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Extremely low thermal conductivity from bismuth selenohalides with 1D soft crystal structure

具有超低热导率的一维铋硒卤族化合物

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Abstract

Materials with intrinsically low thermal conductivity are of fundamental interests. Here we report a new sort of simple one-dimensional (1D) crystal structured bismuth selenohalides (BiSeX, X = Br, I) with extremely low thermal conductivity of ∼0.27 W m−1 K−1 at 573 K. The mechanism of the extremely low thermal conductivity in 1D BiSeX is elucidated systematically using the first-principles calculations, neutron powder-diffraction measurements and temperature tunable aberration-corrected scanning transmission electron microscopy (STEM). Results reveal that the 1D structure of BiSeX possesses unique soft bonding character, low phonon velocity, strong anharmonicity of both acoustic and optical phonon modes, and large off-center displacement of Bi and halogen atoms. Cooperatively, all these features contribute to the minimal phonon transport. These findings provide a novel selection rule to search low thermal conductivity materials with potential applications in thermoelectrics and thermal barrier coatings.

摘要

本征低热导率材料的研究具有重要的科学意义, 已引起广泛关注. 本工作报道了一类具有简单一维晶体结构的超低热导率材料: 铋硒卤族化合物(BiSeX, X = Br, I). 研究发现, BiSeI的热导率在573 K仅为∼0.27 W m−1 K−1, 达到了最低本征热导率的理论极限值. 本研究采用第一性原理计算结合粉末中子衍射和变温球差扫描透射电子显微镜表征, 深入探究了其超低热导率的机制. 研究表明, BiSeX的一维结构赋予了材料低热导特性: 弱的成键特性、 低的声子速度、 声学支和光学支的强非简谐性以及Bi和卤族元素较大的偏移效应, 从而有效阻碍了声子输运, 使得BiSeX具有超低的热导率. 本研究提出了在具有一维结构的材料中寻找低传导特性的新思路, 该研究思路在热电材料和热障涂层材料等低热传导需求领域中具有广阔的应用前景.

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Acknowledgements

We appreciate the help from Prof. Shubin Yang and Dr. Yongzheng Shi for ionic conductivity measurement. This work was supported by the National Key Research and Development Program of China (2018YFA0702100 and 2018YFB0703600), the National Natural Science Foundation of China (51772012 and 51632005), Shenzhen Peacock Plan team (KQTD2016022619565991), Beijing Natural Science Foundation (JQ18004), China Postdoctoral Science Foundation Grant (2019M650429), 111 Project (B17002) and the National Science Foundation for Distinguished Young Scholars (51925101). Wu H acknowledges the financial support from Singapore Ministry of Education Tier 1 grant (R-284-000-212-114) for Lee Kuan Yew Postdoctoral Fellowship. Wang G is grateful to the High Performance Computing Center of Henan Normal University. Wang D thanks the high performance computing (HPC) resources at Beihang University.

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Author notes

  1. These authors contributed equally to this work.

Authors and Affiliations

  1. School of Materials Science and Engineering, Beihang University, Beijing, 100191, China

    Dongyang Wang  (王东洋), Zhiwei Huang  (黄志伟) & Li-Dong Zhao  (赵立东)

  2. State Key Laboratory for Mechanical Behavior of Materials, Xi’an Jiaotong University, Xi’an, 710049, China

    Haijun Wu  (武海军)

  3. Instrumental Analysis Center of Xi’an Jiaotong University, Xi’an Jiaotong University, Xi’an, 710049, China

    Yang Zhang  (张杨)

  4. Department of Materials Science and Engineering, National University of Singapore, Singapore, 117575, Singapore

    Yang Zhang  (张杨), Stephen J. Pennycook & Haijun Wu  (武海军)

  5. Department of Nuclear Physics, Neutron Scattering Laboratory, China Institute of Atomic Energy, Beijing, 102413, China

    Lijie Hao  (郝丽杰) & Hongliang Wang  (王洪亮)

  6. School of Physics, Henan Normal University, Xinxiang, 453007, China

    Guangtao Wang  (王广涛)

  7. Spallation Neutron Source Science Center, Dongguan, 523803, China

    Sihao Deng  (邓司浩) & Lunhua He  (何伦华)

  8. Beijing National Laboratory for Condensed Matter Physics, Institute of Physics, Chinese Academy of Sciences, Beijing, 100190, China

    Lunhua He  (何伦华)

  9. Songshan Lake Materials Laboratory, Dongguan, 523808, China

    Jie Chen  (陈洁) & Lunhua He  (何伦华)

  10. State Key Laboratory of Solidification Processing, Northwestern Polytechnical University, Xi’an, 710072, China

    Bao Xiao  (肖宝) & Yadong Xu  (徐亚东)

Authors
  1. Dongyang Wang  (王东洋)
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  2. Zhiwei Huang  (黄志伟)
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  3. Yang Zhang  (张杨)
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  4. Lijie Hao  (郝丽杰)
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  5. Guangtao Wang  (王广涛)
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  6. Sihao Deng  (邓司浩)
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  7. Hongliang Wang  (王洪亮)
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  8. Jie Chen  (陈洁)
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  9. Lunhua He  (何伦华)
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  10. Bao Xiao  (肖宝)
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  11. Yadong Xu  (徐亚东)
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  12. Stephen J. Pennycook
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  13. Haijun Wu  (武海军)
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  14. Li-Dong Zhao  (赵立东)
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Contributions

Author contributions Wang D and Zhao LD initiated the work, analyzed the results, and wrote the paper. Wang D and Wang G performed the DFT calculations. Huang Z and Zhao LD synthesized the samples and carried out the thermal and electrical properties measurements. Zhang Y, Wang H and Pennycook SJ carried out the STEM measurements. He L, Wang H, Deng S, Chen J and He L carried out the high temperature neutron powder-diffraction (NPD) measurements and Rietveld refinements. All authors conceived the experiments, analyzed the results, and coedited the manuscript.

Corresponding authors

Correspondence to Haijun Wu  (武海军) or Li-Dong Zhao  (赵立东).

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

Additional information

Dongyang Wang obtained his BSc and MSc degrees in physics from Henan Normal University, China in 2014 and 2017, respectively. He obtained his PhD degree in materials science from Beihang University in 2020. His current research focuses on the exploration and design of low thermal conductivity materials.

Zhiwei Huang has been a post-doctoral fellow in Prof. Li-Dong Zhao’s group at Beihang University since 2018. He got the BE degree in applied chemistry from Jilin University and PhD degree in physical chemistry from Dalian Institute of Chemical Physics, Chinese Academy of Sciences in 2018. His research interests are metal chalcogenides-based thermoelectric materials.

Haijun Wu is a Lee Kuan Yew Postdoctoral fellow at the Department of Materials Science and Engineering, National University of Singapore (NUS), Singapore. He obtained his BSc and MSc degrees from Xi’an Jiaotong University, China in 2009 and 2012, respectively. He obtained his PhD degree from NUS in 2019. His research interests are STEM and EELS, and structure-property correlation in energy materials, e.g., thermoelectrics, piezoelectrics/ferroelectrics, and functional oxide interfaces.

Li-Dong Zhao is a full professor of materials science and engineering at Beihang University, China. He received his PhD degree from the University of Science and Technology Beijing, China, in 2009. He was a postdoctoral research associate at the Université Paris-Sud and Northwestern University from 2009 to 2014. His research interests include electrical and thermal transport behaviors in the compounds with layered structures. Group website: http://shi.buaa.edu.cn/zhaolidong/zh_CN/index.htm

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Wang, D., Huang, Z., Zhang, Y. et al. Extremely low thermal conductivity from bismuth selenohalides with 1D soft crystal structure. Sci. China Mater. 63, 1759–1768 (2020). https://doi.org/10.1007/s40843-020-1407-x

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