Controlling reaction process to realize high thermoelectric performance in filled skutterudites
Controlling reaction process to realize high thermoelectric performance in filled skutterudites
复制标题
控制反应过程实现填充方钴矿的高热电性能
DOI：
10.1016/j.jallcom.2020.157971
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发表时间：
2020-11
影响因子：
6.2
通讯作者：
Lixia Zhang
中科院分区：
文献类型：
--
作者：
Jialun Zhang;Wei Ren;Hangbin Feng;Huiyuan Geng;Lixia Zhang
将Yb原子填充到方钴矿的纳米空隙中一直是获得高热电性能的主要策略。然而，文献中的ZT和Yb实际总填充分数（ATFF）都存在很大差异。这种差异背后的潜在机制仍然是个谜。本文从动力学角度对未填充、单填充和多填充方钴矿的固溶体和相变进行了理论和实验研究。因此，ZT和ATFF的差异可以用复杂的反应过程来解释。密度泛函理论计算结果表明，Yb原子在CoSb 3中的固溶过程存在一个极大的能垒，其他填充原子的引入会进一步降低Yb原子的扩散速率，延缓整个反应过程.随着反应的进行，ATFF先急剧增加，最后保持不变，表现出从非平衡微结构到平衡微结构的复杂相变行为。通过优化合成路线，成功地将反应过程推进到Yb0. 3Ca0. 1Al0. 1Ga0. 1In0. 1Co3. 75Fe0. 25Sb12样品的极限。理论转换效率为14.12%，具有良好的稳定性和重现性。我们的研究结果提供了一个内在的理解，从材料科学的要领，这是适用于设计其他高性能的功能材料的化学掺杂。
Filling Yb atoms into the nanovoid of skutterudites has been long the main strategy to achieve high thermoelectric performance. However, both theZTand the Yb actual total filling fraction (ATFF) show great discrepancies among the literature. The underlying mechanisms behind such discrepancy still keep mysterious. Here, we theoretically and experimentally study the solid solution and phase transformation in the un-filled, single-filled, and multiple-filled skutterudites from a kinetics perspective. TheZTand ATFF discrepancies are thus explained by the complex reaction process. Our density functional theory calculations indicate that an extraordinarily large energy barrier exists in the solid solution process of Yb atoms in CoSb3.The introduction of other filling atoms can further reduce the Yb diffusion rate, putting off the overall reaction process. As the reaction progresses, the ATFF first increases sharply and finally keeps constant, representing the complex phase transition behaviors from non-equilibrium microstructures to equilibrium microstructures. Through optimizing the synthesis route, we successfully promote the reaction process to the ultimate limit in the Yb0.3Ca0.1Al0.1Ga0.1In0.1Co3.75Fe0.25Sb12sample. A remarkable theoretical conversion efficiency of 14.12% is achieved, exhibiting excellent stability and reproducibility as expected. Our results provide an intrinsic understanding of chemical doping from materials science essentials, which is applicable for designing other high-performance functional materials.
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影响因子：
13.6
作者：
Zhen Liu;Teng Lu;Fei Xue;Hengchang Nie;R. Withers;A. Studer;F. Kremer;N. Narayanan;Xianlin Dong;D. Yu;Long-qing Chen;Yun Liu;Genshui Wang
通讯作者：
Zhen Liu;Teng Lu;Fei Xue;Hengchang Nie;R. Withers;A. Studer;F. Kremer;N. Narayanan;Xianlin Dong;D. Yu;Long-qing Chen;Yun Liu;Genshui Wang
DOI：
10.1002/pssa.201532539
发表时间：
2016-03
期刊：
physica status solidi (a)
影响因子：
--
作者：
A. Schmitz;C. Schmid;C. Stiewe;J. de Boor;E. Müller
通讯作者：
A. Schmitz;C. Schmid;C. Stiewe;J. de Boor;E. Müller
影响因子：
6.2
作者：
Shuye Zhang;Sunwu Xu;Hui Gao;Qingshuang Lu;Tiesong Lin;P. He;H. Geng
通讯作者：
Shuye Zhang;Sunwu Xu;Hui Gao;Qingshuang Lu;Tiesong Lin;P. He;H. Geng
DOI：
10.1016/j.actamat.2019.04.025
发表时间：
2019-03
期刊：
AMI: Acta Materialia
影响因子：
--
作者：
G. Rogl;K. Yubuta;M. Kerber;A. Grytsiv;M. Zehetbauer;E. Bauer;P. Rogl
通讯作者：
G. Rogl;K. Yubuta;M. Kerber;A. Grytsiv;M. Zehetbauer;E. Bauer;P. Rogl
影响因子：
64.8
作者：
Biswas, Kanishka;He, Jiaqing;Kanatzidis, Mercouri G.
通讯作者：
Kanatzidis, Mercouri G.