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Stable cycling of high-voltage lithium metal batteries in ether electrolytes

Abstract

The key to enabling long-term cycling stability of high-voltage lithium (Li) metal batteries is the development of functional electrolytes that are stable against both Li anodes and high-voltage (above 4 V versus Li/Li+) cathodes. Due to their limited oxidative stability ( <4 V), ethers have so far been excluded from being used in high-voltage batteries, in spite of their superior reductive stability against Li metal compared to conventional carbonate electrolytes. Here, we design a concentrated dual-salt/ether electrolyte that induces the formation of stable interfacial layers on both a high-voltage LiNi1/3Mn1/3Co1/3O2 cathode and the Li metal anode, thus realizing a capacity retention of >90% over 300 cycles and ~80% over 500 cycles with a charge cut-off voltage of 4.3 V. This study offers a promising approach to enable ether-based electrolytes for high-voltage Li metal battery applications.

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Fig. 1: Electrochemical behaviour of different ether electrolytes in Li||NMC batteries and on the Pt electrode.
Fig. 2: Characterization of the CEI components on cycled NMC electrodes by XPS.
Fig. 3: TEM characterization of NMC cathodes.
Fig. 4: SEM characterization of the cycled Li anodes.
Fig. 5: XPS characterization of the SEI components on cycled Li anodes.

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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 (DOE) through the Advanced Battery Materials Research (BMR) program (Battery500 Consortium) under contract no. DE-AC02-05CH11231. The SEM, EDX, XRD, XPS and computational calculations were conducted in the William R. Wiley Environmental Molecular Sciences Laboratory (EMSL), a national scientific user facility sponsored by the DOE’s Office of Biological and Environmental Research and located at PNNL. PNNL is operated by Battelle for the DOE under Contract DE-AC05-76RLO1830. The LiDFOB salt was produced at the US DOE Materials Engineering Research Facility (MERF) and provided by K. Z. Pupek and T. L. Dzwiniel of ANL. The NMC442 electrode was made by the Cell Analysis, Modelling, and Prototyping (CAMP) Facility and provided by B. J. Polzin of ANL. The MERF and CAMP Facilities are fully supported by the DOE Vehicle Technologies Program within the core funding of the Applied Battery Research (ABR) for Transportation Program. This work was performed, in part, at the Center for Nanoscale Materials, a US Department of Energy Office of Science User Facility, and supported by the US Department of Energy, Office of Science, under contract no. DE-AC02-06CH11357.

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W.X. and J.-G.Z. proposed the research. W.X., S.J., X.R. and R.C. designed the experiments. S.J. and X.R. contributed equally to this work. S.J. and X.R. performed the electrochemical measurements with assistance from R.C. X.R., R.C. and J.Z. conducted the SEM and EDX observations. M.H.E. performed XPS measurements. Y.L. conducted TEM characterizations. D.H. performed IR measurements. W.Z. helped with XRD analysis. R.C. and J.-G.Z. participated in data analyses and discussion. D.M. and N.L. performed molecular dynamics calculations. Q.L. prepared the NMC electrodes. B.D.A. helped with the Li CE calculation with 50 μm Li foil. C.M. analysed the TEM results. S.J., X.R. and W.X. prepared this manuscript with inputs from all other co-authors.

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Correspondence to Ji-Guang Zhang or Wu Xu.

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Supplementary Figures 1–21, Supplementary Tables 1–4, Supplementary References

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Jiao, S., Ren, X., Cao, R. et al. Stable cycling of high-voltage lithium metal batteries in ether electrolytes. Nat Energy 3, 739–746 (2018). https://doi.org/10.1038/s41560-018-0199-8

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