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Ultrastable cathodes enabled by compositional and structural dual-gradient design

Nature Energy (2024)Cite this article

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An Author Correction to this article was published on 21 August 2024

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Abstract

Cathodes for next-generation batteries are pressed for higher voltage operation (≥4.5 V) to achieve high capacity with long cyclability and thermal tolerance. Current cathodes fail to meet these requirements owing to structural and electrochemical strains at high voltages, leading to fast capacity fading. Here we present a cathode with a coherent architecture ranging from ordered to disordered frameworks with concentration gradient and controllable Ni oxidation activities, which can overcome voltage ceilings imposed by existing cathodes. This design enables simultaneous high-capacity and high-voltage operation at 4.5 V without capacity fading, and up to 4.7 V with negligible capacity decay. Multiscale diffraction and imaging techniques reveal the disordered surface is electrochemically and structurally indestructible, preventing surface parasitic reactions and phase transitions. Structural coherence from ordering to disordering limits lattice parameter changes, mitigating lattice strain and enhancing morphological integrity. The dual-gradient design also notably improves thermal stability, driving the advancement of high-performance cathode materials.

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Fig. 1: The SCDG cathode design principle and initial morphology, structure and composition properties.
Fig. 2: The surface structure ordering and valence states of Ni within SCDG cathode.
Fig. 3: The electrochemical performance of SCDG, FCG and NMC cathodes.
Fig. 4: The valence state changes and structure evolution of SCDG and NMC cathodes.
Fig. 5: Structure stability during cycles and thermal stability of SCDG and NMC cathodes.

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

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Acknowledgements

This work gratefully acknowledges support from the US Department of Energy (DOE), Office of Energy Efficiency and Renewable Energy, Vehicle Technologies Office. Argonne National Laboratory is operated for DOE Office of Science by UChicago Argonne, LLC, under contract number DE-AC02-06CH11357. This research used resources of the Advanced Photon Source (8-BM-B, 11-BM, 11-ID-C, 26-ID-C and 29 ID), a US DOE Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under contract no. DE-AC02-06CH11357. We also thank Y. Ren, S. Lapidus and J. Freeland for their support of the synchrotron-based experiments at APS. Use of the National Synchrotron Light Source II (beamline 3-ID, 7-BM and 18-ID) is supported by the US DOE, an Office of Science user Facility operated by Brookhaven National Laboratory under contract number DE-SC0012704. Work performed at the Center for Nanoscale Materials, a US DOE Office of Science User Facility, was supported by the US DOE, Office of Basic Energy Sciences, under contract no. DE-AC02-06CH11357.

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Authors and Affiliations

  1. Chemical Sciences and Engineering Division, Argonne National Laboratory, Lemont, IL, USA

    Tongchao Liu, Junxiang Liu, Alvin Dai, Jing Wang, Weiyuan Huang, Matthew Li & Khalil Amine

  2. Center for Nanoscale Materials, Argonne National Laboratory, Lemont, IL, USA

    Lei Yu, Tao Zhou & Jianguo Wen

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

    Luxi Li & Tianyi Li

  4. National Synchrotron Light Source II, Brookhaven National Laboratory, Upton, NY, USA

    Xiaojing Huang, Xianghui Xiao, Mingyuan Ge, Lu Ma, Yong S. Chu & Wah-Keat Lee

  5. Advanced Light Source, Lawrence Berkeley National Laboratory, Berkeley, CA, USA

    Zengqing Zhuo

  6. Material Science Division, Argonne National Laboratory, Lemont, IL, USA

    Rachid Amine

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Contributions

T. Liu and K.A. conceived of and designed the experiments. T. Liu, A.D. and W.H. synthesized all the materials and conducted electrochemical measurements. L.Y., T.Z. and J. Wen carried out the TEM, EELS and SEND results. T. Liu, J. Wang., J.L., R.A., T. Li and L.M., performed ex situ/in situ synchrotron HEXRD and XAS. T. Liu, L.L., X.H., X.X., G.M., Y.S.C. and W.-K.L. performed XRF, TXM and data analysis. T. Liu and K.A. wrote the paper, and all authors edited the paper.

Corresponding authors

Correspondence to Tongchao Liu or Khalil Amine.

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Competing interests

T. Liu and K.A. report two US non-provisional patent applications filed by the Argonne National Laboratory, patent application no. 16/809,332. The patent is related to the composition and structure design reported in this work. The other authors declare no competing interests.

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

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Supplementary Tables 1–3 and Figs. 1–23.

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Liu, T., Yu, L., Liu, J. et al. Ultrastable cathodes enabled by compositional and structural dual-gradient design. Nat Energy (2024). https://doi.org/10.1038/s41560-024-01605-8

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