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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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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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).
The authors declare no competing interests.
Peer review information Nature Nanotechnology thanks Peter Ercius and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.
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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.
Cryo-STEM-EDS tomography showing 3D structure and elemental distribution of a Si nanowire after the first cycle.
Cryo-STEM-EDS tomography showing cross-sectional information of a Si nanowire after the first cycle.
Cryo-STEM-EDS tomography showing 3D structure and elemental distribution of a Si nanowire after the 36th cycle.
Cryo-STEM-EDS tomography showing cross-sectional information of a Si nanowire after the 36th cycle.
Cryo-STEM-EDS tomography showing 3D structure and elemental distribution of a Si nanowire after the 100th cycle.
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