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Non-topotactic reactions enable high rate capability in Li-rich cathode materials

Abstract

High-rate cathode materials for Li-ion batteries require fast Li transport kinetics, which typically rely on topotactic Li intercalation/de-intercalation because it minimally disrupts Li transport pathways. In contrast to this conventional view, here we demonstrate that the rate capability in a Li-rich cation-disordered rocksalt cathode can be significantly improved when the topotactic reaction is replaced by a non-topotactic reaction. The fast non-topotactic lithiation reaction is enabled by facile and reversible transition metal octahedral-to-tetrahedral migration, which improves rather than impedes Li transport. Using this concept, we show that high-rate performance can be achieved in Mn- and Ni-based cation-disordered rocksalt materials when some of the transition metal content can reversibly switch between octahedral and tetrahedral sites. This study provides a new perspective on the design of high-performance cathode materials by demonstrating how the interplay between Li and transition metal migration in materials can be conducive to fast non-topotactic Li intercalation/de-intercalations.

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Fig. 1: Structural characterization of Li1.2Mn0.4−xTi0.4CrxO2.
Fig. 2: Electrochemistry of Li1.2Mn0.4−xTi0.4CrxO2 at room temperature.
Fig. 3: Redox mechanism and structural change of Li1.2Mn0.4−xTi0.4CrxO2.
Fig. 4: Effect of TM migration on Li kinetics.
Fig. 5: Structural characterization and electrochemistry of Li1.2Ni0.2−xTi0.6−xCr2xO2.

Data availability

All data generated and analysed during this study are included in the published article and its Supplementary Information. Source data are provided with this paper.

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Acknowledgements

This work was supported by the Assistant Secretary for Energy Efficiency and Renewable Energy, Vehicle Technologies Office, under the Applied Battery Materials Program of the US Department of Energy under contract no. DE-AC02-05CH11231. The XAS measurements were performed at the Advanced Photon Source at Argonne National Laboratory, which is supported by the US Department of Energy under contract no. DE-AC02-06CH11357. Work at the Advanced Light Source was supported by the US DOE Office of Science User Facility under contract no. DE-AC02-05CH11231. Work at the Molecular Foundry was supported by the Office of Science, Office of Basic Energy Sciences, of the US Department of Energy under contract no. DE-AC02-05CH11231. The computational analysis was performed using computational resources sponsored by the US Department of Energy’s Office of Energy Efficiency and Renewable Energy and located at the National Renewable Energy Laboratory, as well as computational resources provided by the Extreme Science and Engineering Discovery Environment (XSEDE), supported by National Science Foundation grant no. ACI1053575, and the National Energy Research Scientific Computing Center (NERSC), a DOE Office of Science User Facility supported by the Office of Science and the US Department of Energy under contract no. DE-AC02-05CH11231. We thank H. Kim and Z. Lun for assistance with the XAS measurements.

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J.H. and G.C. planned the project. G.C. supervised all aspects of the research. J.H. synthesized, characterized and electrochemically tested the proposed materials. With help from M.B., J.H. also analysed the ex situ XAS data. P.Z. performed the theoretical calculations and analysed the results. D.-H.K. performed the TEM characterization. Y.H. collected and analysed the RIXS data with W.Y. With input from B.D.M., M.J.C. collected and analysed the DEMS data. Y.T. performed the SEM characterization. The manuscript was written by J.H. and G.C. and was revised by the other co-authors. All the authors contributed to discussions.

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Correspondence to Gerbrand Ceder.

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Peer review information Nature Energy thanks Naoaki Yabuuchi, Yujie Zhu and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Supplementary information

Supplementary Information

Supplementary Figs. 1–19, Tables 1 and 2, Notes 1–6 and references.

Source data

Source Data Fig. 1

XRD data.

Source Data Fig. 2

Electrochemical performance.

Source Data Fig. 3

XAS at Mn and Cr K-edge.

Source Data Fig. 5

XRD, electrochemistry, XAS and RIXS of LNTO and LNTC02O.

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Huang, J., Zhong, P., Ha, Y. et al. Non-topotactic reactions enable high rate capability in Li-rich cathode materials. Nat Energy 6, 706–714 (2021). https://doi.org/10.1038/s41560-021-00817-6

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