Gd/Ce双填充P型方钴矿的制备与热电性能研究

填充方钴矿材料（skutterudite，SKD）是目前最有可能实现商业化应用的中温热电材料之一，然而P型填充式方钴矿发展缓慢，制约了方钴矿基热电发电器件的最大转换效率。和传统的填充原子相比，重稀土元素Gd的原子质量更大，原子半径更小，有着更好的降低晶格热导率效果。为了获得更低的晶格热导率，本研究引入Ce原子，分别在富铁基RFe3CoSb12和富钴基RFe1.5Co2.5Sb12中开展了Gd/Ce双填的热电性能研究。
本研究使用固相熔融法合成了P型填充式方钴矿，使用XRD和SEM对其进行物相分析，使用Hall、ZEM和LFA467对其电热性能进行测试。从结果来看，Gd在富铁基中填充有限，增加的Gd主要以杂项GdSb的形式出现；而在富钴基中Gd可以按照名义组分填充，通过调整Ce和Gd的含量，小幅度提高功率因子的同时，有效地降低了晶格热导率，Ce0.1Gd0.2Fe1.5Co2.5Sb12在673 K时有最小的晶格热导率0.87 W·m-1·K-1，较基体下降了52%。同时，在723 K时Ce0.1Gd0.2Fe1.5Co2.5Sb12最大ZT值达到1.06。
在COMSOL软件中建立TEG三维仿真模型，系统性的研究单段式发电器件单偶Π对的输出特性随几何结构的变化；在此基础上，采用“两段式—三段式”不断迭代的方法研究宽温域三段式热电发电器件的几何结构优化，通过调整N、P热电臂上各段的高度比，在TEG高温端温度为1023 K，低温端温度为300 K的工况下，最优仿真模型的最大转换效率达到了15.55%；最后在仿真模型的指导下，通过优化批量化制备器件的工艺，快速制备了单段式TEG（8对），在高温端温度为873 K、低温端温度为300 K时，器件实测的最大转换效率为6.72%。

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