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Imaging solid–electrolyte interphase dynamics using operando reflection interference microscopy

Nature Nanotechnology volume 18, pages 780–789 (2023)Cite this article

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Abstract

The quality of the solid–electrolyte interphase is crucial for the performance of most battery chemistries, but its formation dynamics during operation are not well understood due to a lack of reliable operando characterization techniques. Herein, we report a dynamic, non-invasive, operando reflection interference microscope to enable the real-time imaging of the solid–electrolyte interphase during its formation and evolution processes with high sensitivity. The stratified structure of the solid–electrolyte interphase formed during four distinct steps includes the emergence of a permanent inner inorganic layer enriched in LiF, a transient assembly of an interfacial electrified double layer and a consequent emergence of a temporary outer organic-rich layer whose presence is reversible with electrochemical cycling. Reflection interference microscope imaging reveals an inverse correlation between the thicknesses of two interphasial subcomponents, implying that the permanent inorganic-rich inner layer dictates the organic-rich outer layer formation and lithium nucleation. The real-time visualization of solid–electrolyte interphase dynamics provides a powerful tool for the rational design of battery interphases.

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Fig. 1: Operando characterization of SEI formation dynamics using RIM.
Fig. 2: The growth and evolution of the SEI layers.
Fig. 3: XPS analysis of the SEIs.
Fig. 4: Imaging localized SEI formation dynamics using RIM.
Fig. 5: The spatial correlation between the LiF-rich and the organic-rich SEI layers.
Fig. 6: SEI affects the Li nucleation process.

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All the data used to plot the figures are available via zenodo.org.

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Acknowledgements

X.S. acknowledges the funding support from the start-up fund at the University of Houston, the University of Houston’s Center for Carbon Management in Energy, UL Research Institutes, Beyond Bits Technology, the US Department of Agriculture’s Small Business Innovation Research programme (awards no. 2022-70012-36900 and no. 2019-33610-29769) and University Training and Research for Fossil Energy Applications (US Department of Energy DE-FE-0032092). The work performed at Pacific Northwest National Laboratory (PNNL) was supported by the Assistant Secretary for Energy Efficiency and Renewable Energy, and Vehicle Technologies Office of the US Department of Energy through the Advanced Battery Materials Research programme under contract no. DE-AC05-76RL01830. PNNL is operated by Battelle for the US Department of Energy under contract no. DE-AC05-76RL01830. Y.Y. acknowledges the funding support from the US Department of Energy’s Office of Energy Efficiency and Renewable Energy under the Vehicle Technologies Program under contract no. DE-EE0008864. K.X. acknowledges the support from the Joint Center for Energy Storage Research, an energy hub funded by the US Department of Energy’s Basic Energy Sciences programme. X.S. thanks Z. Zhu from PNNL for his insightful discussions of SEI formation, and thanks P. Ruchhoeft for providing the thermal evaporator for the electrode fabrication.

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Author notes

  1. These authors contributed equally: Guangxia Feng, Hao Jia, Yaping Shi.

Authors and Affiliations

  1. Department of Electrical and Computer Engineering, University of Houston, Houston, TX, USA

    Guangxia Feng, Yaping Shi, Xu Yang, Yanliang Liang, Chaojie Yang, Yan Yao & Xiaonan Shan

  2. Energy and Environment Directorate, Pacific Northwest National Laboratory, Richland, WA, USA

    Hao Jia & Wu Xu

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

    Mark H. Engelhard

  4. Materials Science and Engineering Program, University of Houston, Houston, TX, USA

    Ye Zhang & Yan Yao

  5. Battery Science Branch, Energy Science Division, Sensor and Electron Devices Directorate, Army Research Laboratory, Adelphi, MD, USA

    Kang Xu

  6. Texas Center for Superconductivity at the University of Houston, University of Houston, Houston, TX, USA

    Yan Yao

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Contributions

X.S., W.X., Y.Y. and K.X. conceived the idea and designed the research. X.S. supervised the research. G.F. carried out and managed most of the experiments, including performing all the RIM measurements on SEI formation and Li nucleation, characterizing the SEI chemical compositions using XPS and conducting atomic force microscopy and profilometer calibrations. G.F. analysed the data and prepared the figures. H.J. prepared the electrolytes, electrochemical depositions of SEI and Li on Cu foils and samples for XPS depth profiling. Y.S. helped with RIM instrument development and data analysis. M.H.E. performed the XPS depth profiling experiment and provided insight to understand the data. X.Y., Y.Z., Y.L. and C.Y. provided suggestions on the experiments. Y.L. provided insight on understanding the RIM response. X.S., G.F., W.X., Y.Y. and K.X. discussed the data and wrote the manuscript.

Corresponding authors

Correspondence to Kang Xu, Yan Yao, Wu Xu or Xiaonan Shan.

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Competing interests

X.S. has equity interest in Pani Clean, Inc. Y.Y. has equity interest in LiBeyond, LLC and Solid Design Instruments, LLC. Y.L. has equity interest in LiBeyond, LLC. The University of Houston reviewed and approved their relationship in compliance with its conflict-of-interest policy. The remaining authors declare no competing interests.

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Supplementary Information

Supplementary Figs. 1–21, Tables 1 and 2 and Discussion Sections 1–9.

Supplementary Video 1

The formation dynamics of the LiF-rich SEI layer (thickness map) during the CV scanning process in the potential window of 2.2–1.4 V.

Supplementary Video 2

The formation dynamics of the organic-rich SEI layer (thickness map) during the CV scanning process in the potential window of 0.8–0.1 V.

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Feng, G., Jia, H., Shi, Y. et al. Imaging solid–electrolyte interphase dynamics using operando reflection interference microscopy. Nat. Nanotechnol. 18, 780–789 (2023). https://doi.org/10.1038/s41565-023-01316-3

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