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Additive engineering for robust interphases to stabilize high-Ni layered structures at ultra-high voltage of 4.8 V

Abstract

Nickel-rich layered cathode materials promise high energy density for next-generation batteries when coupled with lithium metal anodes. However, the practical capacities accessible are far less than the theoretical values due to their structural instability during cycling, especially when charged at high voltages. Here we demonstrate that stable cycling with an ultra-high cut-off voltage of 4.8 V can be realized by using an appropriate amount of lithium difluorophosphate in a common commercial electrolyte. The Li||LiNi0.76Mn0.14Co0.10O2 cell retains 97% of the initial capacity (235 mAh g–1) after 200 cycles. The cycling stability is ascribed to the robust interphase on the cathode. It is formed by lithium difluorophosphate decomposition, which is facilitated by the catalytic effect of transition metals. The decomposition products (Li3PO4 and LiF) form a protective interphase. This suppresses transition metal dissolution and cathode surface reconstruction. It also facilitates uniform Li distribution within the cathode, effectively mitigating the strain and crack formation.

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Fig. 1: Electrochemical performance of Li || NMC76 cells using different electrolytes at ultra-high voltage.
Fig. 2: CEI XPS characterization and LiDFP additive decomposition mechanism.
Fig. 3: HAADF-STEM and soft XAS characterizations for cycled NMC76 cathode.
Fig. 4: Electrode-level quantification of the deposited TM on lithium anode.
Fig. 5: Electrode-level characterization of the chemo-mechanical interaction when using the electrolytes with and without the LiDFP additive.
Fig. 6: X-ray diffraction and tomography analysis of cycled NMC76 cathode.

Data availability

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

Code availability

The source code of the analysis of synchrotron phase contrast nano-tomography cathode data is available at our GitHub repository: https://github.com/YijinLiu-Lab/LIBNet.

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Acknowledgements

S.T., Z.S., X.-Q.Y. and E.H. are 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 Program, including the Battery500 Consortium under contract no. DE-SC0012704. S.T., Z.S., X.-Q.Y. and E.H. also acknowledge the support from the Assistant Secretary for Energy Efficiency and Renewable Energy, Vehicle Technology Office of the US DOE through the Applied Battery Research for Transportation programme under contract no. DE-SC0012704. HAADF-STEM measurements and DFT computational work used the resources of the Center for Functional Nanomaterials, a US DOE Office of Science User Facility at Brookhaven National Laboratory, under contract no. DE-SC0012704. This research used beamlines 5-ID, 7-BM, 23-ID-2 and 28-ID-2 of the NSLS 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. The hard X-ray phase contrast tomography was conducted at the nano-imaging beamline ID16A-NI at the European Synchrotron Radiation Facility, Grenoble, France. A.C. and K.X. thank the Joint Center of Energy Storage Research, an energy hub funded by the US DOE Office of Science, for support. Y.L. and J.L. acknowledge the support from the US DOE Laboratory Directed Research and Development programme at SLAC National Accelerator Laboratory under contract DE-AC02-76SF00515.

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E.H., K.X. and S.T. conceived the idea and designed the experiments. S.T. and Z.S. carried out the electrochemical measurements. S.T., Z.S., E.H., Y.Y., A.H., I.W. and L.M. conducted the synchrotron soft and hard XAS, X-ray diffraction and XRF mapping experiments. J.L., Y.L., F.M. and P.C. carried out the synchrotron tomography experiments and machine-learning-assisted data analysis. X.W. performed the DFT calculation. R.L. carried out the HAADF-STEM experiments. J.H. and J.X. synthesized the cathode materials. A.C. and K.X. carried out the XPS measurement. S.T., Z.S., J.L., Y.L., X.-Q.Y., K.X. and E.H. wrote the manuscript with input from all the authors.

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Correspondence to Yijin Liu, Xiao-Qing Yang, Kang Xu or Enyuan Hu.

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Nature Energy thanks Mérièm Anouti, Shiyou Li and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Supplementary Figs. 1–22, Tables 1 and 2, notes and references.

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Tan, S., Shadike, Z., Li, J. et al. Additive engineering for robust interphases to stabilize high-Ni layered structures at ultra-high voltage of 4.8 V. Nat Energy 7, 484–494 (2022). https://doi.org/10.1038/s41560-022-01020-x

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