Heuristic solution for achieving long-term cycle stability for Ni-rich layered cathodes at full depth of discharge

Abstract

The demand for energy sources with high energy densities continues to push the limits of Ni-rich layered oxides, which are currently the most promising cathode materials in automobile batteries. Although most current research is focused on extending battery life using Ni-rich layered cathodes, long-term cycling stability using a full cell is yet to be demonstrated. Here, we introduce Li[Ni0.90Co0.09Ta0.01]O2, which exhibits 90% capacity retention after 2,000 cycles at full depth of discharge (DOD) and a cathode energy density >850 Wh kg−1. In contrast, the currently most sought-after Li[Ni0.90Co0.09Al0.01]O2 cathode loses ~40% of its initial capacity within 500 cycles at full DOD. Cycling stability is achieved by radially aligned primary particles with [003] crystallographic texture that effectively dissipate the internal strain occurring in the deeply charged state, while the substitution of Ni3+ with higher valence ions induces ordered occupation of Ni ions in the Li slab and stabilizes the delithiated structure.

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Fig. 1: Correlation between primary particle morphology and electrochemical performance.
Fig. 2: Morphology and orientation of primary particles as a function of the dopant and calcination temperature.
Fig. 3: Li/TM ordered structure observed in the NCTa90 cathode lithiated at 730 °C.
Fig. 4: Twin defect structure observed in the NCTa90 cathode lithiated at 730 °C.
Fig. 5: Electrochemical performances of NCA90 and NCTa90 cathodes lithiated at different temperatures.
Fig. 6: Structural and mechanical stability of NCTa90 cathode verified by structure characterization.
Fig. 7: Mechanisms that enable superior cycling stability of NCTa90 cathode in comparison with other metal-doped NC cathodes.

Data availability

All the data generated or analysed during this study are included in this published article and its Supplementary Information files. The data that support the plots within this paper and other findings of this study are available from the corresponding author upon reasonable request.

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Acknowledgements

This work was supported by a National Research Foundation of Korea (NRF) grant funded by the Korea government Ministry of Education and Science Technology (MEST) (no. NRF-2018R1A2B3008794). Additionally, this work was also supported by the Human Resources Development program (no. 20184010201720) of the Korea Institute of Energy Technology Evaluation and Planning funded by the Ministry of Trade, Industry and Energy of the Korean government. J.L. thanks the University of Washington for supporting his effort on this manuscript.

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U.-H.K. and Y.-K.S. conceived and designed the research. U.-H.K., G.-T.P., B.-K.S. and G.W.N. performed the experiments and characterization of materials. U.-H.K., C.S.Y. and Y.-K.S. analysed the data. L.-Y.K. and P.K. performed the theoretical calculations. U.-H.K., C.S.Y., J.L. and Y.-K.S. contributed to the discussion of the results. C.S.Y. and Y.-K.S. wrote the manuscript. All the authors commented on and revised the manuscript.

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Correspondence to Chong S. Yoon or Yang-Kook Sun.

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Supplementary Information

Supplementary Note 1, refs. 1–4, Figs. 1–14 and Tables 1–3.

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Kim, U., Park, G., Son, B. et al. Heuristic solution for achieving long-term cycle stability for Ni-rich layered cathodes at full depth of discharge. Nat Energy (2020). https://doi.org/10.1038/s41560-020-00693-6

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