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Identification of LiH and nanocrystalline LiF in the solid–electrolyte interphase of lithium metal anodes

Nature Nanotechnology volume 16, pages 549–554 (2021)Cite this article

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Abstract

A comprehensive understanding of the solid–electrolyte interphase (SEI) composition is crucial to developing high-energy batteries based on lithium metal anodes. A particularly contentious issue concerns the presence of LiH in the SEI. Here we report on the use of synchrotron-based X-ray diffraction and pair distribution function analysis to identify and differentiate two elusive components, LiH and LiF, in the SEI of lithium metal anodes. LiH is identified as a component of the SEI in high abundance, and the possibility of its misidentification as LiF in the literature is discussed. LiF in the SEI is found to have different structural features from LiF in the bulk phase, including a larger lattice parameter and a smaller grain size (<3 nm). These characteristics favour Li+ transport and explain why an ionic insulator, like LiF, has been found to be a favoured component for the SEI. Finally, pair distribution function analysis reveals key amorphous components in the SEI.

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Fig. 1: Characterization of the interphase by XRD.
Fig. 2: Air-exposure experiment of the interphase sample.
Fig. 3: Analysis of amorphous components and relative quantification of crystalline components in the interphase.

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All relevant data in the article are available from the corresponding author upon reasonable request.

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Acknowledgements

The work done at Brookhaven National Laboratory was supported by the Assistant Secretary for Energy Efficiency and Renewable Energy, Vehicle Technology Office of the US Department of Energy (DOE) through the Advanced Battery Materials Research (BMR) Program, including Battery500 Consortium under contract no. DE-SC0012704. The work done at Pacific Northwest National Laboratory was supported by the Assistant Secretary for Energy Efficiency and Renewable Energy, Office of Vehicle Technologies of the US DOE through the Advanced Battery Materials Research (BMR) Program (Battery500 Consortium) under contract no. DE-AC02-05CH11231. The work at the Army Research Laboratory was performed under JCESR, an Energy Research Hub funded by Basic Energy Sciences, US DOE. This research used beamline 28-ID-2 of the National Synchrotron Light Source II, a US DOE Office of Science user facility operated for the DOE Office of Science by Brookhaven National Laboratory under contract no. DE-SC0012704.

Author information

Author notes

  1. Hongkyung Lee

    Present address: Department of Energy Science and Engineering, Daegu Gyeongbuk Institute of Science and Technology (DGIST), Daegu, Republic of Korea

Authors and Affiliations

  1. Chemistry Division, Brookhaven National Laboratory, Upton, NY, USA

    Zulipiya Shadike, Xuelong Wang, Ruoqian Lin, Seong-Min Bak, Xiao-Qing Yang & Enyuan Hu

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

    Hongkyung Lee, Xia Cao, Jun Liu & Jie Xiao

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

    Oleg Borodin & Kang Xu

  4. Department of Chemical and Biomolecular Engineering, University of Maryland, College Park, MD, USA

    Xiulin Fan & Chunsheng Wang

  5. National Synchrotron Light Source II, Brookhaven National Laboratory, Upton, NY, USA

    Sanjit Ghose

  6. Department of Materials Science and Engineering, University of Washington, Seattle, WA, USA

    Jun Liu & Jie Xiao

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  1. Zulipiya Shadike
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Contributions

J.X., E.H. and X.-Q.Y. proposed the research. J.X., J.L. and X.-Q.Y. organized and guided scientific discussions. H.L. and X.C. performed electrochemical characterization and SEI sample preparation. Z.S., X.W., O.B., S.G., C.W., X.F., S.-M.B., R.L. and E. H. performed XRD and PDF measurements and carried out the analysis. Z.S., J.X., E.H., K.X. and X.-Q.Y. prepared the manuscript with critical input from all other authors.

Corresponding authors

Correspondence to Jie Xiao, Xiao-Qing Yang or Enyuan Hu.

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

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Supplementary Figs. 1–5, Tables 1–14, note and refs. 1 and 2.

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Shadike, Z., Lee, H., Borodin, O. et al. Identification of LiH and nanocrystalline LiF in the solid–electrolyte interphase of lithium metal anodes. Nat. Nanotechnol. 16, 549–554 (2021). https://doi.org/10.1038/s41565-020-00845-5

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