Polymer–inorganic solid–electrolyte interphase for stable lithium metal batteries under lean electrolyte conditions

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Abstract

The solid–electrolyte interphase (SEI) is pivotal in stabilizing lithium metal anodes for rechargeable batteries. However, the SEI is constantly reforming and consuming electrolyte with cycling. The rational design of a stable SEI is plagued by the failure to control its structure and stability. Here we report a molecular-level SEI design using a reactive polymer composite, which effectively suppresses electrolyte consumption in the formation and maintenance of the SEI. The SEI layer consists of a polymeric lithium salt, lithium fluoride nanoparticles and graphene oxide sheets, as evidenced by cryo-transmission electron microscopy, atomic force microscopy and surface-sensitive spectroscopies. This structure is different from that of a conventional electrolyte-derived SEI and has excellent passivation properties, homogeneity and mechanical strength. The use of the polymer–inorganic SEI enables high-efficiency Li deposition and stable cycling of 4 V Li|LiNi0.5Co0.2Mn0.3O2 cells under lean electrolyte, limited Li excess and high capacity conditions. The same approach was also applied to design stable SEI layers for sodium and zinc anodes.

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Fig. 1: Illustration of the molecular-level design of a polymer–inorganic SEI using a reactive polymer composite.
Fig. 2: SEI chemistry ruled by the RPC rather than the electrolyte.
Fig. 3: Polymer–inorganic composite structure of the RPC-derived SEI.
Fig. 4: Interfacial stability of RPC-stabilized Li anodes.
Fig. 5: Electrochemical performance of Li|NCM 523 batteries under lean electrolyte conditions.

Data availability

The datasets generated during and/or analysed during the current study are available from the corresponding author on reasonable 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, through the Advanced Battery Materials Research (BMR) Program (Battery500 Consortium) award no. DE-EE0008198. Z.Y., Y.C.L. and T.E.M. acknowledge support from the National Science Foundation under grant DMR-1807116. X.H. and S.H.K. acknowledge support from the National Science Foundation under grant CMMI-1435766.

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Y.G., T.E.M. and Do.W. conceived the idea, Y.G. and Do.W. designed the experiments, and Do.W. directed the project. Y.G. performed the material preparation and chemical and morphological characterization. Z.Y. prepared the graphene oxide materials. H.W. prepared the samples for cryo-TEM experiments. J.L.G. performed the cryo-TEM experiments. Y.G. and T.C. performed the battery tests. X.H. conducted the AFM indentation test. Y.G. and Y.C.L. performed the electrochemical impedance spectroscopy test. Y.G. and Da.W. conducted the SEM test. All authors discussed and analysed the data. Y.G., S.H.K, T.E.M. and Do.W. wrote the manuscript.

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Correspondence to Donghai Wang.

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Supplementary Figures 1–42, Supplementary Table 1, Supplementary References 1–9

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Gao, Y., Yan, Z., Gray, J.L. et al. Polymer–inorganic solid–electrolyte interphase for stable lithium metal batteries under lean electrolyte conditions. Nat. Mater. 18, 384–389 (2019). https://doi.org/10.1038/s41563-019-0305-8

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