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Subnano-sized silicon anode via crystal growth inhibition mechanism and its application in a prototype battery pack

Nature Energy volume 6, pages 1164–1175 (2021)Cite this article

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Abstract

Due to the large volume variation of high-capacity alloy-based anodes during cycling, it is desirable to use small anode particles for an extended battery cycle life. However, it is still challenging to realize subnano-sized particles (<1 nm). Here we show a growth inhibition mechanism that prevents continuous enlargement of size immediately after nucleation during chemical vapour deposition. The growth inhibition is successfully applied to the synthesis of silicon, thereby yielding subnano-sized (<1 nm) silicon embedded in a highly stable dual matrix composed of carbon and silicon carbide. Ethylene not only functions as a silicon growth inhibitor, thereby slowing the growth of nucleated silicon via Si–C bond formation, but also acts as a source to create the dual matrix. The subnano-sized silicon anode enhances the cycling stability (Coulombic efficiency reaching 99.96% over 50 cycles). Finally, the practical application of the fabricated energy storage system (103.2 kWh) containing 110 Ah full-cells with 91% capacity retention for 2,875 cycles and a calendar life of 97.6% for 1 year is demonstrated.

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Fig. 1: Simulation regarding the behaviour of Si growth inhibitor.
Fig. 2: Investigating the growth of subnano-sized Si through MD.
Fig. 3: Chemical characterization of composition and bonding in CSi layer.
Fig. 4: Investigation of crystallite size in CSi layer.
Fig. 5: Electrochemical characterization of various anodes.
Fig. 6: Behaviour of Si and LixSi in the CSi layer during cycles.
Fig. 7: Practical application of subnano-sized Si.

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Data generated and analysed in this study are included in the article and its Supplementary Information.

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Acknowledgements

This work was supported by the Korea Institute of Energy Technology Evaluation and Planning and the Ministry of Trade, Industry and Energy of the Republic of Korea (no. 20172410100140). This research was also supported by the Basic Science Research Program through the National Research Foundation of Korea, funded by the Ministry of Education (2019R1A6A3A13095900). Fabrication of the 1 Ah and 110 Ah cells was supported by K. Kim and Samsung SDI.

Author information

Author notes

  1. Jaekyung Sung & Moonsu Yoon

    Present address: Department of Nuclear Science and Engineering, Massachusetts Institute of Technology, Cambridge, MA, USA

  2. Namhyung Kim

    Present address: Energy & Environment Directorate, Pacific Northwest National Laboratory (PNNL), Richland, WA, USA

  3. These authors contributed equally: Jaekyung Sung, Namhyung Kim.

Authors and Affiliations

  1. Department of Energy Engineering, School of Energy and Chemical Engineering, Ulsan National Institute of Science and Technology (UNIST), Ulsan, Republic of Korea

    Jaekyung Sung, Namhyung Kim, Jeong Hyeon Lee, Se Hun Joo, Taeyong Lee, Moonsu Yoon, Sang Kyu Kwak & Jaephil Cho

  2. Gwangju Bio/Energy R&D Center, Korea Institute of Energy Research (KIER), Gwangju, Republic of Korea

    Jiyoung Ma

  3. Department of Industrial Chemistry, Pukyong National University, Busan, Republic of Korea

    Sujong Chae

  4. Advanced Battery Development Team, Hyundai Motor Company, Hwaseong, Republic of Korea

    Yoonkwang Lee & Jaeseong Hwang

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Contributions

J.S., J.M. and N.K. conceived and designed the experiments. J.S., J.M. and N.K. prepared the samples and carried out the main experiments. J.H.L., S.H.J. and S.K.K. performed the simulation using MD and DFT. S.C. conducted dilatometry. M.Y. and J.H. participated in electrochemical measurements. T.L. and Y.L. assisted with sample preparation. J.S., N.K. and J.H.L. wrote the paper. J.C., N.K. and S.K.K. discussed the results and revised or commented on the manuscript.

Corresponding authors

Correspondence to Sang Kyu Kwak or Jaephil Cho.

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Competing interests

The authors have patents (J.C., J.S. and J.M., Patent Cooperation Treaty patent publication no. WO/2020/036397, published 20 February 2020. J.C., J.S. and J.M., Korean patent application no. 1021312620000, registered 1 July 2020. J.C., J.S. and J.M., Korean patent application no. 1022130820000, registered 1 February 2021. J.C. and J.S., Korean patent application no. 1021596930000, registered 18 September 2020.) related to the processes described in this article.

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Peer review information Nature Energy thanks Taylor Garrick and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Supplementary Information

Supplementary Figs. 1–34, Notes 1–5, Tables 1–7 and references.

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Sung, J., Kim, N., Ma, J. et al. Subnano-sized silicon anode via crystal growth inhibition mechanism and its application in a prototype battery pack. Nat Energy 6, 1164–1175 (2021). https://doi.org/10.1038/s41560-021-00945-z

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