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Inhibiting collective cation migration in Li-rich cathode materials as a strategy to mitigate voltage hysteresis

Nature Materials volume 22, pages 353–361 (2023)Cite this article

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Abstract

Lithium-rich cathodes are promising energy storage materials due to their high energy densities. However, voltage hysteresis, which is generally associated with transition metal migration, limits their energy efficiency and implementation in practical devices. Here we reveal that voltage hysteresis is related to the collective migration of metal ions, and that isolating the migration events from each other by creating partial disorder can create high-capacity reversible cathode materials, even when migrating transition metal ions are present. We demonstrate this on a layered Li-rich chromium manganese oxide that in its fully ordered state displays a substantial voltage hysteresis (>2.5 V) associated with collective transition metal migration into Li layers, but can be made to achieve high capacity (>360 mAh g−1) and energy density (>1,100 Wh kg−1) when the collective migration is perturbed by partial disorder. This study demonstrates that partially cation-disordered cathode materials can accommodate a high level of transition metal migration, which broadens our options for redox couples to those of mobile cations.

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Fig. 1: Structure characterization of L-LCMO and PD-LCMO.
Fig. 2: Electrochemistry of LCMO samples at room temperature.
Fig. 3: Redox mechanism and structural change in PD-LCMO.
Fig. 4: Redox mechanism and structural change in L-LCMO.
Fig. 5: Cr migration and tetrahedral dumb-bell formation in layered and disordered structures.
Fig. 6: Proposed reaction mechanisms in L-LCMO and PD-LCMO.

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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 Advanced Battery Materials Research (BMR) Program, of the US Department of Energy (DOE) under contract no. DE-AC02-05CH11231. The XRD and XAS measurements were performed at the Advanced Photon Source at Argonne National Laboratory, which is supported by the US DOE under contract no. DE-AC02-06CH11357. Use of the Stanford Synchrotron Radiation Lightsource, SLAC National Accelerator Laboratory, is supported by the US DOE Office of Science, Office of Basic Energy Sciences under contract no. DE-AC02-76SF00515. This work used resources at the Spallation Neutron Source, a DOE Office of Science User Facility operated by the Oak Ridge National Laboratory. Work at the Molecular Foundry was supported by the Office of Science, Office of Basic Energy Sciences, of the US DOE under contract no. DE-AC02-05CH11231. The computational analysis was performed using computational resources sponsored by the DOE’s Office of Energy Efficiency and Renewable Energy and located at the National Renewable Energy Laboratory, as well as computational resources provided by Extreme Science and Engineering Discovery Environment (XSEDE) supported by National Science Foundation grant number 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 DOE under contract no. DE-AC02-05CH11231. M.B. is supported by the US DOE Office of Energy Efficiency and Renewable Energy (EERE) Vehicle Technologies Office (VTO) under contract no. DE-AC05-00OR22725. We thank H. Kim for assistance with the XAS measurements.

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Author notes

  1. These authors contributed equally: Jianping Huang, Bin Ouyang.

Authors and Affiliations

  1. Materials Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, CA, USA

    Jianping Huang, Bin Ouyang, Yaqian Zhang, Deok-Hwang Kwon, Zijian Cai, Zhengyan Lun & Gerbrand Ceder

  2. Department of Materials Science and Engineering, University of California, Berkeley, CA, USA

    Bin Ouyang, Yaqian Zhang, Deok-Hwang Kwon, Zijian Cai, Zhengyan Lun, Guobo Zeng & Gerbrand Ceder

  3. X-ray Science Division, Advanced Photon Source, Argonne National Laboratory, Argonne, IL, USA

    Liang Yin

  4. Electrification and Energy Infrastructures Division, Oak Ridge National Laboratory, Oak Ridge, TN, USA

    Mahalingam Balasubramanian

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Contributions

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. J.H. also collected and analysed the ex situ XRD and XAS data. B.O. performed and analysed the theoretical calculations. Y.Z. and D.-H.K. performed the TEM characterization. L.Y. performed refinement of XRD and neutron diffraction. Z.C. helped with material characterization. Z.L. helped with the synthesis and electrochemistry. G.Z. performed the SEM characterization. M.B. helped with the XAS data collection and analyses. The manuscript was written by J.H. and G.C. and was revised by the other co-authors. All authors contributed to discussions.

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Correspondence to Gerbrand Ceder.

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Supplementary information

Supplementary Information

Supplementary Notes 1–4, Figs. 1–20, Tables 1–5 and references.

Source data

Source Data Fig. 1

XRD data.

Source Data Fig. 2

Electrochemistry data.

Source Data Fig. 3

XAS data of PD-LCMO.

Source Data Fig. 4

XAS data of L-LCMO.

Source Data Fig. 5

Fitted tetrahedral Cr fractions.

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Huang, J., Ouyang, B., Zhang, Y. et al. Inhibiting collective cation migration in Li-rich cathode materials as a strategy to mitigate voltage hysteresis. Nat. Mater. 22, 353–361 (2023). https://doi.org/10.1038/s41563-022-01467-z

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