摘要
作为一种新型的能源技术，燃料电池优点良多，被誉为21世纪的绿色电源。其中，固体氧化物燃料电池(Solid Oxide Fuel Cells，SOFCs)因能量转化率高以及燃料适应范围广等突出优点脱颖而出，成为优先发展的一类。
目前较为成熟的SOFC技术均基于氧离子导体电解质，如稳定氧化锆(YSZ)，掺杂氧化铈(DCO)等。然而，它们分别存在中温下电导率不足，还原气氛下化学组成不稳定等缺点。就SOFC的操作原理而言，实际上质子导体与氧离子导体同样都能作为电解质，且基于钙钛矿型物质的质子导体电解质在很多方面也有其超越氧离子导体的优点，但目前其发展相对比较滞后。另外，随着市场上对SOFC的小型化，集散化和可移动化日益高涨的需求，液体燃料越来越受到青睐，而目前SOFC的常用燃料为氢气或烃类物质，前者价格昂贵，难以储运；后者易于积碳，给阳极材料的选择带来很大的难题。
针对以上问题，本论文致力于发展质子导体SOFC电解质以及极易液化的工业液氨燃料。论文首先综述了SOFC的工作原理，关键材料，并讨论了部分关键的工作机理(第一，二章)；而后从降低烧结温度，提高电池输出的角度出发，分别研究了厚膜与薄膜质子导体SOFC的制备以及性能表征(第三章)；其后针对氢和烃类燃料的缺点，尝试以氨气作为质子导体或氧离子导体SOFC的燃料，研究其电池性能，评价氨代替氢和烃类燃料的可能性(第四章)；另外，盐-氧化物复合电解质也被初步考虑作为中低温SOFC的电解质(第五章)。主要研究成果归纳如下：
1．质子导体SOFC的制备和性能研究：目前已有文献报道的质子导体SOFC多使用钙钛矿型材料作为电解质，其电池构型均为厚膜的电解质支撑。这种构型的一大问题是烧结温度过高(＞1500℃)，从而增加了制备成本。本论文中，掺杂助烧结剂与粒子级配法被试用于降低掺杂BaCeO_3材料的烧结温度。通过添加合适剂量的氧化钴以及使用不同大小的初始粒子，掺杂BaCeO_3的烧结温度可被降低到1300℃左右。进一步的优化研究显示，如兼顾烧结与电导两方面因素，氧化钴的最佳掺杂量应为1％。另外，实验中也发现了掺钴样品的开路电压(OCV)在低温区反常下降的现象，进而初步讨论钴的掺入改变掺杂BaCeO_3导电方式的
As a novel power technology, feul cells have many excellences, and are so called "green power of 21st century". In various fuel cells, solid sxide fuel cells(SOFCs) are of high energy efficiency and extensive fuel flexibility, and are in preferential development among all kinds of fuel cells.
Untill now, the more developed SOFCs technologies were all based on oxygen-ion conductors, such like stabilized ZrO_2(YSZ), doped CeO_2 (DCO), etc. But, compared with oxygen-ion conductors, proton conductor has it's own specialty. SOFC based on proton conductors produce water vapor at the cathode side, which helps to improve the EMF and the conversion efficiency of SOFCs system, and also, proton conductors result in lower conducting activation energies than those of oxygen-ion conductors. But compared with oxygen-ion conductors, proton conductors are less concerned. In addition, the now extensively used fuels of SOFCs are hydrogen and hydrocarbons, but the former is too expensive to be used commercially, and the latter will cause a anode-choking problem.
According to the above problems, we concentrate on the unconventional electrolytes and fuels. First of all, the technical principal and key materials of SOFCs are summarized, and some key mechanisms are discussed (Chapter 1 and 2). Secondly, in order to decrease the sintering temperature and increase fuel cell output, the preparation, expression and performance of SOFCs based on body and thin film proton conductors are researched (Chapter 3). Thirdly, ammonia are concerned to substrate hydrogen and hydrocarbons as the fuel of SOFCs, the performance of SOFCs based on proton or oxygen-ion conductors fuelled by ammonia are tested (Chapter 4). Fourthly, in order to decrease the operating temperature of SOFCs to lower level (150-500℃), composite salts are primarily considered as the electrolyte of SOFCs used below 500℃.
Proton conducting SOFCs usually use doped BaCeO_3 as electrolyte, the common construction of cells are electrolyte support. The key problem of this kind of SOFCs is the high sintering temperatures (above 1600℃), which greatly increases the cost. A
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