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Synergistically enhanced thermoelectric properties of Bi2S3 bulk materials via Cu interstitial doping and BiCl3 alloying

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Abstract

Bi2S3 is composed of inexpensive and environmental friendliness elements, which has received extensive interests and been investigated as a promising mid-temperature thermoelectric material for years. Even pure Bi2S3 possesses a high Seebeck coefficient and low thermal conductivity, its low electrical conductivity leads to a low figure of merit (ZT) value. In this work, Bi2S3 fabricated by solid-state melting combined with spark plasma sintering can significantly enhance the thermoelectric performance via introducing small amounts of Cu and BiCl3. Cu interstitial doping and Cl substitution on S site result in a large increase in electrical conductivity. Additionally, the enhanced phonon scattering is derived from the point defects caused by element doping, the grain boundaries, and the small amount of secondary phase, which leads to the low thermal conductivity. Finally, a high ZT value of 0.7 is obtained at 773 K and reaches a large average ZT of 0.36 in the temperature range from room temperature (RT) to 773 K for the Cu-interstitial-doped and BiCl3-alloyed (Cu0.01Bi2S3 + 0.175 mol% BiCl3) sample. Furthermore, the mechanical properties of the Cu0.01Bi2S3 + 0.175 mol% BiCl3 sample are lower than those of other Bi2S3 samples, which stem from the weak chemical bonding strength.

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摘要

硫化铋是一种价格低廉, 环境友好的材料, 近年来作为一种有前景的中温热电材料受到了广泛的关注和研究。尽管纯的硫化铋具有高的塞贝克系数和低的导热系数, 但其低的电导率导致了其低的ZT值。在本工作中, 利用少量的Cu掺杂和BiCl3合金化, 通过固态熔融结合放电等离子体烧结制备的硫化铋可以显著提高其热电性能. Cu的间隙掺杂和Cl在S位上的取代导致了电导率的大幅度提高。此外, 元素掺杂、晶界和少量二次相导致的点状缺陷导致声子散射增强, 从而导致热导率低。最后, 在773 K时获得了较高的ZT值为0.7, 在RT ~ 773 K的温度范围内, Cu掺杂复合BiCl3合金(Cu0.01Bi2S3 + 0.175 mol% BiCl3)样品的ZT平均值为0.36。此外, Cu0.01Bi2S3 + 0.175 mol% BiCl3样品的力学性能低于其他硫化铋样品, 这是由于化学结合强度较弱所致。

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Acknowledgements

This work was financially supported by the National Natural Science Foundation of China (No. 11764025), the Academician (Expert) Workstation of Yunnan Province Program (No. 202005AF150010), and Yunnan Provincial Natural Science Key Fund (No. 202101AS070015).

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Authors and Affiliations

  1. Faculty of Materials Science and Engineering, Kunming University of Science and Technology, Kunming, 650093, China

    Jun Guo, Zi-Yuan Wang, Yu-Ke Zhu, Lin Chen, Jing Feng & Zhen-Hua Ge

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  1. Jun Guo
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  2. Zi-Yuan Wang
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  4. Lin Chen
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Correspondence to Zhen-Hua Ge.

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Guo, J., Wang, ZY., Zhu, YK. et al. Synergistically enhanced thermoelectric properties of Bi2S3 bulk materials via Cu interstitial doping and BiCl3 alloying. Rare Met. 41, 931–941 (2022). https://doi.org/10.1007/s12598-021-01848-4

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