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Voltage decay and redox asymmetry mitigation by reversible cation migration in lithium-rich layered oxide electrodes

Abstract

Despite the high energy density of lithium-rich layered-oxide electrodes, their real-world implementation in batteries is hindered by the substantial voltage decay on cycling. This voltage decay is widely accepted to mainly originate from progressive structural rearrangements involving irreversible transition-metal migration. As prevention of this spontaneous cation migration has proven difficult, a paradigm shift toward management of its reversibility is needed. Herein, we demonstrate that the reversibility of the cation migration of lithium-rich nickel manganese oxides can be remarkably improved by altering the oxygen stacking sequences in the layered structure and thereby dramatically reducing the voltage decay. The preeminent intra-cycle reversibility of the cation migration is experimentally visualized, and first-principles calculations reveal that an O2-type structure restricts the movements of transition metals within the Li layer, which effectively streamlines the returning migration path of the transition metals. Furthermore, we propose that the enhanced reversibility mitigates the asymmetry of the anionic redox in conventional lithium-rich electrodes, promoting the high-potential anionic reduction, thereby reducing the subsequent voltage hysteresis. Our findings demonstrate that regulating the reversibility of the cation migration is a practical strategy to reduce voltage decay and hysteresis in lithium-rich layered materials.

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Fig. 1: Comparison of crystal structures and cation migration paths.
Fig. 2: Suppression of voltage decay in O2-LLNMOs.
Fig. 3: Highly reversible cation migration in O2-LLNMOs.
Fig. 4: Mitigation of structural evolution in O2-LLNMOs for 40 cycles.
Fig. 5: Anomalous anionic redox behaviour in O2-LLNMOs.

Data availability

All relevant data within the article are available from the corresponding author on reasonable request. Source data for Figs. 2, 4 and 5 are provided with the paper.

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Acknowledgements

This work was supported by Project Code (grant no. IBS-R006-A2) and the research programme of LG Chem. This research was supported by the National Research Foundation of Korea (NRF) grant funded by the Korea government (MSIP) (no. 2018R1A2A1A05079249), and Creative Materials Discovery Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Science, ICT and Future Planning (NRF-2017M3D1A1039553).

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D.E., B.K. and K.K. designed the project. D.E. carried out the synthesis, structural characterization and electrochemical test and performed synchrotron-based measurements such as XRD, XANES and STXM. B.K. conducted the DFT calculations and analysed the experimental results. S.J.K. performed the HR-TEM measurement and interpreted all TEM data with simulations. H.P. and S.-P.C. conducted the Raman spectroscopy and Cs-STEM analysis, respectively. G.Y. provided the fundamental idea for the DFT calculations. M.H.L. and O.T. acquired the ex situ XRD and scanning electron microscopy data, respectively. S.-K.J. provided constructive advice for the experimental design. J.W. and W.Y. measured and processed the mRIXS data. W.M.S., K.K., S.K.P. and I.H. offered valuable comments for this project. D.E., B.K. and K.K. wrote the manuscript, and K.K supervised all aspects of the research.

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Correspondence to Kisuk Kang.

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Eum, D., Kim, B., Kim, S.J. et al. Voltage decay and redox asymmetry mitigation by reversible cation migration in lithium-rich layered oxide electrodes. Nat. Mater. 19, 419–427 (2020). https://doi.org/10.1038/s41563-019-0572-4

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