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Progressive growth of the solid–electrolyte interphase towards the Si anode interior causes capacity fading

Nature Nanotechnology volume 16, pages 1113–1120 (2021)Cite this article

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Abstract

The solid–electrolyte interphase (SEI), a layer formed on the electrode surface, is essential for electrochemical reactions in batteries and critically governs the battery stability. Active materials, especially those with extremely high energy density, such as silicon (Si), often inevitably undergo a large volume swing upon ion insertion and extraction, raising a critical question as to how the SEI interactively responds to and evolves with the material and consequently controls the cycling stability of the battery. Here, by integrating sensitive elemental tomography, an advanced algorithm and cryogenic scanning transmission electron microscopy, we unveil, in three dimensions, a correlated structural and chemical evolution of Si and SEI. Corroborated with a chemomechanical model, we demonstrate progressive electrolyte permeation and SEI growth along the percolation channel of the nanovoids due to vacancy injection and condensation during the delithiation process. Consequently, the Si–SEI spatial configuration evolves from the classic ‘core–shell’ structure in the first few cycles to a ‘plum-pudding’ structure following extended cycling, featuring the engulfing of Si domains by the SEI, which leads to the disruption of electron conduction pathways and formation of dead Si, contributing to capacity loss. The spatially coupled interactive evolution model of SEI and active materials, in principle, applies to a broad class of high-capacity electrode materials, leading to a critical insight for remedying the fading of high-capacity electrodes.

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Fig. 1: Experimental set-up, battery performance and structural evolution of Si.
Fig. 2: Cryo-STEM-HAADF image and EDS elemental composition mapping to illustrate the structural and chemical evolution of Si and the SEI upon cycling.
Fig. 3: Cryo-STEM-EDS tomography on 3D structure and elemental distribution of the Si–SEI composite after 36 cycles.
Fig. 4: Segmented viewing of 3D cryo-STEM-EDS chemical composition from two directions to illustrate the spatially correlated evolution of the Si and SEI layer with battery cycles.
Fig. 5: Microstructure-based modelling of the SEI inward growth during lithiation/delithiation cycles.

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Data availability

All data that support the findings of this study have been included in the main text, Supplementary Information and Supplementary Videos 1–6. The original data are kept at the Environmental Molecular Sciences Laboratory at Pacific Northwest National Laboratory and are available from the corresponding authors upon request.

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Acknowledgements

This work was supported by the Assistant Secretary for Energy Efficiency and Renewable Energy, Office of Vehicle Technologies of the US Department of Energy. This work was performed partly at the William R. Wiley Environmental Molecular Sciences Laboratory, a national scientific user facility sponsored by the US Department of Energy, Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory. Pacific Northwest National Laboratory is operated by Battelle for the US Department of Energy under contract DE-AC05-76RL01830. The cryo-STEM-EDS tomography was performed at the Hillsboro Nanoport of Thermo Fisher Scientific. We thank R. Warren for his assistance on the tomography data processing. This work was also performed, in part, at the Center for Integrated Nanotechnologies, an Office of Science User Facility operated for the US Department of Energy, Office of Science. S.Z. acknowledges support by the National Science Foundation (CBET-2034899).

Author information

Author notes

  1. Yang He

    Present address: Beijing University of Science and Technology, Beijing, China

  2. These authors contributed equally: Yang He, Lin Jiang, Tianwu Chen, Yaobin Xu, Haiping Jia, Ran Yi.

Authors and Affiliations

  1. Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory, Richland, WA, USA

    Yang He, Yaobin Xu & Chongmin Wang

  2. Materials and Structural Analysis Division, Thermo Fisher Scientific, Hillsboro, OR, USA

    Lin Jiang, Arda Genc, Cedric Bouchet-Marquis, Lee Pullan & Ted Tessner

  3. Department of Engineering Science and Mechanics, Pennsylvania State University, University Park, PA, USA

    Tianwu Chen, Dingchuan Xue & Sulin Zhang

  4. Energy and Environmental Directorate, Pacific Northwest National Laboratory, Richland, WA, USA

    Haiping Jia, Ran Yi, Xiaolin Li & Ji-Guang Zhang

  5. Physical and Computational Science Directorate, Pacific Northwest National Laboratory, Richland, WA, USA

    Miao Song

  6. Center for Integrated Nanotechnologies, Los Alamos National Laboratory, Los Alamos, NM, USA

    Jinkyoung Yoo

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Contributions

C.W., J.-G.Z. and X.L. conceived the project. Y.H. and X.L. designed the experiment. J.Y. synthesized the Si nanowire on the stainless-steel anode. H.J. and R.Y. assembled and cycled the coin cells. Y.H. and Y.X. performed the cryo-TEM experiments. Y.H., L.J., A.G., and C.B.-M. conducted the cryo-STEM-EDS tomography experiments under the supervision of L.P. and T.T.; L.J. and M.S. conducted the tomography data reconstruction and visualization. T.C., D.X. and S.Z. carried out the modelling calculation. Y.H., L.J., C.W. and S.Z. draughted the manuscript. All authors contributed to the revision of the manuscript.

Corresponding authors

Correspondence to Jinkyoung Yoo, Xiaolin Li, Sulin Zhang or Chongmin Wang.

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The authors declare no competing interests.

Additional information

Peer review information Nature Nanotechnology thanks Peter Ercius and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

Publisher’s note Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Supplementary information

Supplementary Information

Supplementary Figs. 1–37, Table 1, Discussion, evaluation of electron beam effect and optimization of imaging conditions, additional information about the background and signal intensity, and reference.

Supplementary Video 1

Cryo-STEM-EDS tomography showing 3D structure and elemental distribution of a Si nanowire after the first cycle.

Supplementary Video 2

Cryo-STEM-EDS tomography showing cross-sectional information of a Si nanowire after the first cycle.

Supplementary Video 3

Cryo-STEM-EDS tomography showing 3D structure and elemental distribution of a Si nanowire after the 36th cycle.

Supplementary Video 4

Cryo-STEM-EDS tomography showing cross-sectional information of a Si nanowire after the 36th cycle.

Supplementary Video 5

Cryo-STEM-EDS tomography showing 3D structure and elemental distribution of a Si nanowire after the 100th cycle.

Supplementary Video 6

Cryo-STEM-EDS tomography showing cross-sectional information of a Si nanowire after the 100th cycle.

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He, Y., Jiang, L., Chen, T. et al. Progressive growth of the solid–electrolyte interphase towards the Si anode interior causes capacity fading. Nat. Nanotechnol. 16, 1113–1120 (2021). https://doi.org/10.1038/s41565-021-00947-8

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