高性能PbTe基热电材料及器件的制备与性能研究

热电材料能够直接实现热能和电能之间的相互转换，能够将自然界和人类生产生活中随处可见的各种余热转变为潜在的能源。其转换过程不产生任何污染，符合当前新能源发展战略，且热电器件体积小巧，工作时没有额外的运动部件，能够广泛应用于如微区制冷、航空航天等民用和尖端领域，被认为是未来科技发展的重要组成部分。在众多热电材料体系中，中温区热电材料PbTe在材料和器件性能方面表现优异。但科技的发展对热电材料提出了更高的要求，且n型和p型PbTe的性能依然有很大的提升空间。本论文以PbTe为研究对象，依据其能带结构，分别针对n型和p型PbTe材料使用不同的优化策略提升材料性能并探讨其优化机理。并依托高性能PbTe材料研究了如何制备高性能的发电器件和制冷器件，推进了PbTe基热电材料的产业化进程。本论文获得的主要成果如下：

（1）Pb空位消除优化n型PbTe材料与器件性能。阴离子位置的少量掺杂行为不影响n型PbTe的导带形状，不会减小材料的有效质量；I元素作为施主掺杂剂可以为材料提供电子；在Te位置掺杂S元素可以减少材料中的Pb空位，能够有效地提升材料的载流子浓度和迁移率，有效地提高材料的电性能；同时，S元素还能通过诱导晶格畸变，在不产生第二相的情况下有效地降低材料的晶格热导率。在S和I元素的协同作用下，材料PbTe_0.987S_0.01I_0.003的最大zT值在750 K优化至1.7以上，以此材料为n型热电臂制备的单级在559 K时热电转换效率达到9.4%，分段器件在510 K时热电转换效率达到12.2%。

（2）掺杂效率提升优化n型PbTe材料性能。高掺杂效率可以通过极少的掺杂剂产生足够的载流子浓度，从而有效避免电离杂质对电子的散射，使材料具有更高的迁移率；低温熔炼可以减少Pb空位，使Br具有比I元素更高的掺杂效率；结合S元素掺杂减少材料中的Pb空位可以使Br的掺杂效率进一步得到提升。在S和Br元素的协同作用下，材料PbTe_0.991S_0.008Br_0.001的室温功率因子提升至48.0 μWcm^-1K^-2，材料在300-850 K下的平均zT值达到了1.2。

（3）迁移率优化提升n型PbTe材料与器件性能。铸锭材料中具有更少的载流子散射，能够进一步提高材料迁移率；Cr元素在Pb位置掺杂不影响材料的有效质量同时可以提高I元素的掺杂效率；I元素在Cr掺杂的基础上可以显著降低材料的晶格热导率。在I和Cr元素的协同作用下，铸锭材料Pb_0.995Cr_0.005Te_0.9999I_0.0001的室温功率因子提高到~52.0 μWcm^-1K^-2，室温zT值提升至0.7，在300-700 K之间的平均zT值提升至1.2。以此材料为n型热电臂，商用Bi₂Te₃材料为p型热电臂制备的发电器件在温差为272 K时，转换效率达到6.5%；制冷器件在高温端为75 ℃时实现了73 K的最大温差，在温差ΔT=1 K时，制冷效率最大为COP=11.7。

（4）多策略协同优化p型PbTe材料与器件性能。在p型PbTe中，Na元素掺杂可以提高载流子浓度；Mg和Ge元素掺杂不仅可以诱导晶格畸变减小晶格热导率，Mg掺杂还可以促进能带简并提高Seebeck系数以及增大材料的禁带宽度抑制双极扩散；Ge原子掺杂后形成原子偏心结构且声学支和光学支频率降低材料非谐性增强，进一步降低晶格热导率。在Na，Mg和Ge元素的协同作用下，材料Pb_0.97Na_0.03Te-2%MgTe-0.75%GeTe的最大zT值在850 K时达到2.8，300-850 K的平均zT值达到1.7。

（5）高性能的热电材料结合尺寸优化提高器件的能量转换效率。以Na-Mg-Ge共掺杂p型PbTe和S-I共掺杂n型PbTe为热电臂制备的热电器件在553 K的温差下，单极器件能量转换效率达到10.5%，分段器件的能量转换效率达到15.5%。

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