多掺杂协同调控碲化锡热导率和功率因子提升热电性能

doi:10.15541/jim20180273

无机材料学报 ›› 2019, Vol. 34 ›› Issue (3): 335-340.DOI: 10.15541/jim20180273

多掺杂协同调控碲化锡热导率和功率因子提升热电性能

檀小芳^1,2, 端思晨¹, 王泓翔^1,3, 吴庆松⁴, 李苗苗⁵, 刘国强^1,3, 徐静涛^1,3, 谈小建^{1, 3}, 邵和助^1,3, 蒋俊^1,3

1. 中国科学院宁波材料技术与工程研究所, 宁波 315201;
2. 中国科学技术大学纳米科学技术学院, 苏州 215123;
3. 中国科学院大学, 北京 100049;
4. 复旦大学先进材料实验室, 上海 200438;
5. 河海大学力学与材料学院, 南京 210098

收稿日期:2018-06-21 出版日期:2019-03-20 网络出版日期:2019-02-26
作者简介:檀小芳. E-mail: txf082@mail.ustc.edu.cn

Multi-doping in SnTe: Improvement of Thermoelectric Performance due to Lower Thermal Conductivity and Enhanced Power Factor

TAN Xiao-Fang^1,2, DUAN Si-Chen¹, WANG Hong-Xiang^1,3, WU Qing-Song⁴, LI Miao-Miao⁵, LIU Guo-Qiang^1,3, XU Jing-Tao^1,3, TAN Xiao-Jian^1,3, SHAO He-Zhu^1,3, JIANG Jun^1,3

1. Ningbo Institute of Materials Technology and Engineering, Chinese Academy of Science, Ningbo 315201, China;
2. Nano Science and Technology Institute, University of Science and Technology of China, Suzhou 215123, China;
3. University of Chinese Academy of Sciences, Beijing 100049, China;
4. Laboratory of Advanced Materials, Fudan University, Shanghai 200438, China;
5. College of Mechanics and Materials, Hohai University, Nanjing 210098, China;

Received:2018-06-21 Published:2019-03-20 Online:2019-02-26
About author:TAN Xiao-Fang (1993-), female, Master. E-mail: txf082@mail.ustc.edu.cn
Supported by:
National Key Research and Development Program of China (2016YFC0101801, 2017YFC0111602);Natural Science Foundation of Zhejiang Province (LY18A040008, LY18E020017);Zhejiang Provincial Science Fund for Distinguished Young Scholars (LR16E020001);Youth Innovation Promotion Association of CAS under Grant No. 2018337

摘要/Abstract

摘要：

碲化锡(SnTe)是一种碲化铅的无铅替代物, 在热电领域有广阔的应用前景。但是, 纯相碲化锡样品具有较高的热导率与较低的塞贝克系数, 导致热电性能较差。本研究通过多重掺杂可以显著降低热导率, 提升塞贝克系数, 从而提升热电性能。SnTe热压样品的晶格热导率随着Se和S的引入明显降低,比如SnTe_0.7S_0.15Se_0.15室温下晶格热导率仅为0.99 W•m^-1•K^-1。透射电子显微镜显示, SnTe掺杂样品内存在大量的纳米沉淀相与晶格位错。在此基础上, 掺杂In在价带顶引入共振态大幅提高了样品的塞贝克系数。实验表明通过多重掺杂可以有效提升碲化锡的热电性能, 其中样品Sn_0.99In_0.01Te_0.7S_0.15Se_0.15在850 K时峰值ZT值达到0.8, 这说明碲化锡的确是一种有应用前景的中温区热电材料。

关键词: 碲化锡, 热电性能, 共振态, 晶格热导率

Abstract:

In recent years, tin telluride (SnTe) has attracted considerable interest due to its potential thermoelectric application as a lead-free rock-salt analogue of PbTe. However, pristine SnTe samples show high thermal conductivity and low Seebeck coefficients, resulting in poor thermoelectric performance. In this study, the thermoelectric performance of SnTe was enhanced by well-designed multi-doping, where significantly reduced thermal conductivity and improved Seebeck coefficientswere achieved at the same time. The doped SnTe samples were prepared by hot pressing. The lattice thermal conductivity of SnTe samples is obviously decreased by alloying with Se and S. The transmission electron microscope shows the existence of larger amount of nano-precipitates and the lattice distortions in the alloyed samples. For example, the lattice thermal conductivity of SnTe_0.7S_0.15Se_0.15 sample is reduced to 0.99 W•m^-1•K^-1 at 300 K. The results reveal that the Seebeck coefficients are improved by introducing In resonant state in the band structure of SnTe. The experiments suggest the effectiveness of designed multi-doping in the thermoelectric performance enhancement of SnTe, and a promising ZT of 0.8 at 850 K is achieved in Sn_0.99In_0.01Te_0.7S_0.15Se_0.15. The discovery suggests that SnTe is a promising medium-temperature thermoelectric candidate.

Key words: tin telluride, thermoelectric performance, resonant state, lattice thermal conductivity

中图分类号:

TQ174

檀小芳, 端思晨, 王泓翔, 吴庆松, 李苗苗, 刘国强, 徐静涛, 谈小建, 邵和助, 蒋俊. 多掺杂协同调控碲化锡热导率和功率因子提升热电性能[J]. 无机材料学报, 2019, 34(3): 335-340.

TAN Xiao-Fang, DUAN Si-Chen, WANG Hong-Xiang, WU Qing-Song, LI Miao-Miao, LIU Guo-Qiang, XU Jing-Tao, TAN Xiao-Jian, SHAO He-Zhu, JIANG Jun. Multi-doping in SnTe: Improvement of Thermoelectric Performance due to Lower Thermal Conductivity and Enhanced Power Factor[J]. Journal of Inorganic Materials, 2019, 34(3): 335-340.

图/表 10

Fig.1 Temperature-dependent (a) total thermal conductivities(κtot) and (b) lattice thermal conductivities (κlat) of SnTe1-2xSxSex (x = 0, 0.05, 0.1, and 0.15) samples

Fig. 2 Temperature-dependent (a) total thermal conductivities(κtot) and (b) lattice thermal conductivities (κlat) of Sn1-yInyTe0.7S0.15Se0.15 (y=0, 0.0025, 0.005, 0.01, and 0.015) samples

Fig.3 Microstructures of Sn0.99In0.01Te0.7S0.15Se0.15(a) Medium-magnification TEM and (b) low-magnification images show the presence of nanoscale secondary phase; The inset in (a) is the SAED pattern along [004]; (c) HRTEM image focusing on the secondary phase with distorted connection between the precipitate and the matrix; The top-right and bottom-right insets are the respective FFT images showing lattice distortion between them; (d) the same TEM image with (c) showing the IFFT image (the bottom-right inset) of the selected region reflecting lattice distortion; and strain maps reflect high strain states inside (e) and around (f) the precipitates

Fig.4 Temperature dependent thermoelectric properties: (a) electrical conductivity σ, (b) the Seebeck coefficients S,(c) the power factors S2σ, and (d) ZT values for Sn1-yInyTe0.7S0.15Se0.15 (y=0, 0.0025, 0.005, 0.01, and 0.015) samples

Table 1 The density ρ, hole concentration n, mobility μ, electrical conductivity σ, Seebeck coefficient S, and power factor S2σ for Sn1-yInyTe0.7S0.15Se0.15 (y=0, 0.0025, 0.005, 0.01, and 0.015) samples at room temperature

Samples	ρ/(g•cm^-3)	N/(× 10²⁰, cm^-3)	μ/(cm²•V^-1•s^-1)	σ/(S•cm^-1)	S/(μV•K^-1)	S²σ/(μW•cm^-1•K^-2)
y=0	6.247	1.3	164	3480	7.6	0.2
y=0.0025	6.209	1.4	100	2300	34	2.7
y=0.005	6.161	1.6	57	1510	50	3.7
y=0.01	6.161	2.0	39	1240	63	4.9
y=0.015	6.195	2.2	26	910	71	4.6

Fig.S1 Room temperature (a) powder XRD patterns, (b) lattice parameter of SnTe1-2xSxSex (x=0, 0.05, 0.1, and 0.15) samples

Fig.S2 Temperature dependent (a) electrical conductivity and (b) Seebeck coefficient of SnTe1-2xSxSex (x=0, 0.05, 0.1, and 0.15) samples

Fig.S3 Room temperature (a) powder XRD patterns, (b) lattice parameter a, (c) Hall carrier density Np, and (d) carrier mobility μ of Sn1-yInyTe0.7S0.15Se0.15 (y=0, 0.0025, 0.005, 0.01, and 0.015) samples

Fig.S4 Temperature dependent heat diffusivity of Sn1-yInyTe0.7S0.15Se0.15 (y=0, 0.0025, 0.005, 0.01, and 0.015) samples

Fig.S5 Room temperature Pisarenko plot for Sn1-yInyTe0.7(SeS)0.15 (y=0,0.0025,0.005,0.01,0.015). The solid curve is experted from Zhang[18]

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多掺杂协同调控碲化锡热导率和功率因子提升热电性能

Multi-doping in SnTe: Improvement of Thermoelectric Performance due to Lower Thermal Conductivity and Enhanced Power Factor

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