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Enhanced performance of Si-based Li-ion batteries through elastic cushioning with hollow graphene shells

石墨烯空心球的弹性缓冲效应助力高性能硅基锂离子电池

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Abstract

Silicon (Si) is a promising anode material for next-generation Li-ion batteries. The nanometer-sized Si could alleviate the pulverization caused by large volume changes during deep cycling. However, compression between agglomerated Si particles causes Si cracking and electrode failure. Considering this, we engineered a mechanical cushioning space between Si particles via elastic hollow graphene shells (GSs) to flexibly buffer volume changes and maintain the stability of the electrode structure. The stress generated from the Si volume expansion during lithiation was mechanically buffered and gently released by compression of the hollow space of the GS. In this Si/GS composite electrode, GS also reduced the local agglomeration of Si particles and effectively improved the overall conductivity. Considering these advantages, the designed Si/GS electrode showed an enhanced cycling performance with more than 1200 mA h g−1 at 0.8 A g−1 and an excellent rate capability of 1025 mA h g−1 at 4 A g−1 after 200 cycles.

摘要

硅被认为是下一代锂离子电池极具潜力的负极材料. 纳米硅的使用缓解了其在锂化时因体积变化引起的颗粒粉碎化. 然而, 团聚的硅颗粒间的相互挤压仍然会引起硅负极的迅速失效. 为此, 我们以弹性的石墨烯空心球为媒介在硅粒子之间引入机械缓冲空间, 来灵活缓冲硅的体积变化, 保持电极结构的稳定性. 在锂化过程中, 硅体积膨胀产生的应力通过压缩石墨烯空心球的内部空心得到了机械式的缓冲. 除此之外, 石墨烯空心球还减少了硅颗粒的局部团聚, 有效地提高了整体电导率. 基于这些优势, 所设计的Si/GS电极在0.8 A g−1的电流密度下循环 200圈后性能仍维持在1200 mA h g−1以上; 在4 A g−1的电流密度下, 200次循环后仍可达到1025 mA h g−1.

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Acknowledgements

This work was supported by the National Natural Science Foundation of China (52071225, 52172240, 51702225 and 51672181), Czech Republic through the ERDF “Institute of Environmental Technology-Excellent Research” grant (CZ.02.1.01/0.0/0.0/16_019/0008533), the Sino-German Research Institute for their support (Project GZ 1400), the Fundamental Research Funds for the Central Universities (20720200075), Beijing Municipal Science and Technology Commission (Z161100002116020), and the Natural Science Foundation of Jiangsu Province (BK20170336).

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  1. These authors contributed equally to this work.

Authors and Affiliations

  1. Soochow Institute for Energy and Materials Innovation, College of Energy, Key Laboratory of Advanced Carbon Materials and Wearable Energy Technologies of Jiangsu Province, Soochow University, Suzhou, 215006, China

    Qitao Shi  (施启涛), Haiming Wang  (王海明), Xueyu Lian  (连雪玉), Junhua Zhou  (周军华), Lingli Guo  (郭伶俐), Jingyu Sun  (孙靖宇) & Mark H. Rümmeli

  2. State Key Lab of Physical Chemistry of Solid Surfaces, College of Materials, Xiamen University, Xiamen, 361005, China

    Weibin Ye  (叶伟彬) & Ming-Sheng Wang  (王鸣生)

  3. Centre of Polymer and Carbon Materials, Polish Academy of Sciences, M. Curie-Sklodowskiej 34, Zabrze, 41-819, Poland

    Klaudia Kurtyka, Barbara Trzebicka & Mark H. Rümmeli

  4. Institute for Complex Materials, IFW Dresden, Dresden, 01069, Germany

    Huy Quang Ta

  5. School of Energy and Power Engineering, Xi’an Jiaotong University, Xi’an, 710049, China

    Xiaoqin Yang  (杨晓琴), Lijun Liu  (刘立军) & Mark H. Rümmeli

  6. Institute of Environmental Technology, VSB-Technical University of Ostrava, 17. Listopadu 15, Ostrava, 708 33, Czech Republic

    Mark H. Rümmeli

Authors
  1. Qitao Shi  (施启涛)
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Contributions

Author contributions Shi Q and Ye W performed the experiments and co-wrote the paper. Kurtyka K, Wang H, Lia X and Ta HQ helped analyze the data and reviewed the paper. Rümmeli MH conceived and supervised the study. All authors contributed to the general discussion.

Corresponding authors

Correspondence to Ming-Sheng Wang  (王鸣生) or Mark H. Rümmeli.

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

Additional information

Supplementary information Experimental details and supporting data are available in the online version of the paper.

Qitao Shi received his bachelor of science degree from the Department of Physics and Optoelectronic Energy, Soo-chow University, in 2016. He is currently working as a doctoral researcher at Soochow Institute for Energy and Materials Innovations (SIEMIS) and College of Energy, Soochow University in Prof. Mark H. Rümmeli’s group. His current research focuses on solving the pulverization issues of Si particles used as anode materials via space engineering or structure optimization.

Ming-Sheng Wang is currently a Minjiang Scholar Chair professor at Xiamen University, and he leads the Advanced Electron Microscopy group at the College of Materials. He received his bachelor’s degree in physics from Nanjing University (2001) and PhD degree in physical electronics from Peking University (2006) in China. He did his postdoctoral research at the National Institute for Materials Science (NIMS) in Japan and Massachusetts Institute of Technology (MIT) from 2008 to 2012. His research interests concentrate on the in-situ electron microscopy, TEM-based precise nanomanufacturing, and the design and characterization of high-performance energy storage devices based on low-dimensional material architectures. Group website: http://mswang.xmu.edu.cn.

Mark H. Rümmeli headed the Electron Microscopy and LIN laboratories at SIEMIS, Soochow University, where he is a full professor. He is also the director of the characterization center of the College of Energy and SIEMES. He obtained his PhD degree from London Metropolitan University and worked as a postdoc at German Aerospace Center. His research focuses on the growth mechanisms of 2D nanostructures and their functionalization.

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Shi, Q., Ye, W., Kurtyka, K. et al. Enhanced performance of Si-based Li-ion batteries through elastic cushioning with hollow graphene shells. Sci. China Mater. 65, 2343–2353 (2022). https://doi.org/10.1007/s40843-021-2031-8

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