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Hard-carbon-stabilized Li–Si anodes for high-performance all-solid-state Li-ion batteries

Nature Energy volume 8, pages 800–813 (2023)Cite this article

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Abstract

All-solid-state batteries (ASSBs) with Li metal anodes or Si anodes are promising candidates to achieve high energy density and improved safety, but they suffer from undesirable lithium dendrite growth or huge volume expansion, respectively. Here we synthesize a hard-carbon-stabilized Li–Si alloy anode in which sintering of Si leads to the transformation of micro-metre particles into dense continuum. A 3D ionic-electronic-conductive network composed of plastically deformable Li-rich phases (Li15Si4 and LiC6) that enlarges active area and relieves stress concentration is created in the anode, leading to improved electrode kinetics and mechanical stability. With the hard-carbon-stabilized Li-Si anode, full cells using LiCoO2 or LiNi0.8Co0.1Mn0.1O2 cathodes and Li6PS5Cl electrolyte achieve favourable rate capability and cycle stability. In particular, the ASSB with LiNi0.8Co0.1Mn0.1O2 at high loading of 5.86 mAh cm−2 delivers 5,000 cycles at 1 C (5.86 mA cm−2), demonstrating the potential of using hard-carbon-stabilized Li–Si alloy anodes for practical applications of ASSBs.

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Fig. 1: Electrochemical performance and cross-section SEM images of Si and Li–Si anodes.
Fig. 2: Hard-carbon-stabilized Li–Si alloy anodes.
Fig. 3: Different carbon adds into LiSi alloy anode.
Fig. 4: High rate capability of full cells with a LiSH46 anode.
Fig. 5: Long-term cycle of full cells with a LiSH46 anode.
Fig. 6: High loading performance of full cells with a LiSH46 anode.
Fig. 7: Characterization of the LiSH46 anode.
Fig. 8: Schematic illustration of mechanisms for Si, LiSi and LiSH46 anodes in ASSBs.

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All data generated and analysed in this study are included in the paper and Supplementary Information. Source data are provided with this paper.

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Acknowledgements

This work is supported by Outstanding Youth Fund Project by the Department of Science and Technology of Jiangsu Province (grant number BK20220045), Key R&D Project funded by Department of Science and Technology of Jiangsu Province (grant number BE2020003), Key Program-Automobile Joint Fund of the National Natural Science Foundation of China (grant number U1964205), General Program of the National Natural Science Foundation of China (grant number 51972334), General Program of National Natural Science Foundation of Beijing (grant number 2202058), cultivation project of leading innovative experts in Changzhou City (CQ20210003), National Overseas High-level Expert Recruitment Program (grant number E1JF021E11), Talent Program of the Chinese Academy of Sciences, ‘Scientist Studio Program Funding’ from Yangtze River Delta Physics Research Center and Tianmu Lake Institute of Advanced Energy Storage Technologies (grant number TIES-SS0001) and Science and Technology Research Institute of China Three Gorges Corporation (grant number 202103402).

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Authors and Affiliations

  1. Tianmu Lake Institute of Advanced Energy Storage Technologies, Liyang, China

    Wenlin Yan, Zhixuan Wang, Dengxu Wu, Pushun Lu, Jiaze Lu, Jieru Xu, Yujing Wu, Tenghuan Ma, Ming Yang, Xiang Zhu, Liquan Chen, Hong Li & Fan Wu

  2. Beijing Advanced Innovation Center for Materials Genome Engineering, Key Laboratory for Renewable Energy, Beijing Key Laboratory for New Energy Materials and Devices, Institute of Physics, Chinese Academy of Sciences, Beijing, China

    Wenlin Yan, Zhixuan Wang, Yuli Huang, Dengxu Wu, Pushun Lu, Jiaze Lu, Jieru Xu, Yujing Wu, Liquan Chen, Hong Li & Fan Wu

  3. College of Materials Science and Opto-Electronic Technology, University of Chinese Academy of Sciences, Beijing, China

    Wenlin Yan, Yuli Huang, Dengxu Wu, Pushun Lu, Jiaze Lu, Jieru Xu, Yujing Wu, Liquan Chen, Hong Li & Fan Wu

  4. ByteDance Research, Beijing, China

    Zhenliang Mu, Yu Xia & Shaochen Shi

  5. Nano Science and Technology Institute, University of Science and Technology of China, Suzhou, China

    Tenghuan Ma, Ming Yang, Xiang Zhu, Liquan Chen, Hong Li & Fan Wu

  6. Yangtze River Delta Physics Research Center, Liyang, China

    Liquan Chen, Hong Li & Fan Wu

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  1. Wenlin Yan
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Contributions

W.Y. and F.W. conceived and designed the experimental work. W.Y. prepared samples and carried out experiments. Z.M., Y.X. and S.S. performed the simulation using phase field simulation. M.Y., T.M. and X.Z. assisted with sample preparation. Y.H. and Y.W. assisted with characterization. W.Y., Z.M. and F.W. wrote the paper. D.W., Y.H. and P.L. helped with visualization. Z.W., J.L., J.X., P.L., F.W., H.L. and L.C. discussed the results and revised or commented on the manuscript. F.W. acquired funding and supervised/managed the whole project.

Corresponding author

Correspondence to Fan Wu.

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Competing interests

Z.M., Y.X. and S.S. are employed by ByteDance Research. The other authors declare no competing interests.

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Nature Energy thanks Felix Hippauf, Dong-Wan Kim and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Supplementary information

Supplementary Information

Supplementary Figs, 1–36, Notes 1–4 and Tables 1–12.

Supplementary Table

The raw data about thicknesses in this article.

Source data

Source Data Fig. 1

Cycle test data and rate test data.

Source Data Fig. 2

Battery test source data and phase field simulation data.

Source Data Fig. 3

Cycle test data, rate test data, XRD source data and surface area source data.

Source Data Fig. 4

Rate test data and comparison data.

Source Data Fig. 5

Cycle test data and comparison data.

Source Data Fig. 6

Charge–discharge test source data, cycle test data, fast discharge test data and comparison data.

Source Data Fig. 7

XRD and XPS data.

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Yan, W., Mu, Z., Wang, Z. et al. Hard-carbon-stabilized Li–Si anodes for high-performance all-solid-state Li-ion batteries. Nat Energy 8, 800–813 (2023). https://doi.org/10.1038/s41560-023-01279-8

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