casting technique[J]. ECS Transactions, 2007,7(1):633-637.
[48]	Sui J, Liu J . Slip-cast Ce_0.8Sm_0.2O_1.9 cone-shaped SOFC[J]. Journal of the American Ceramic Society, 2008,91(4):1335-1337.
[49]	Zhang Y H, Liu J, Yin J , et al. Fabrication and performance of cone-shaped segmented-in-series solid oxide fuel cells[J]. International Journal of Applied Ceramic Technology, 2008,5(6):568-573.
[50]	Bai Y H, Liu J, Gao H B , et al. Dip-coating technique in fabrication of cone-shaped anode-supported solid oxide fuel cells[J]. Journal of Alloys and Compounds, 2009,480(2):554-557.
[51]	Bai Y H, Liu J, Wang C L . Performance of cone-shaped tubular anode-supported segmented-in-series solid oxide fuel cell stack fabricated by dip-coating technique[J]. International Journal of Hydrogen Energy, 2009,34(17):7311-7315.
[52]	Ding J, Liu J . A novel design and performance of cone-shaped tubular anode-supported segmented-in-series solid oxide fuel cell stack[J]. Journal of Power Sources, 2009,193(2):769-773.
[53]	Xiao J, Liu J, Ding J . Electrochemical performance of cone-shaped tubular anode supported solid oxide fuel cells fabricated by low-pressure injection moulding technique[J]. ECS Transactions, 2011,35(1):609-614.
[54]	Wang H D, Liu J . Effect of anode structure on performance of cone-shaped solid oxide fuel cells fabricated by phase inversion[J]. International Journal of Hydrogen Energy, 2012,37(5):4339-4345.
[55]	Liu Y, Tang Y B, Ding J , et al. Electrochemical performance of cone-shaped anode-supported segmented-in-series SOFCs fabricated by gel-casting technique[J]. International Journal of Hydrogen Energy, 2012,37(1):921-925.
[56]	Bai Y H, Wang C L, Ding J , et al. Direct operation of cone-shaped anode-supported segmented-in-series solid oxide fuel cell stack with methane[J]. Journal of Power Sources, 2010,195(12):3882-3886.
[57]	Liu Y, Bai Y H, Liu J . Carbon monoxide fueled cone-shaped tubular solid oxide fuel cell with(Ni_0.75Fe_0.25-5%MgO)/YSZ anode(vol 160, F13, 2013)[J]. Journal of The Electrochemical Society, 2013,160(4):X5-X5.
[58]	Wang X Q( 王晓强), Liu J( 刘江), Xie Y M( 谢永敏 ), et al. A high performance direct carbon solid oxide fuel cell stack for portable applications[J]. Acta Physico - Chimica Sinica( 物理化学学报), 2017,33(8):1614-1620.
[59]	Liu J( 刘江), Zhang L( 张莉), Liu Y( 刘燕 ), et al. A solid oxide fuel cell stack based on a single piece of electrolyte plate: Chinese Patent, ZL201420173772.0[P]. October 8, 2014.
[60]	Wang W, Liu Z J, Zhang Y P , et al. A direct carbon solid oxide fuel cell stack on a single electrolyte plate fabricated by tape casting technique[J]. Journal of Alloys and Compounds, 2019,794:294-302.
[61]	Cai W Z, Zhou Q, Xie Y M , et al. A direct carbon solid oxide fuel cell operated on a plant derived biofuel with natural catalyst[J]. Applied Energy, 2016,179:1232-1241.
[62]	Risnes H, Fjellerup J, Henriksen U , et al. Calcium addition in straw gasification[J]. Fuel, 2003,82(6):641-651.
[63]	Quyn D M, Hayashi J, Li C Z . Volatilisation of alkali and alkaline earth metallic species during the gasification of a victorian brown coal in CO₂[J]. Fuel Processing Techno-logy, 2005,86(12/13):1241-1251.
[64]	Zhou Q, Cai W Z, Zhang Y P , et al. Electricity generation from corn cob char through a direct carbon solid oxide fuel cell[J]. Biomass and Bioenergy, 2016,91:250-258.
[65]	Cai W Z, Liu J, Liu P P , et al. A direct carbon solid oxide fuel cell fueled with char from wheat straw, International Journal of Energy Research, 2019,43(7):2468-2477.
[66]	Qiu Q Y, Zhou M Y, Cai W Z , et al. A comparative investigation on direct carbon solid oxide fuel cells operated with fuels of biochar derived from wheat straw, corncob, and bagasse[J]. Biomass and Bioenergy, 2019,121:56-63.
[67]	Qiu Q Y( 丘倩媛), Chen Q Y( 陈倩阳), Liu Z J( 刘志军 ), et al. Biochar derived from coconut as fuel for the direct carbon solid oxide fuel cell[J]. Journal of Fuel Chemistry and Technology( 燃料化学学报), 2019,47(3):352-360.
[68]	Xie Y M( 谢永敏), Li J L( 李江霖), Hou J X( 侯金醒 ), et al. Direct use of coke in a solid oxide fuel cell[J]. Journal of Fuel Chemistry and Technology( 燃料化学学报), 2018,46(10):1168-1174.
[69]	Wu H, Xiao J, Zeng X Y , et al. A high performance direct carbon solid oxide fuel cell — a green pathway for brown coal utilization[J]. Applied Energy, 2019,248:679-687.
[70]	Xie Y M, Xiao J, Liu D D , et al. Electrolysis of carbon dioxide in a solid oxide electrolyzer with silver-gadolinium-doped ceria cathode[J]. Journal of The Electrochemical Society, 2015,162(4):F397-F402.

Temperature/^oC	ΔH/(kJ·mol^-1)	ΔS/(J·K^-1·mol^-1)	ΔG/(kJ·mol^-1)	ΔG/ΔH
700	-394.54	1.31	-395.82	100.43%
750	-394.65	1.21	-395.88	100.42%
800	-394.75	1.11	-395.94	100.40%
850	-394.86	1.01	-395.99	100.38%