热变形协同优化BiSbSe1.50Te1.50材料电热输运

doi:10.15541/jim20240190

无机材料学报 ›› 2024, Vol. 39 ›› Issue (12): 1316-1324.DOI: 10.15541/jim20240190 CSTR: 32189.14.10.15541/jim20240190

所属专题：【能源环境】热电材料(202412)

热变形协同优化BiSbSe_1.50Te_1.50材料电热输运

田震¹(), 蒋全伟¹, 李建波¹, 于砺锋¹, 康慧君¹^,²(), 王同敏¹^,²

1.大连理工大学材料科学与工程学院, 辽宁省凝固控制与数字化制备技术重点实验室, 大连 116024
2.大连理工大学宁波研究院, 宁波 315000

收稿日期:2024-04-12 修回日期:2024-06-06 出版日期:2024-07-03 网络出版日期:2024-07-03
通讯作者: 康慧君, 教授. E-mail: kanghuijun@dlut.edu.cn
作者简介:田震(1994-), 男, 博士研究生. E-mail: drtianzhen@mail.dlut.eud.cn
基金资助:
国家自然科学基金(52271025);国家自然科学基金(51927801);国家自然科学基金(U22A20174);辽宁省科技计划联合计划(2023JH2/101700295);大连市科技创新基金(2023JJ12GX021)

Simultaneous Optimization of Electrical and Thermal Transport Properties of BiSbSe_1.50Te_1.50 Thermoelectrics by Hot Deformation

TIAN Zhen¹(), JIANG Quanwei¹, LI Jianbo¹, YU Lifeng¹, KANG Huijun¹^,²(), WANG Tongmin¹^,²

1. Liaoning Provincial Key Laboratory of Solidification Control and Digital Preparation Technology, School of Materials Science and Engineering, Dalian University of Technology, Dalian 116024, China
2. Ningbo Institute of Dalian University of Technology, Ningbo 315000, China

Received:2024-04-12 Revised:2024-06-06 Published:2024-07-03 Online:2024-07-03
Contact: KANG Huijun, professor. E-mail: kanghuijun@dlut.edu.cn
About author:TIAN Zhen (1994-), male, PhD candidate. E-mail: drtianzhen@mail.dlut.eud.cn
Supported by:
National Natural Science Foundation of China(52271025);National Natural Science Foundation of China(51927801);National Natural Science Foundation of China(U22A20174);Science and Technology Planning Project of Liaoning Province(2023JH2/101700295);Innovation Foundation of Science and Technology of Dalian(2023JJ12GX021)

摘要/Abstract

摘要：

作为一种能够同时制备具有相同化学成分的n型与p型热电材料, BiSbSe_1.50Te_1.50材料在开发设计性能优良的热电器件方面具有极大的应用潜力。但其电导率较低, 热电性能较差, 阻碍了进一步推广应用。因此, 在保持较低热导率的前提下, 提升BiSbSe_1.50Te_1.50的电输运性能, 对改善其热电性能具有重要意义。本研究结合封管熔炼和真空热压烧结, 对n型BiSbSe_1.50Te_1.50进行多次重复热变形。研究发现, 热变形使样品产生大量具有择优排列方向和较大表面积的纳米层片, 使其不但可以保持较高载流子浓度, 而且具有高的载流子迁移率, 从而有效提高了BiSbSe_1.50Te_1.50的电导率。与此同时, 热变形还可以在样品中引入多尺度缺陷, 有效散射全尺度声子, 极大地降低了BiSbSe_1.50Te_1.50的热导率。因此, 热变形实现了样品电输运和热输运之间的解耦, 同时改善了电性能和热性能。在500 K时, BiSbSe_1.50Te_1.50的热电优值由未变形样品的0.21提高至0.50, 提升了约138%, 热电性能得到显著改善。本工作为制备具有较高转换效率和均匀结构的BiSbSe_1.50Te_1.50热电器件提供了基础。

关键词: n型BiSbSe_1.50Te_1.50, 热电材料, 热变形, 协同优化

Abstract:

As a typical multi-layered compound thermoelectric (TE) material, BiSbSe_1.50Te_1.50, can be utilized to fabricate p-n junctions with the same chemical composition. It has great potential in the development and design of high-performance TE devices due to its ability to avoid lattice mismatch incompatibility and harmful band misalignment. However, the TE performance of n-type BiSbSe_1.50Te_1.50 is limited due to poor electrical transport properties, which hinders its further application in TE devices. Therefore, it is of great significance to improve the TE performance by enhancing the electrical transport properties while maintaining low thermal conductivity. In this work, a series of n-type BiSbSe_1.50Te_1.50hot deformation samples were prepared by solid-state reaction combined with hot pressed sintering. It is found that the preferred orientation and nanoscale lamellar structures with large surface areas form in hot-deformed samples. The donor-like effect elevates the carrier concentration, while these lamellar structures facilitate higher carrier mobility by providing expressways for carriers, giving rise to the enhanced electrical conductivity. Additionally, various and abundant multiscale defects are introduced into samples, evoking strong phonon scattering with different frequencies and thus lowering the thermal conductivity. The electrical and thermal transport properties have been synergistically optimized by hot deformation, realizing the improvement of TE properties for n-type BiSbSe_1.50Te_1.50. As a result, a peak thermoelectric figure of merit (ZT) of 0.50 at 500 K is achieved for the hot-deformed sample, which increased ~138% compared to the undeformed sample (0.21). This work establishes a foundation for further advancement of the preparation for BiSbSe_1.50Te_1.50 TE devices with high conversion efficiency and homogeneous structure.

Key words: n-type BiSbSe_1.50Te_1.50, thermoelectric material, hot deformation, simultaneous optimization

中图分类号:

TN377

田震, 蒋全伟, 李建波, 于砺锋, 康慧君, 王同敏. 热变形协同优化BiSbSe_1.50Te_1.50材料电热输运[J]. 无机材料学报, 2024, 39(12): 1316-1324.

TIAN Zhen, JIANG Quanwei, LI Jianbo, YU Lifeng, KANG Huijun, WANG Tongmin. Simultaneous Optimization of Electrical and Thermal Transport Properties of BiSbSe_1.50Te_1.50 Thermoelectrics by Hot Deformation[J]. Journal of Inorganic Materials, 2024, 39(12): 1316-1324.

图/表 8

图1 HD0、HD1和HD2样品的制备工艺流程图

Fig. 1 Schematic diagram of preparation method of HD0, HD1 and HD2 samples

图2 BiSbSe1.50Te1.50粉体、未变形块体和变形块体样品的XRD图谱

Fig. 2 XRD patterns of BiSbSe1.50Te1.50 powder, bulk samples before and after hot deformation

图3 HD0和HD2块体样品的织构测试图

Fig. 3 Texture patterns of HD0 and HD2 bulk samples (a) Pole figures along (006), (015), (1010), and (0018) directions; (b) Inverse pole figures (IPFs) and (c) orientation distribution function (ODF) patterns of HD0 and HD2 samples

图4 HD0、HD1和HD2样品的(a, c, e)断口SEM照片及(b, d, f)对应的3D重构图

Fig. 4 (a, c, e) SEM images of the fractured surface, and (b, d, f) the corresponding reconstructed 3D morphologies of HD0, HD1 and HD2 bulk samples (a, b) HD0; (c, d) HD1; (e, f) HD2

图5 HD0、HD1和HD2块体样品的电输运性能

Fig. 5 Electrical transport properties of HD0, HD1 and HD2 bulk samples (a) Seebeck coefficient S; (b) Electrical conductivity σ; (c) Carrier concentration nH and carrier mobility μH at 323 K; (d) Power factor PF

图6 HD0、HD1和HD2块体样品的本征电输运性质

Fig. 6 Intrinsic electrical transport properties of HD0, HD1 and HD2 bulk samples (a) nH-dependent |S|; (b) Carrier effective mass m* and reduced Fermi level η; (c) Temperature-dependent weighted carrier mobility μw

图7 HD0、HD1和HD2块体样品的热输运性能

Fig. 7 Thermal transport properties of HD0, HD1 and HD2 bulk samples (a) Total thermal conductivity κtotal; (b) Electrical thermal conductivity κele; (c) Sum of the lattice thermal conductivity and bipolar thermal conductivity κL+κb; (d) Ratio μw/(κL+κb) as a function of temperature

图8 HD0、HD1和HD2块体样品的热电优值

Fig. 8 ZT of HD0, HD1 and HD2 bulk samples (a, b) Temperature-dependent (a) quality factor B and (b) ZT; (c) Average ZT in the temperature range of 323-550 K

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热变形协同优化BiSbSe_1.50Te_1.50材料电热输运

Simultaneous Optimization of Electrical and Thermal Transport Properties of BiSbSe_1.50Te_1.50 Thermoelectrics by Hot Deformation

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热变形协同优化BiSbSe1.50Te1.50材料电热输运

Simultaneous Optimization of Electrical and Thermal Transport Properties of BiSbSe1.50Te1.50 Thermoelectrics by Hot Deformation

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热变形协同优化BiSbSe_1.50Te_1.50材料电热输运

Simultaneous Optimization of Electrical and Thermal Transport Properties of BiSbSe_1.50Te_1.50 Thermoelectrics by Hot Deformation