乙醇在铈基阳极SOFC上发电性能的研究
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摘要
随着世界各国经济的迅猛发展,能源问题和环境污染问题成为当今社会亟待解决的问题。具有污染少、效率高、不需要贵重金属催化剂等特点的固体氧化物燃料电池(Solid Oxide Fuel Cell, SOFC)在能源与环境日益紧张的今天受到了格外的重视。但其广泛应用仍面临极大的挑战性。
本文主要研究了乙醇应用到高温固体氧化物燃料电池上的发电性能；探究了其发电性能随操作条件的变化规律；同时制备了新型抗积碳催化剂,测试了其抗积碳性能。具体工作及结论如下：
(1)以乙醇的水蒸汽重整反应为基础,将其应用到高温固体氧化物燃料电池中。以添加水蒸汽的乙醇蒸汽为燃料对电解质支撑的Ni-YSZ/YSZ/LSM单体进行了发电性能测试。实验结果表明：电池的性能曲线很平滑,规律性很好。但是,阳极积碳严重,严重影响了电池运行的稳定性,亟待解决。
(2)采用柠檬酸溶胶.凝胶法制备了Ce1.16Ni0.36Zno.32O3-δ(CNZ)乙醇水蒸气重整反应及阳极抗积碳的催化剂材料。通过XRD表征,制备的催化剂在1200℃焙烧后能够形成完整的晶相,并出现ZrO2的四方晶相和单斜晶相特征峰,且以四方晶相为主。TEM分析了催化剂颗粒的微观性状,无明显团聚。
(3)制备了CNZ-YSZ阳极SOFC单体,进行发电试验。并将其与Ni-YSZ阳极SOFC的发电性能进行了对比。结果发现,前者的发电性能明显优于后者,且前者对添加水蒸汽的乙醇蒸汽重整反应的催化性能及抗积碳性能比后者好得多。
(4)探究了不同操作条件下以添加水蒸汽的乙醇蒸汽为燃料时,CNZ-YSZ阳极SOFC的发电性能及其随操作条件的变化规律。开路状态下对阳极尾气进行气相色谱分析；实验结束后对电池阳极表面进行了SEM表征。结果表明：该催化剂对改善阳极积碳现象效果明显。
Energy shortage and environmental pollution become serious problems in today society with the rapid development of the world economy. Solid oxide fuel cell (SOFC), with the advantage of high efficiency, little pollution and no expensive metal catalyst, attracts more and more attention all over the world. However, its wide application is still facing great challenges.
The power generation performances of high temperature solid oxide fuel cell with ethanol as fuel are mainly studied in this paper; the laws of its power generation performances with the variation of operating conditions are explored; a new anti-carbon deposition catalyst is prepared, and its resistance to carbon formation is tested. The specific work and conclusions are as the follows:
(1) Mixture of ethanol and water vapor is applied to high temperature solid oxide fuel cell based on the ethanol steam reforming reaction. The performances of electrolyte-supported Ni-YSZ/YSZ/LSM with mixture of ethanol and water vapor as fuel are tested. The experimental results show that the cell has a good power generation performance. But carbon deposition is very serious on the anode, which seriously affects the operational stability of the cell, need to be solved.
(2) Ce1.16Ni0.36Zn0.32O3-δ(CNZ) catalyst is prepared by citric acid sol-gel method, which can promote ethanol steam reforming reaction and reduce the carbon deposition. It can be seen that catalyst is well crystallized at 1200℃from the XRD spectrum. The characteristic peaks of cubic and orthorhombic phase of ZrO2 can be found in the XRD spectrum, and the cubic phase is the main phase. The microcosmic shape of the catalyst particles is analyzed through TEM, and no apparent reunion.
(3) The SOFC with CNZ-YSZ anode is prepared, and its power generation performances are tested. And it is compared with those of the SOFC with Ni-YSZ anode. The comparison results show that the power generation performances of the former are much better than the latter's, and the performances of promoting ethanol steam reforming reaction and reducing the carbon deposition of the former are also much better than the latter's.
(4) The power generation performances of the SOFC with CNZ-YSZ anode fed with mixture of ethanol and water vapor are studied at different operating conditions, simultaneously, the laws of which with the variation of operating conditions are studied. The anode exhaust gas is analyzed by the gas chromatography at the condition of open circuit. The surfaces of the cells are characterized by SEM after experiments. The results show that the catalyst can improve carbon formation on the anode obviously.
本文主要研究了乙醇应用到高温固体氧化物燃料电池上的发电性能；探究了其发电性能随操作条件的变化规律；同时制备了新型抗积碳催化剂,测试了其抗积碳性能。具体工作及结论如下：
(1)以乙醇的水蒸汽重整反应为基础,将其应用到高温固体氧化物燃料电池中。以添加水蒸汽的乙醇蒸汽为燃料对电解质支撑的Ni-YSZ/YSZ/LSM单体进行了发电性能测试。实验结果表明：电池的性能曲线很平滑,规律性很好。但是,阳极积碳严重,严重影响了电池运行的稳定性,亟待解决。
(2)采用柠檬酸溶胶.凝胶法制备了Ce1.16Ni0.36Zno.32O3-δ(CNZ)乙醇水蒸气重整反应及阳极抗积碳的催化剂材料。通过XRD表征,制备的催化剂在1200℃焙烧后能够形成完整的晶相,并出现ZrO2的四方晶相和单斜晶相特征峰,且以四方晶相为主。TEM分析了催化剂颗粒的微观性状,无明显团聚。
(3)制备了CNZ-YSZ阳极SOFC单体,进行发电试验。并将其与Ni-YSZ阳极SOFC的发电性能进行了对比。结果发现,前者的发电性能明显优于后者,且前者对添加水蒸汽的乙醇蒸汽重整反应的催化性能及抗积碳性能比后者好得多。
(4)探究了不同操作条件下以添加水蒸汽的乙醇蒸汽为燃料时,CNZ-YSZ阳极SOFC的发电性能及其随操作条件的变化规律。开路状态下对阳极尾气进行气相色谱分析；实验结束后对电池阳极表面进行了SEM表征。结果表明：该催化剂对改善阳极积碳现象效果明显。
Energy shortage and environmental pollution become serious problems in today society with the rapid development of the world economy. Solid oxide fuel cell (SOFC), with the advantage of high efficiency, little pollution and no expensive metal catalyst, attracts more and more attention all over the world. However, its wide application is still facing great challenges.
The power generation performances of high temperature solid oxide fuel cell with ethanol as fuel are mainly studied in this paper; the laws of its power generation performances with the variation of operating conditions are explored; a new anti-carbon deposition catalyst is prepared, and its resistance to carbon formation is tested. The specific work and conclusions are as the follows:
(1) Mixture of ethanol and water vapor is applied to high temperature solid oxide fuel cell based on the ethanol steam reforming reaction. The performances of electrolyte-supported Ni-YSZ/YSZ/LSM with mixture of ethanol and water vapor as fuel are tested. The experimental results show that the cell has a good power generation performance. But carbon deposition is very serious on the anode, which seriously affects the operational stability of the cell, need to be solved.
(2) Ce1.16Ni0.36Zn0.32O3-δ(CNZ) catalyst is prepared by citric acid sol-gel method, which can promote ethanol steam reforming reaction and reduce the carbon deposition. It can be seen that catalyst is well crystallized at 1200℃from the XRD spectrum. The characteristic peaks of cubic and orthorhombic phase of ZrO2 can be found in the XRD spectrum, and the cubic phase is the main phase. The microcosmic shape of the catalyst particles is analyzed through TEM, and no apparent reunion.
(3) The SOFC with CNZ-YSZ anode is prepared, and its power generation performances are tested. And it is compared with those of the SOFC with Ni-YSZ anode. The comparison results show that the power generation performances of the former are much better than the latter's, and the performances of promoting ethanol steam reforming reaction and reducing the carbon deposition of the former are also much better than the latter's.
(4) The power generation performances of the SOFC with CNZ-YSZ anode fed with mixture of ethanol and water vapor are studied at different operating conditions, simultaneously, the laws of which with the variation of operating conditions are studied. The anode exhaust gas is analyzed by the gas chromatography at the condition of open circuit. The surfaces of the cells are characterized by SEM after experiments. The results show that the catalyst can improve carbon formation on the anode obviously.
引文
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