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Unravelling the convoluted and dynamic interphasial mechanisms on Li metal anodes

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Abstract

Accurate understanding of the chemistry of solid-electrolyte interphase (SEI) is key to developing new electrolytes for high-energy batteries using lithium metal (Li0) anodes1. SEI is generally believed to be formed by the reactions between Li0 and electrolyte2,3. However, our new study shows this is not the whole story. Through synchrotron-based X-ray diffraction and pair distribution function analysis, we reveal a much more convoluted formation mechanism of SEI, which receives considerable contributions from electrolyte, cathode, moisture and native surface species on Li0, with highly dynamic nature during cycling. Using isotope labelling, we traced the origin of LiH to electrolyte solvent, moisture and a new source: the native surface species (LiOH) on pristine Li0. When lithium accessibility is very limited as in the case of anode-free cells, LiOH develops into plate-shaped large crystals during cycling. Alternatively, when the lithium source is abundant, as in the case of Li||NMC811 cells, LiOH reacts with Li0 to form LiH and Li2O. While the desired anion-derived LiF-rich SEI is typically found in the concentrated electrolytes or their derivatives, we found it can also be formed in low-concentration electrolyte via the crosstalk effect, emphasizing the importance of formation cycle protocol and opening up opportunities for low-cost electrolyte development.

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Fig. 1: Characterization method illustration and its advantages.
Fig. 2: Investigation of hydrogen source for LiH.
Fig. 3: Cathode to anode crosstalk and formation cycle protocol optimization.
Fig. 4: Evolution pathways of LiOH.

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Data availability

The data that support the findings of this study are available within the paper and its Supplementary Information. Any other data are available from the corresponding author on request.

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Acknowledgements

S.T., A.C., P.K., X.-Q.Y. and E.H. at BNL are supported by the Assistant Secretary for Energy Efficiency and Renewable Energy (EERE), Vehicle Technology Office (VTO) of the US Department of Energy (DOE) through the Advanced Battery Materials Research (BMR) Program, including Battery500 Consortium under contract no. DE-SC0012704. This research used 28-ID-2 and 7-BM beamlines of the National Synchrotron Light Source II, US DOE Office of Science User Facilities operated for the DOE Office of Science by BNL under contract no. DE-SC0012704. DFT computational work used the resources of the Center for Functional Nanomaterials, a US DOE Office of Science User Facility at BNL, under contract no. DE-SC0012704. J-M.K., J.X., J.L. and X.C. at Pacific Northwest National Laboratory (PNNL) also thank support from EERE and VTO of the US DOE through the BMR program including Battery500 Consortium. The XPS were conducted in the William R. Wiley Environmental Molecular Sciences Laboratory (EMSL), a national scientific user facility sponsored by DOE’s Office of Biological and Environmental Research and located at PNNL. PNNL is operated by Battelle for US DOE under contract DE-AC05-76RL01830. The electrodes used in this study were produced at the US DOE’s CAMP (Cell Analysis, Modelling and Prototyping) Facility, Argonne National Laboratory. The CAMP Facility is fully supported by VTO, EERE of US DOE. K.X. thanks the financial aid from Joint Center of Energy Storage Research, an Energy Hub funded by US DOE, Office of Basic Energy Science.

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Authors and Affiliations

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

    Sha Tan, Ning Rui, Xuelong Wang, Sanjaya Senanayake, Peter Khalifah, Xiao-Qing Yang & Enyuan Hu

  2. Department of Chemistry, Stony Brook University, Stony Brook, NY, USA

    Sha Tan, Adam Corrao & Peter Khalifah

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

    Ju-Myung Kim, Jie Xiao, Jun Liu & Xia Cao

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

    Sanjit Ghose

  5. Department of Joint Photon Sciences Institute, Stony Brook University, Stony Brook, NY, USA

    Hui Zhong

  6. Chemical Sciences and Engineering Division, Argonne National Laboratory, Argonne, IL, USA

    Bryant J. Polzin

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

    Jie Xiao & Jun Liu

  8. Battery Science Branch, Energy Science Division, Sensors and Electron Devices Directorate, US Army Research Laboratory, Adelphi, MD, USA

    Kang Xu

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  1. Sha Tan
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Contributions

S.T., X.C. and E.H. conceived the idea and designed the experiments. B.J.P. provided NMC811 electrodes. S.T. and J.-M.K. carried out electrochemical measurements and prepared interphase samples. S.G. and H.Z. carried out the synchrotron experiments. J.-M.K., N.R., S.S. and X.C. performed the XPS measurements. X.W. did the DFT calculation. S.T., A.C., P.K. and E.H. analysed the XRD and PDF results. S.T., K.X. and E.H. wrote the manuscript with input from all the authors.

Corresponding authors

Correspondence to Xia Cao or Enyuan Hu.

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Nature Nanotechnology thanks Yong Yang, Xiqian Yu and Guanglei Cui for their contribution to the peer review of this work.

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Supplementary Information

Supplementary Figs. 1–14, Tables 1 and 2 and Note.

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Tan, S., Kim, JM., Corrao, A. et al. Unravelling the convoluted and dynamic interphasial mechanisms on Li metal anodes. Nat. Nanotechnol. 18, 243–249 (2023). https://doi.org/10.1038/s41565-022-01273-3

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