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Anisotropic lithium-ion migration and electro-chemo-mechanical coupling in Sb2Se3 single crystals

Sb2Se3单晶中的各向异性锂离子迁移和电化学-力学 耦合

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Abstract

Harvesting the promising high energy density of advanced electrode materials in lithium-ion batteries is critically dependent on a mechanistic understanding on how the materials function and degrade along with the battery cycling. Here, we tracked phase transformations during (de)lithiation of Sb2Se3 single crystals using in situ high-resolution transmission electron microscopy (HRTEM) technique, and revealed electro-chemo-mechanical evolution at the reaction interface. The effect of this electro-chemo-mechanical coupling has a complicated interplay on the lithiation kinetics and causes various types of defects at the reaction front, including dislocation dipoles, antiphase boundaries, and cracks. In return, the formed cracks and related defects build a path for fast diffusion of lithium ions and trigger a highly anisotropic lithiation at the twisted reaction front, giving rise to the formation of presumably “dead” Sb2Se3 nanodomains in amorphous LixSb2Se3. The detailed mechanistic understanding may facilitate the rational design of high-capacity electrode materials for battery applications.

摘要

高能量密度的锂离子电池先进电极材料的开发, 依赖于对材料 在电池循环中的运行和失效机制的理解. 本文使用原位高分辨TEM技 术跟踪了Sb2Se3单晶锂化/脱锂过程中的相变, 并揭示了反应界面处的 电化学-力学耦合. 这种电化学-力学耦合效应对锂化动力学具有复杂 的相互作用, 并在反应前端引起各种类型的缺陷, 包括位错对、反相边 界和裂纹. 另一方面, 形成的裂缝和相关缺陷为锂离子的快速扩散开辟 了道路, 并在扭曲的反应前沿引发高度各向异性的锂化, 从而在无定形 LixSb2Se3中形成可能“失效”的Sb2Se3畴. 我们对Sb2Se3电化学过程机理的 详细研究有助于更合理地设计和制备高容量电极材料.

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Acknowledgements

The work was supported by the National Key R&D Program of China (2018YFB1304902), the National Natural Science Foundation of China (11904372, U1813211, and 12004034), Beijing Institute of Technology Research Fund Program for Young Scholars, Beijing Institute of Technology Laboratory Research Project (2019BITSYA03), and China Postdoctoral Science Foundation Funded Project (2021M690386).

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Authors and Affiliations

  1. School of Environmental and Safety Engineering, North University of China, Taiyuan, 030051, China

    Chunhao Sun  (孙春浩) & Tiansheng Liu  (刘天生)

  2. Beijing Advanced Innovation Center for Intelligent Robots and Systems, School of Medical Technology, Beijing Institute of Technology, Beijing, 100081, China

    Weikang Dong  (董伟康), Xintao Zuo  (左鑫涛), Ran Cai  (蔡然) & Ruiwen Shao  (邵瑞文)

  3. Beijing Key Laboratory of Lightweight Multi-Functional Composite Materials and Structures, Institute of Advanced Structure Technology, Beijing Institute of Technology, Beijing, 100081, China

    Le Yang  (杨乐) & Haosen Chen  (陈浩森)

  4. Analysis & Testing Center, Beijing Institute of Technology, Beijing, 100081, China

    Lixia Bao  (暴丽霞), Ze Hua  (华泽) & Xiaoxue Chang  (常晓雪)

  5. Beijing Key Laboratory of Microstructure and Property of Advanced Materials, Beijing University of Technology, Beijing, 100124, China

    Xiaodong Han  (韩晓东)

  6. Beijing Advanced Innovation Center for Materials Genome Engineering, School of Materials Science and Engineering, University of Science and Technology Beijing, Beijing, 100083, China

    Yang He  (何洋)

  7. Department of Biomedical Engineering, City University of Hong Kong, Hong Kong, China

    Lixin Dong  (董立新)

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  1. Chunhao Sun  (孙春浩)
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  3. Le Yang  (杨乐)
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  4. Xintao Zuo  (左鑫涛)
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  6. Ze Hua  (华泽)
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Contributions

Shao R and Dong L conceived the idea; Sun C and Hua Z prepared the TEM sample; Zuo X, Bao L, and Chang X conducted the characterization of materials. Yang L and Chen H conceived the finite-element analysis; Liu T, He Y, and Han X wrote the paper. All authors contributed to the general discussion.

Corresponding authors

Correspondence to Yang He  (何洋), Tiansheng Liu  (刘天生), Ruiwen Shao  (邵瑞文) or Lixin Dong  (董立新).

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Conflict of interest

The authors declare that they have no conflict of interest.

Supplementary information

Supporting data are available in the online version of the paper.

Chunhao Sun received his BS degree from the North University of China in 2019 and he is now a master’s student at the North University of China. His current research focuses on solid-state ionics, and the structure and properties of crystal defects and interfaces by in-situ TEM.

Ruiwen Shao is an assistant professor at the School of Medical Technology, Beijing Institute of Technology, Beijing, China. He received his PhD degree in condensed mater physics from the Institute of Microstructure and Properties of Advanced Materials, Beijing University of Technology in 2016. He was a postdoctor at the School of Physics, Peking University (2016–2018), and research associate at the Technical Institute of Physics and Chemistry (2018–2019). He joined Beijing Institute of Technology in 2019. His research interests include electron microscopy, solid-state ionics, and structure and properties of crystal defects and interfaces.

Tiansheng Liu is a second-level professor of the North University of China (Department of Chemical Engineering and Special Energy). He won the second and third National Invention Awards, and was a visiting scholar of Haven National Laboratory, New York, USA. His main research interests are high-temperature and high-pressure condensed matter physics and chemical reactions and new materials and application engineering.

Yang He is a professor at the School of Materials Science and Engineering, University of Science and Technology Beijing, China. He received his PhD degree from the Department of Mechanical Engineering, University of Pittsburgh in 2018. He was a postdoctor in Pacific Northwest National Laboratory from 2018 to 2019. His research interests mainly focus on exploring the structure-activity relationship of materials by in-situ TEM method and their potential applications in metal structural materials, second batteries, catalysis, etc.

Lixin Dong received his PhD degree from Nagoya University in 2003. Between 2003 and 2004, he was an assistant professor at Nagoya University, and between 2004 and 2008, he held a Senior Research Scientist at ETH Zurich. Prior to joining the City University of Hong Kong as a professor, he had been an associate professor at Michigan State University by 2019. His current interests include micro-/nanorobotics and enabling technologies for mechatronic, fluidic, photonic, and biomedical systems.

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Sun, C., Dong, W., Yang, L. et al. Anisotropic lithium-ion migration and electro-chemo-mechanical coupling in Sb2Se3 single crystals. Sci. China Mater. 65, 2657–2664 (2022). https://doi.org/10.1007/s40843-022-2051-3

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