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Origin and regulation of oxygen redox instability in high-voltage battery cathodes

Abstract

Oxygen redox at high voltage has emerged as a transformative paradigm for high-energy battery cathodes such as layered transition-metal oxides by offering extra capacity beyond conventional transition-metal redox. However, these cathodes suffer from voltage hysteresis, voltage fade and capacity drop upon cycling. Single-crystalline cathodes have recently shown some improvements, but these challenges remain. Here we reveal the fundamental origin of oxygen redox instability to be from the domain boundaries that are present in single-crystalline cathode particles. By investigating single-crystalline cathodes with different domain boundaries structures, we show that the elimination of domain boundaries enhances the reversible lattice oxygen redox while inhibiting the irreversible oxygen release. This leads to significantly suppressed structural degradation and improved mechanical integrity during battery cycling and abuse heating. The robust oxygen redox enabled through domain boundary control provides practical opportunities towards high-energy, long-cycling, safe batteries.

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Fig. 1: Structural characterization of pristine cathodes.
Fig. 2: Electrochemical performance of the investigated cathodes.
Fig. 3: O K-edge mRIXS characterization during cycling.
Fig. 4: In situ synchrotron X-ray characterizations of cathodes.
Fig. 5: Correlation between boundary structures and OR.

Data availability

The data supporting the findings of this study are available within the article and its Supplementary Information files.

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Acknowledgements

Research at the Argonne National Laboratory was funded by the US Department of Energy (DOE), Vehicle Technologies Office. Support from Tien Duong of the US DOE’s Office of Vehicle Technologies Program is gratefully acknowledged. Use of the Advanced Photon Source (APS) and the Centre for Nanoscale Materials, both Office of Science user facilities, was supported by the US Department of Energy, Office of Science and Office of Basic Energy Sciences, under contract no. DE-AC02-06CH11357. Soft X-ray spectroscopy experiments were performed at the Advanced Light Source of the Lawrence Berkeley National Laboratory, a U.S. DOE Office of Science User Facility under contract no. DE-AC02-05CH11231. X.L., G.-L.X., M.O. and K.A. thank the Clean Vehicle Consortium, US–China Clean Energy Research Centre (CERC-CVC2) for support. The authors thank G. Ceder for helpful discussion of DFT simulation on the OR behaviour of boundary-tailored layered cathodes, and B. Lai for technical support with ptychography characterization.

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Contributions

G.-L.X. and X.L. conceived the idea and designed the experiments. G.-L.X., M.O. and K.A. initiated and supervised the project. X.L. synthesized and obtained all the battery materials. X.L. and C.Z. carried out the electrochemical tests. X.L., L.Y., A.D., Y.R. and Z.C. carried out in situ and ex situ XRD measurements and analysis. X.L. conducted the in situ heating HEXRD and mass spectroscopy with the assistance of W.X. Q.L., Z.Z. and W.Y. conducted the RIXS characterization and analysis on the samples prepared by X.L. and C.Z. W.L conducted synchrotron X-ray Laue diffraction characterization and analysis. X.Z., Y.L. and T.Z. performed the SEM and transmission electron microscopy characterization and analysis. D.R. and X.L. performed the ARC testing. X.L. and X.F. carried out the TGA-MS testing with different temperature rates. X.L., I.H. and C.S. performed the XAS measurement and analysis. J.D. performed X-ray ptychography characterization and analysis with the help of M.D. J.-J.F. conducted the DEMS under the supervision of L.H. and S.-G.S. V.S.C.K. and M.K.Y.C. performed DFT calculations. G.-L.X., X.L. and W.Y. wrote the manuscript with input from all authors.

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Correspondence to Gui-Liang Xu, Wanli Yang, Minggao Ouyang or Khalil Amine.

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Nature Energy thanks Jin Xie and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Liu, X., Xu, GL., Kolluru, V.S.C. et al. Origin and regulation of oxygen redox instability in high-voltage battery cathodes. Nat Energy 7, 808–817 (2022). https://doi.org/10.1038/s41560-022-01036-3

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