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Nanostructuring and band engineering boosting thermoelectric performance of Bi-Sb-Te alloys via CsBr doping

纳米结构和能带工程提高Bi-Sb-Te合金的热电性能

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Abstract

Bismuth telluride has become a widely commercially utilized thermoelectric material due to its exceptional properties. However, there remains space for further improvement in the properties of p-type Bi-Sb-Te thermoelectric materials obtained through the melting method. In this work, CsBr was employed to enhance the thermoelectric properties of Bi0.42Sb1.58Te3 (BST) materials. The bulk materials of BST + x wt% CsBr (x = 0, 0.10, 0.20, 0.30) were fabricated using a combination of melting method and spark plasma sintering. Cs and Br co-doping could significantly increase the electrical conductivity of BST alloy, while reducing thermal conductivity, resulting in a maximum figure of merit (ZT) value of 1.2 at 323 K and an average ZT value of 1.1 below 400 K for x = 0.20 sample. Density functional theory and transmission electron microscopy analyses reveal that Cs doping effectively reduces the band gap, increases the density of states near the Fermi level, and flattens the energy band, resulting in the great enhancement of electrical transport properties (with a maximum power factor of approximately 3500 µ−1 K−2). Furthermore, Cs doping causes Sb to dissociate from the lattice and combine with free oxygen to form nanoscale Sb2O3, which efficiently scatters mid-frequency phonons and reduces thermal conductivity while maintaining a high Seebeck coefficient. This study presents a novel approach to resolving the trade-off between electrical and thermal conductivity in thermoelectric materials by solely utilizing CsBr doping.

摘要

碲化铋由于其优异的性能, 已成为商业上广泛使用的热电材料. 然而, 通过熔化方法获得的p型Bi-Sb-Te热电材料的性能仍有进一步改进的空间. 在这项工作中, CsBr化合物被用来提高Bi0.42Sb1.58Te3 (BST) 材料的热电性能. 采用熔化法和放电等离子体烧结相结合的方法制备了BST + x wt%CsBr (x = 0, 0.10, 0.20, 0.30)的块状材料. Cs和Br共掺杂可以显著提高BST合金的电导率, 同时降低其热导率, 使其在323 K下的最大ZT值为1.2. 对于x = 0.20的样品, 在400 K以下具有1.1的平均ZT. 密度泛函理论和透射电子显微镜分析表明, Cs掺杂有效地减小了带隙, 增加了费米能级附近的态密度, 并使能带变平缓, 从而使电输运特性得到了明显增强(最大功率因子接近3500 μW mK−2). 此外, Cs掺杂可以使得Sb从晶格中脱离出来并与晶格中的游离氧结合形成纳米级Sb2O3, 使其能够有效地散射中频声子并降低热导率, 同时保持相对较高的塞贝克系数. 这项研究提出了一种新的方法, 可以仅单独通过CsBr掺杂来解决热电材料中电导率和热导率之间的矛盾.

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Acknowledgements

This work was supported by the National Natural Science Foundation of China (52162029), Yunnan Provincial Natural Science Key Fund (202101AS070015), the National Key R&D Program of China (2022YFF0503804), and the Outstanding Youth Fund of Yunnan Province (202201AV070005).

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  1. These authors contributed equally to this work.

Authors and Affiliations

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

    Yu Wang  (王宇), Xing Yang  (杨星), Jing Feng  (冯晶) & Zhen-Hua Ge  (葛振华)

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  1. Yu Wang  (王宇)
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  2. Xing Yang  (杨星)
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  3. Jing Feng  (冯晶)
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Contributions

Author contributions Wang Y designed and engineered the samples; Wang Y and Yang X performed the experiments and wrote the paper with support from Feng J and Ge ZH. All authors contributed to the general discussion.

Corresponding author

Correspondence to Zhen-Hua Ge  (葛振华).

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Conflict of interest The authors declare that they have no conflict of interest.

Additional information

Yu Wang received his Bachelor’s degree from Kunming University of Science and Technology in 2019 and Master’s degree from Sichuan University in 2022. Now, he is a PhD candidate at Kunming University of Science and Technology under the supervisor of Prof. Zhen-Hua Ge. His research interest focuses on the thermoelectric properties of p-type Bi-Sb-Te alloys and DFT.

Xing Yang received his Bachelor’s degree from Kunming University of Science and Technology in 2019. Now, he is a PhD candidate at Kunming University of Science and Technology under the supervisor of Prof. Zhen-Hua Ge. His research interest focuses on the thermoelectric properties of SnSe and Bi-Sb-Te alloys.

Jing Feng is a full professor in materials science and engineering at Kunming University of Science and Technology. He worked on his BS and PhD degrees from Faculty of Materials Science and Engineering, Kunming University of Science and Technology, and School of Materials Science and Engineering, Tsinghua University, respectively. His research interests are engineering materials at high temperatures, the structure-property relationship, and design of advanced materials.

Zhen-Hua Ge is a full professor at Kunming University of Science and Technology. He received his PhD degree in 2013 from the University of Science and Technology Beijing, China. He worked as a post-doctoral researcher at the University of South Florida and Southern University of Science and Technology from February 2013 to July 2015. His research interests focus on the synthesis and property improvements of thermoelectric materials.

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Wang, Y., Yang, X., Feng, J. et al. Nanostructuring and band engineering boosting thermoelectric performance of Bi-Sb-Te alloys via CsBr doping. Sci. China Mater. 66, 3991–4000 (2023). https://doi.org/10.1007/s40843-023-2531-1

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