自蔓延高温合成固体氧化物燃料电池阴极材料La_（1-x）Sr_xMnO_3
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摘要
固体氧化物燃料电池(Solid oxide fuel cell,SOFC)是一种新型绿色能源技术,具有其它燃料电池不具备的全固体、无漏液、寿命长等优点,因而受到世界各国的重视。SOFC是由阴极、电解质、阳极和连接材料等基本元件构成的,每一种元件的性能都关系着SOFC的总效率和性能。La1-xSrxMnO3(LSM)具有高电导率、低反应性以及同电解质材料YSZ兼容性好的特点,是目前固体氧化物燃料电池使用最广泛的阴极材料。传统技术制备的LSM成本过高,阻碍了固体氧化物燃料电池快速发展的步伐,因此探索一种即能够保证产品性能又能有效降低成本的新型制备技术势在必行。
本课题探索采用自蔓延高温合成法( Self-propagation high temperature synthesis,SHS)合成固体氧化物燃料电池阴极材料La0.7Sr0.3MnO3,达到降低材料制备成本的目的。文中设计了4大体系9个自蔓延反应制备La0.7Sr0.3MnO3,研究了各体系自蔓延反应的点火温度、反应温度及自蔓延速度,考查了试样反应前后的失重与收缩情况,并采用扫描电镜、X射线衍射仪等分析了反应产物的形貌和物相特征。XRD分析表明:4大体系9个反应进行的自蔓延高温合成过程均成功制备出了固体氧化物燃料电池阴极材料La0.7Sr0.3MnO3。同时,研究发现反应体系1由于实验成本低、操作简便以及合成产物性能较好,为制备LSM的最佳自蔓延体系。
以体系1为基础,本文研究了成形压力、稀释剂等参数对反应过程及合成产物物理性能的影响;测试了自蔓延高温合成LSM粉末的烧结性能,包括试样强度、相对密度、孔隙率、膨胀系数以及导电性等;通过热力学计算,从理论上分析了不同工艺条件下反应进行的方向和产物的相组成,探讨SHS法制备La1-xSrxMnO4过程的反应历程,分析出体系中可能产生的杂质及其产生的原因,提出了消除杂质相的方法。
最后,本文研究了使用热处理工艺去除自蔓延高温合成产物的杂质相,考查了不同热处理温度以及热处理时间对LSM物相、形貌及性能的影响。
Solid Oxide Fuel Cell (SOFC), as a new way of power generation, exhibits a great potential in solution of energy crisis and environmental pollution, and gets a wide attention in recent year. SOFC is composed by cathode, electrolyte, anode and interconnect. From the viewpoint of the high electrical conductivity, low reactivity and good compatibility with YSZ, La1-xSrxMnO3(LSM)is considered to be the most popular cathode materials for SOFC. However, the high cost of LSM prepared by traditional technology such as solid state sintering and sol-gel method hinders the application and industrialization of SOFC. Therefore, it is important to explore a new synthesis method for reducing the high cost of preparing LSM.
In this paper, La1-xSrxMnO3 was prepared by self-propagating high-temperature synthesis (SHS) which was an effective way in reducing the cost of preparation. Four systems of SHS reaction that included nine reaction formulas were found to synthesize LSM. Self-propagation speeds of flame, ignition temperature, reaction temperature, weight loss and contraction rate of each SHS reaction were investigated. The pattern and component of product were analyzed by SEM and XRD, which indicated that the rhombohedral La0.7Sr0.3MnO3 was prepared by each SHS reaction. Because of the low cost, simple operation and preferable performance of product, the No.1 system was the best reaction system for preparing LSM by SHS.
Based on No.1 system, the effect of some parameters, such as forming pressure and dilution addition, on reaction process and physical performance of the product was studied. And the sintering performance of the LSM, including intensity, relative density, porosity, expansion coefficient and conductivity was investigated as well.
The reaction mechanism of the SHS system was explored through thermodynamic calculation method. The directions and products of the reaction in different technological conditions were decided. Meanwhile, the cause of impurity of the reaction system was analyzed and some advices were brought forward to eliminate the byproducts.
Finally, the study indicated that the impurity brought by SHS could be removed effective, through the heat treatment method. The organizational structure and performance of LSM, on which the different temperature and time of heat treatment effected, were also studied.
本课题探索采用自蔓延高温合成法( Self-propagation high temperature synthesis,SHS)合成固体氧化物燃料电池阴极材料La0.7Sr0.3MnO3,达到降低材料制备成本的目的。文中设计了4大体系9个自蔓延反应制备La0.7Sr0.3MnO3,研究了各体系自蔓延反应的点火温度、反应温度及自蔓延速度,考查了试样反应前后的失重与收缩情况,并采用扫描电镜、X射线衍射仪等分析了反应产物的形貌和物相特征。XRD分析表明:4大体系9个反应进行的自蔓延高温合成过程均成功制备出了固体氧化物燃料电池阴极材料La0.7Sr0.3MnO3。同时,研究发现反应体系1由于实验成本低、操作简便以及合成产物性能较好,为制备LSM的最佳自蔓延体系。
以体系1为基础,本文研究了成形压力、稀释剂等参数对反应过程及合成产物物理性能的影响;测试了自蔓延高温合成LSM粉末的烧结性能,包括试样强度、相对密度、孔隙率、膨胀系数以及导电性等;通过热力学计算,从理论上分析了不同工艺条件下反应进行的方向和产物的相组成,探讨SHS法制备La1-xSrxMnO4过程的反应历程,分析出体系中可能产生的杂质及其产生的原因,提出了消除杂质相的方法。
最后,本文研究了使用热处理工艺去除自蔓延高温合成产物的杂质相,考查了不同热处理温度以及热处理时间对LSM物相、形貌及性能的影响。
Solid Oxide Fuel Cell (SOFC), as a new way of power generation, exhibits a great potential in solution of energy crisis and environmental pollution, and gets a wide attention in recent year. SOFC is composed by cathode, electrolyte, anode and interconnect. From the viewpoint of the high electrical conductivity, low reactivity and good compatibility with YSZ, La1-xSrxMnO3(LSM)is considered to be the most popular cathode materials for SOFC. However, the high cost of LSM prepared by traditional technology such as solid state sintering and sol-gel method hinders the application and industrialization of SOFC. Therefore, it is important to explore a new synthesis method for reducing the high cost of preparing LSM.
In this paper, La1-xSrxMnO3 was prepared by self-propagating high-temperature synthesis (SHS) which was an effective way in reducing the cost of preparation. Four systems of SHS reaction that included nine reaction formulas were found to synthesize LSM. Self-propagation speeds of flame, ignition temperature, reaction temperature, weight loss and contraction rate of each SHS reaction were investigated. The pattern and component of product were analyzed by SEM and XRD, which indicated that the rhombohedral La0.7Sr0.3MnO3 was prepared by each SHS reaction. Because of the low cost, simple operation and preferable performance of product, the No.1 system was the best reaction system for preparing LSM by SHS.
Based on No.1 system, the effect of some parameters, such as forming pressure and dilution addition, on reaction process and physical performance of the product was studied. And the sintering performance of the LSM, including intensity, relative density, porosity, expansion coefficient and conductivity was investigated as well.
The reaction mechanism of the SHS system was explored through thermodynamic calculation method. The directions and products of the reaction in different technological conditions were decided. Meanwhile, the cause of impurity of the reaction system was analyzed and some advices were brought forward to eliminate the byproducts.
Finally, the study indicated that the impurity brought by SHS could be removed effective, through the heat treatment method. The organizational structure and performance of LSM, on which the different temperature and time of heat treatment effected, were also studied.
引文
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[3] 靳智平.燃料电池发电技术在我国电力系统的应用.电力学报, 2004, 19(1): 4-11
[4] Dan Rastler. Opportunities and challenges for fuel cell in the evolving energy enterprise. Fuel Cells Bulletin, 2000, 3(19): 7-11
[5] Shuo-Jen Lee, Fang-Bor Weng. Recent R&D and future prospects of fuel cell technology in Taiwa. Fuel Cells Bulletin, 2002,5(41): 8-11
[6] Jay B.Benziger, M.Barclay Satterfield, Warren H.J. Hogarth. The power performance curve for engineering analysis of fuel cells. Journal of Power Sources, 2006, 155: 272-285
[7] Chunshan Song. Fuel processing for low-temperature and high-temperature fuel cells Challenges, and opportunities for sustainable development in the 21st century. Catalysis Today, 2002, 77: 17-49
[8] Joseph M. King,Michael J.O’Day. Applying fuel cell experience to sustainable power products. Journal of Power Sources, 2000, 86: 16-22
[9] Ferdinand Panik. Link Fuel Cell Technology with Environmental Strategy: The Plug power Story. Journal of Power Sources, 1996, 6: 270-277
[10] Ferdinand Panik. Fuel cell for vehicle applications in cars-bringing the future closer. Journal of Power Sources, 1998, 71: 36-38
[11] 张志明. 燃料电池的演化及发展探析. 技术与创新管理, 2005, 26(3): 81-84
[12] 倪萌, 梁国熙. 碱性燃料电池研究进展.电池, 2004, 34(5): 364-365
[13] 彭苏萍,韩敏芳,杨翠柏,王玉倩.固体氧化物燃料电池. 物理, 2004,33(2):90-94
[14] S.C. Singhal. Solid oxide fuel cells for stationary, mobile, and military applications. Solid State Ionics, 2002, 152-153: 405-410
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