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Ultra-high-voltage Ni-rich layered cathodes in practical Li metal batteries enabled by a sulfonamide-based electrolyte

Abstract

By increasing the charging voltage, a cell specific energy of >400 W h kg−1 is achievable with LiNi0.8Mn0.1Co0.1O2 in Li metal batteries. However, stable cycling of high-nickel cathodes at ultra-high voltages is extremely challenging. Here we report that a rationally designed sulfonamide-based electrolyte enables stable cycling of commercial LiNi0.8Co0.1Mn0.1O2 with a cut-off voltage up to 4.7 V in Li metal batteries. In contrast to commercial carbonate electrolytes, the electrolyte not only suppresses side reactions, stress-corrosion cracking, transition-metal dissolution and impedance growth on the cathode side, but also enables highly reversible Li metal stripping and plating leading to a compact morphology and low pulverization. Our lithium-metal battery delivers a specific capacity >230 mA h g−1 and an average Coulombic efficiency >99.65% over 100 cycles. Even under harsh testing conditions, the 4.7 V lithium-metal battery can retain >88% capacity for 90 cycles, advancing practical lithium-metal batteries.

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Fig. 1: Challenges for durable high-voltage Li || NMC811 cells.
Fig. 2: Electrochemical performances of Li || NMC811 cells using different electrolytes.
Fig. 3: Characterizations of cathode–electrolyte side reactions and CEIs at 4.7 V cut-off voltage.
Fig. 4: Structural characterizations of the cycled NMC811 cathodes with different electrolytes.
Fig. 5: Proposed stress-corrosion cracking (SCC) mechanism for polycrystalline cathodes and its suppression by limiting reaction-product solubilities in the liquid electrolyte.
Fig. 6: Electrochemical performance and characterizations of the LMA in different electrolytes.
Fig. 7: Electrochemical performance of Li || NMC811 cells under practical conditions.

Data availability

The datasets analysed and generated during the current study are included in the paper and its Supplementary Information.

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Acknowledgements

We acknowledge support by the Department of Energy, Basic Energy Sciences, under award number DE-SC0002633 (Chemomechanics of Far-From-Equilibrium Interfaces). We acknowledge the cathodes provided by the US Department of Energy CAMP Facility, Argonne National Laboratory, and the LiFSI salt by KISCO. This work made use of the Material Research Science and Engineering Center Shared Experimental Facilities supported by the National Science Foundation under award number DMR-1419807. Z.S. acknowledges the research grant at the Department of Materials Science and Engineering at the Massachusetts Institute of Technology. This work used resources of the beamline FXI/18ID of the National Synchrotron Light Source II, a US Department of Energy Office of Science User Facility operated for the Department of Energy Office of Science by Brookhaven National Laboratory under contract no. DE-SC0012704. This work used resources of the Advanced Photon Source, an Office of Science User Facility operated for the US Department of Energy Office of Science by Argonne National Laboratory, and was supported by the US Department of Energy under contract no. DE-AC02-06CH11357 and the Canadian Light Source and its funding partners. J. Lopez acknowledges support by an appointment to the Intelligence Community Postdoctoral Research Fellowship Program at the Massachusetts Institute of Technology, administered by Oak Ridge Institute for Science and Education through an interagency agreement between the US Department of Energy and the Office of the Director of National Intelligence. We also thank C. Mao at Zhu Hai Smooth Way Company for valuable suggestions and G. Leverick from Y. Shao-Horn’s group at the Massachusetts Institute of Technology for the support in measuring the water content by Karl Fisher titration.

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W.X., Y.D., J.A.J., Y.S.-H. and J. Li conceived the concept and the project. M.H., W.Z. and S.L. synthesized the solvent. W.X. designed the electrolyte and conducted electrochemical measurements. Y.L. conducted TOF-SIMS measurements and analysed the results. Y.G.Z. conducted in situ DEMS measurements. R.G. conducted focused ion beam and TEM analysis. W.X., X.X., D.Y., Z.S., C-J.S., I.H. and W.-K.L. conducted in situ synchrotron-based FXI measurements and analysed the results. P.L. conducted ICP-MS measurements. W.X., G.X., J. Lopez, W.F. and R.X. conducted other characterizations. W.X., Y.D., Y.Y., Y.S.-H, J.A.J. and J. Li wrote and revised the manuscript. All authors discussed the results and reviewed the manuscript.

Corresponding authors

Correspondence to Yanhao Dong or Yang Shao-Horn or Jeremiah A. Johnson or Ju Li.

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Supplementary Information

Supplementary Figs. 1–23, Tables 1–6, note and references.

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Xue, W., Huang, M., Li, Y. et al. Ultra-high-voltage Ni-rich layered cathodes in practical Li metal batteries enabled by a sulfonamide-based electrolyte. Nat Energy 6, 495–505 (2021). https://doi.org/10.1038/s41560-021-00792-y

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