硫属化合物热电材料制备与器件仿真设计

利用热电效应进行能量转换是应对能源危机和促进碳减排的重要手段。开发 具有高性能的热电材料，装配设计有高效率、高输出功率的热电器件是促进热电 技术应用的重中之重。在中温区，p 型碲化铅有着超高的热电性能，因此合成与 高性能的 p型材料相匹配的n型材料是提升中温区器件效率的核心。在低温区， 银基硫属化合物以出色的近室温热电性能和可加工性成为低温热电材料的新星， 是制备柔性热电器件的良好载体。本课题利用有限元仿真进行器件结构设计，开 发高效率可大规模应用的中温区热电器件与高功率的近室温银基柔性器件。一方 面，合成高性能的n型PbSe基热电材料，以p型PbTe基热电材料和n型PbSe基 热电材料为载体进行铅基平板型器件的设计，并依此对热电发电器件进行结构优 化，大幅提高转换效率；另一方面，对高性能银基热电材料进行柔性器件仿真设 计，利用仿真结果指导制成有超高归一化功率密度的器件。主要的研究成果如下： 本课题利用中熵策略改善 n型铅基热电材料的性能，该方法显著降低了材料 的晶格热导率，实现材料热电性能大幅优化。中熵工程构造的晶格畸变显著降低 了材料的晶格热导率，此基础上选择 I作为掺杂剂，通过不同的尝试发现其在低 浓度掺杂下的高迁移率有助于电性能的提升。进一步进行Ga的共掺杂，大幅提升 了中熵材料的电性能，其功率因子在450-800 K温度区间均超过20 μW cm-1 K-2。 最终将材料Pb0.97Ga0.03Se0.699I0.001(TeS)0.15在 850 K 时的最大 ZT值提升至 1.82。 本课题通过有限元仿真技术，利用变截面积的高度比仿真方法，实现了对铅 基热电发电机转换效率的大幅提升。以本文所合成PbSe基材料组成的铅基发电器 件为载体进行仿真，调整高度与横截面积的仿真方法可将单级热电器件的能量转 换效率在470 K温差下的仿真理论值从11.0%，提升至12.6%。进一步地，通过分 段器件设计，变截面积高度比仿真方法可提升器件的热电转换效率至14.0%。 本课题利用有限元仿真手段，探究提升柔性器件输出功率办法并指导设计， 实现近室温柔性热电发电机的最大归一化功率密度。利用仿真确定器件各部分尺 寸规格，选取薄基板与厚电极，进行6对面外型银基柔性器件制作。实现在2.2 K 温差时，开路电压达4.4 V，最大电流超过400 mA，最大输出功率高达438 μW， 归一化功率密度的最高达33.6 μW cm-1 K-2，达到当前柔性发电器件的先进水平。

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