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Uncovering the predictive pathways of lithium and sodium interchange in layered oxides

Nature Materials (2024)Cite this article

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Abstract

Ion exchange is a powerful method to access metastable materials with advanced functionalities for energy storage applications. However, high concentrations and unfavourably large excesses of lithium are always used for synthesizing lithium cathodes from parent sodium material, and the reaction pathways remain elusive. Here, using layered oxides as model materials, we demonstrate that vacancy level and its corresponding lithium preference are critical in determining the accessible and inaccessible ion exchange pathways. Taking advantage of the strong lithium preference at the right vacancy level, we establish predictive compositional and structural evolution at extremely dilute and low excess lithium based on the phase equilibrium between Li0.94CoO2 and Na0.48CoO2. Such phase separation behaviour is general in both surface reaction-limited and diffusion-limited exchange conditions and is accomplished with the charge redistribution on transition metals. Guided by this understanding, we demonstrate the synthesis of NayCoO2 from the parent LixCoO2 and the synthesis of Li0.94CoO2 from NayCoO2 at 1–1,000 Li/Na (molar ratio) with an electrochemical assisted ion exchange method by mitigating the kinetic barriers. Our study opens new opportunities for ion exchange in predictive synthesis and separation applications.

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Fig. 1: Phase separation and two-phase equilibrium between Li0.94CoO2 and Na0.48CoO2.
Fig. 2: Revealing structural evolution during Li ion exchange with Na0.67CoO2.
Fig. 3: Reverse conversion from LixCoO2 to NayCoO2.
Fig. 4: Full conversion from Na parent host to LixCoO2 by electrochemically assisted ion exchange.
Fig. 5: Phase diagram of Li and Na interchange in layered cobalt oxides.

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The authors declare that all relevant data are included in the paper and Supplementary Information files and are available from the corresponding author upon reasonable request.

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Acknowledgements

We thank Y. Chen for performing ultramicrotome cutting. This work is supported by the US Department of Energy (DOE), Office of Basic Energy Sciences under award DE-SC0022231. This research used resources of the Advanced Photon Source, a US DOE Office of Science user facility operated for the DOE Office of Science by Argonne National Laboratory under contract DE-AC02-06CH11357. This work made use of instruments in the Electron Microscopy Core of UIC’s Research Resources Center. Acquisition of UIC JEOL ARM200CF was supported by a MRI-R2 grant from the National Science Foundation (DMR-0959470). The Gatan Continuum GIF acquisition at UIC was supported by a MRI grant from the National Science Foundation (DMR-1626056). This work made use of the EPIC facility of Northwestern University’s NUANCE Center, which has received support from the SHyNE Resource (NSF ECCS-2025633), the IIN and Northwestern’s MRSEC programme (NSF DMR-1720139). P.C. acknowledges funding from the National Research Foundation under NRF Fellowship NRFF12-2020-0012. We acknowledge that the computational work involved in this research is supported by National University of Singapore IT Research computing group (https://nusit.nus.edu.sg), and we thank software tuning support from M. Dias Costa and W. Junhong. This work used computational resources of the supercomputer Fugaku provided by RIKEN through the HPCI System Research Project (project ID hp 230188). A proportion of computational work was performed on resources of the National Supercomputing Centre, Singapore (https://www.nscc.sg).

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Authors and Affiliations

  1. Pritzker School of Molecular Engineering, University of Chicago, Chicago, IL, USA

    Yu Han, Grant T. Hill, Gangbin Yan, Siqi Zou, Jiadong Liu, Ronghui Wu & Chong Liu

  2. Department of Materials Science and Engineering, National University of Singapore, Singapore, Singapore

    Weihang Xie

  3. Department of Materials Science and Engineering, Northwestern University, Evanston, IL, USA

    Paul Smeets & Xiaobing Hu

  4. The NUANCE Center, Northwestern University, Evanston, IL, USA

    Paul Smeets & Xiaobing Hu

  5. Electron Microscopy Core, Research Resources Center, University of Illinois Chicago, Chicago, IL, USA

    Fengyuan Shi

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

    Hua Zhou

  7. Department of Electrical and Computer Engineering, University of Houston, Houston, TX, USA

    Pieremanuele Canepa

  8. Texas Center for Superconductivity at the University of Houston, Houston, TX, USA

    Pieremanuele Canepa

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Contributions

C.L. and Y.H. conceived and developed the idea and planned the experiments. P.C. and W.X. performed the DFT calculation. G.T.H., H.Z. and S.Z. performed the synchrotron XRD measurement. P.S., X.H. and Y.H. performed the STEM imaging, EELS and EDS analysis with the assistance of F.S. G.Y. assisted with the ICP-MS data acquirement. S.Z. performed the SEM imaging. J.L. and R.W. helped with data collation during revision. All authors analysed the data and co-wrote the paper.

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Correspondence to Chong Liu.

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Han, Y., Xie, W., Hill, G.T. et al. Uncovering the predictive pathways of lithium and sodium interchange in layered oxides. Nat. Mater. (2024). https://doi.org/10.1038/s41563-024-01862-8

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