工程科学学报，第38卷，第11期：1610-1619,2016年11月 Chinese Journal of Engineering,Vol.38,No.11:1610-1619,November 2016 D0l:10.13374/j.issn2095-9389.2016.11.015:http://journals.ustb.edu.cn 碳基燃料气体组成和运行温度对固体氧化物燃料电 池开路电压的影响 陈志远2》，王丽君》区，赵海雷2》，李福菜》，周国治》 1)北京科技大学钢铁治金新技术国家重点实验室，北京1000832)北京科技大学材料科学与工程学院，北京100083 3)北京科技大学钢铁协同创新中心，北京100083 ☒通信作者，E-mail:ijunwang(@usth.cdu.cm 摘要以最小Gbs自由能法计算固体氧化物燃料电池在不同组成碳基燃料气体组成下的理论积碳量，在此基础上讨论 电池的理论开路电压(OCV),并测试在CO2重整甲烷下N-YSZ‖YSZ LSM阳极支撑固体氧化物燃料电池的OCV.计算表 明，理论积碳量从CH0相图的C角往积碳界线处以均匀速率减小.当积碳全部发生电化学氧化时，建议提高燃料气的碳 氢比以获得较高OCV:反之则建议减小碳氢比.当燃气组分接近位于C-H0相图中OCV界线(OCV=0V)时，OCV会发生 急剧下降.同样地，实验表明，当燃气中C0,体积分数高于80%，会使得0CV大幅下降.综上可知，燃料气组分控制在积碳界 线附近将有利于减少积碳并保证一定的电池发电性能.600℃时，在积碳界线的非积碳区侧，提高燃气中氢含量可提高0CV. 而采用相同含量的C0,稀释时，CH4、H2和C0燃气下电池的OCV则依次降低.另外，实验表明升高外重整比例和降低温度， 并不能显著提高OCV. 关键词固体氧化物燃料电池：热力学：甲烷：开路电压：积碳 分类号TM911.4:0646 Effects of the compositions of carbon-base fuels and temperature on the open circuit voltage of solid oxide fuel cells CHEN Zhi-yuan),WANG Li-jun',ZHAO Hai-lei,LI Fu-shen2),CHOU Kuo-ehih 1)State Key Laboratory of Advanced Metallurgy,University of Science and Technology Beijing,Beijing 100083,China 2)School of Materials Science and Engineering,University of Seience and Technology Beijing,Beijing 100083,China 3)Collaborative Innovation Center of Steel Technology,University of Science and Technology Beijing,Beijing 100083,China Corresponding author,E-mail:lijunwang@ustb.edu.cn ABSTRACT The theoretical open circuit voltage (OCV)of solid oxide fuel cells (SOFCs)fed with carbon-based fuels and the amount of deposited carbon on the anode were calculated by the minimum Gibbs free energy method.The OCV values of Ni-YSZ YSZ LSM anode-supported cells using methane-based fuels were experimentally measured.The results indicate that the amount of deposited carbon decreases from the C-corner of the C-H-O diagram to the carbon deposition boundary at a constant rate.In the case that most of deposited carbon is electrochemically oxidized,feeding fuels with high C:H ratio can enhance the value of OCV; Conversely,fuels with low C:H ratio are suggested.Theoretical analysis shows the rapidly decreasing value of OCV near the OCV boundary (OCV=0V).Experimental results also reveal that the value of OCV dramatically decreases when the volume fraction of CO in fuel gas increases to be higher than 80%.These results imply that the compositions of carbon-based fuels should be near the carbon deposition boundary in the C-H-O diagram,which is beneficial to suppress carbon deposition without significant OCV reduction.A 收稿日期：2016-01-26 基金项目：国家重点基础研究发展计划资助项目(2012cB215405):中国博士后科学基金资助项目(2015M570036)工程科学学报，第 38 卷，第 11 期: 1610--1619，2016 年 11 月 Chinese Journal of Engineering，Vol． 38，No． 11: 1610--1619，November 2016 DOI: 10． 13374 /j． issn2095--9389． 2016． 11． 015; http: / /journals． ustb． edu． cn 碳基燃料气体组成和运行温度对固体氧化物燃料电 池开路电压的影响 陈志远1，2) ，王丽君1，3) ，赵海雷2) ，李福燊2) ，周国治1，3) 1) 北京科技大学钢铁冶金新技术国家重点实验室，北京 100083 2) 北京科技大学材料科学与工程学院，北京 100083 3) 北京科技大学钢铁协同创新中心，北京 100083  通信作者，E-mail: lijunwang@ ustb． edu． cn 摘 要 以最小 Gibbs 自由能法计算固体氧化物燃料电池在不同组成碳基燃料气体组成下的理论积碳量，在此基础上讨论 电池的理论开路电压( OCV) ，并测试在 CO2 重整甲烷下 Ni--YSZ‖YSZ‖LSM 阳极支撑固体氧化物燃料电池的 OCV． 计算表 明，理论积碳量从 C--H--O 相图的 C 角往积碳界线处以均匀速率减小． 当积碳全部发生电化学氧化时，建议提高燃料气的碳 氢比以获得较高 OCV; 反之则建议减小碳氢比． 当燃气组分接近位于 C--H--O 相图中 OCV 界线( OCV = 0 V) 时，OCV 会发生 急剧下降． 同样地，实验表明，当燃气中 CO2 体积分数高于 80% ，会使得 OCV 大幅下降． 综上可知，燃料气组分控制在积碳界 线附近将有利于减少积碳并保证一定的电池发电性能． 600 ℃时，在积碳界线的非积碳区侧，提高燃气中氢含量可提高 OCV． 而采用相同含量的 CO2 稀释时，CH4、H2 和 CO 燃气下电池的 OCV 则依次降低． 另外，实验表明升高外重整比例和降低温度， 并不能显著提高 OCV． 关键词 固体氧化物燃料电池; 热力学; 甲烷; 开路电压; 积碳 分类号 TM911. 4; O646 收稿日期: 2016--01--26 基金项目: 国家重点基础研究发展计划资助项目( 2012cB215405) ; 中国博士后科学基金资助项目( 2015M570036) Effects of the compositions of carbon-base fuels and temperature on the open circuit voltage of solid oxide fuel cells CHEN Zhi-yuan1，2) ，WANG Li-jun1，3)  ，ZHAO Hai-lei 2) ，LI Fu-shen2) ，CHOU Kuo-chih1，3) 1) State Key Laboratory of Advanced Metallurgy，University of Science and Technology Beijing，Beijing 100083，China 2) School of Materials Science and Engineering，University of Science and Technology Beijing，Beijing 100083，China 3) Collaborative Innovation Center of Steel Technology，University of Science and Technology Beijing，Beijing 100083，China  Corresponding author，E-mail: lijunwang@ ustb． edu． cn ABSTＲACT The theoretical open circuit voltage ( OCV) of solid oxide fuel cells ( SOFCs) fed with carbon-based fuels and the amount of deposited carbon on the anode were calculated by the minimum Gibbs free energy method． The OCV values of Ni--YSZ‖ YSZ‖LSM anode-supported cells using methane-based fuels were experimentally measured． The results indicate that the amount of deposited carbon decreases from the C-corner of the C--H--O diagram to the carbon deposition boundary at a constant rate． In the case that most of deposited carbon is electrochemically oxidized，feeding fuels with high C ∶ H ratio can enhance the value of OCV; Conversely，fuels with low C∶ H ratio are suggested． Theoretical analysis shows the rapidly decreasing value of OCV near the OCV boundary ( OCV = 0V) ． Experimental results also reveal that the value of OCV dramatically decreases when the volume fraction of CO2 in fuel gas increases to be higher than 80% ． These results imply that the compositions of carbon-based fuels should be near the carbon deposition boundary in the C--H--O diagram，which is beneficial to suppress carbon deposition without significant OCV reduction． A