热电材料中的高熵结构设计

doi:10.15541/jim20200659

无机材料学报 ›› 2021, Vol. 36 ›› Issue (4): 399-404.DOI: 10.15541/jim20200659

所属专题：能源材料论文精选(2021)；【虚拟专辑】热电材料(2020~2021)；【虚拟专辑】计算材料；【结构材料】高熵陶瓷；【能源环境】热电材料

热电材料中的高熵结构设计

蔡剑锋¹(), 王泓翔¹^,², 刘国强¹^,², 蒋俊¹^,²()

1.中国科学院宁波材料技术与工程研究所, 宁波 315201
2.中国科学院大学, 北京 100049

收稿日期:2020-11-18 修回日期:2020-12-10 出版日期:2021-04-20 网络出版日期:2020-12-10
通讯作者: 蒋俊, 研究员. E-mail: jjun@nimte.ac.cn
作者简介:蔡剑锋(1995-), 男, 硕士研究生. E-mail: caijianfeng@nimte.ac.cn
基金资助:
宁波市科技创新2025重大专项(2019B10085)

Designing High Entropy Structure in Thermoelectrics

CAI Jianfeng¹(), WANG Hongxiang¹^,², LIU Guoqiang¹^,², JIANG Jun¹^,²()

1. Ningbo Institute of Materials Technology and Engineering, Chinese Academy of Sciences, Ningbo 315201, China
2. University of Chinese Academy of Sciences, Beijing 100049, China

Received:2020-11-18 Revised:2020-12-10 Published:2021-04-20 Online:2020-12-10
Contact: JIANG Jun, professor. E-mail: jjun@nimte.ac.cn
About author:CAI Jianfeng(1995-), male, Master candidate. E-mail: caijianfeng@nimte.ac.cn
Supported by:
Ningbo Science and Technology Innovation 2025 Major Project (2019B10085)

摘要/Abstract

摘要：

高熵合金的设计思想在诸多材料领域都有广泛的应用, 本研究从高熵结构对热电输运性质的影响出发, 着重讨论热电材料对高熵结构设计的一些要求。以CuInTe₂为实例, 提出了热电材料的高熵结构应当尽量减小晶格畸变, 尽量选择在不影响费米面结构的格点位进行高熵掺杂。依据这些准则, 设计的高熵化合物Cu_0.8Ag_0.2Zn_0.1Ga_0.4Ge_0.1In_0.4Te₂的室温热导率降到了2.1 W·m^-1·K^-1, 比基体材料降低70%, 最高ZT值达到1.02, 较基体提升90%。在二元化合物SnTe中进行了AgSbSe₂固溶, 其室温热导率降到1.3 W·m^-1·K^-1, 比基体降低80%以上。本研究表明, 遵循一定准则设计的高熵结构对于提升热电材料性能具有重要的意义。

关键词: 高熵合金, 热电材料, 吉布斯自由能, 高熵结构

Abstract:

With the fascinating properties observed in high entropy alloys, the idea of high entropy design has been applied to many material fields. Thermoelectric materials have some particular requirements for high entropy structure according to their transport characteristics. Here, we revealed that the high entropy structure for thermoelectrics required less lattice distortion, and the doping sites should have less influence on the Fermi surface. In the designed compound of Cu_0.8Ag_0.2Zn_0.1Ga_0.4Ge_0.1In_0.4Te₂, the room-temperature thermal conductivity is reduced by 80% as compared to the matrix, and the maximum ZT is enhanced to 1.02. In SnTe, the solid solution of AgSbSe₂ reduces the room-temperature thermal conductivity by 80%, reaching 1.3 W·m^-1·K^-1. This study shows that the high entropy structure following the proposed designing rules could be an important strategy for thermoelectrics.

Key words: high entropy alloys, thermoelectrics, Gibbs free energy, high entropy structure

中图分类号:

TQ174

蔡剑锋, 王泓翔, 刘国强, 蒋俊. 热电材料中的高熵结构设计[J]. 无机材料学报, 2021, 36(4): 399-404.

CAI Jianfeng, WANG Hongxiang, LIU Guoqiang, JIANG Jun. Designing High Entropy Structure in Thermoelectrics[J]. Journal of Inorganic Materials, 2021, 36(4): 399-404.

图/表 7

图1 CuInTe2的晶体结构(a)与电子能带结构(b)

Fig. 1 Crystal structure (a) and electronic structure (b) of CuInTe2

图2 CuInTe2的电子能态密度, 包括Cu-d与Te-p分波态密度

Fig. 2 Density of State (DOS) of CuInTe2, including the partial DOS for Cu-d and Te-p orbitals

图3 CuInTe2及其高熵固溶化合物的XRD图谱

Fig. 3 XRD patterns for CuInTe2 and its high entropy solid solutions

图4 CuInTe2及其高熵固溶化合物的电导率(a)及塞贝克系数(b)

Fig. 4 Electrical conductivity (a) and Seebeck coefficient (b) for CuInTe2 and its high entropy solid solutions

表1 室温下不同组分样品的载流子浓度与迁移率

Table 1 Carrier concentrations and mobilities of samples with different components at room temperature

Sample	n_H/cm^-3	μ_H/ (cm²·V^-1·s^-1)
CuInTe₂	3.1×10¹⁸	78.1
Cu_0.5Ag_0.5Ga_0.5In_0.5Te₂	1.3×10¹⁸	10.4
Cu_0.5Ag_0.5Zn_0.25Ga_0.25Ge_0.25In_0.25Te₂	5.6×10¹⁹	1.2
Cu_0.8Ag_0.2Zn_0.1Ga_0.4Ge_0.1In_0.4Te₂	3.2×10¹⁹	17.8

图5 CuInTe2及其高熵固溶化合物的热导率(a)及热电优值(b)

Fig. 5 Thermal conductivity (a) and ZT (b) for CuInTe2 and its high entropy solid solutions

图6 SnTe-AgSbSe2固溶体的电导率(a)及热导率(b)[28]

Fig. 6 Electrical conductivity (a) and thermal conductivity (b) for SnTe-AgSbSe2 solid solutions[28] Solid lines refer to total thermal conductivity, dash lines refer to lattice thermal conductivity. and black, red and green refer to SnTe, SnTe+ 10%AgSbSe2 and SnTe+20%AgSbSe2, respectively

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热电材料中的高熵结构设计

Designing High Entropy Structure in Thermoelectrics

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