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Effect of pre-intercalation on Li-ion diffusion mapped by topochemical single-crystal transformation and operando investigation

Nature Materials (2024)Cite this article

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Abstract

Limitations in electrochemical performance as well as supply chain challenges have rendered positive electrode materials a critical bottleneck for Li-ion batteries. State-of-the-art Li-ion batteries fall short of accessing theoretical capacities. As such, there is intense interest in the design of strategies that enable the more effective utilization of active intercalation materials. Pre-intercalation with alkali-metal ions has attracted interest as a means of accessing higher reversible capacity and improved rate performance. However, the structural basis for improvements in electrochemical performance remains mostly unexplored. Here we use topochemical single-crystal-to-single-crystal transformations in a tunnel-structured ζ-V2O5 positive electrode to illustrate the effect of pre-intercalation in modifying the host lattice and altering diffusion pathways. Furthermore, operando synchrotron X-ray diffraction is used to map Li-ion site preferences and occupancies as a function of the depth of discharge in pre-intercalated materials. Na- and K-ion intercalation ‘props open’ the one-dimensional tunnel, reduces electrostatic repulsions between inserted Li ions and entirely modifies diffusion pathways, enabling orders of magnitude higher Li-ion diffusivities and accessing higher capacities. Deciphering the atomistic origins of improved performance in pre-intercalated materials on the basis of single-crystal-to-single-crystal topochemical transformation and operando diffraction studies paves the way to site-selective modification approaches for positive electrode design.

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Fig. 1: Structural and morphological characterization.
Fig. 2: Electrochemical characterization of β-Na0.25V2O5 and β-K0.27V2O5.
Fig. 3: Single-crystal XRD mapping of lithium-ion diffusion in pre-intercalated β-NaxV2O5 and β-KxV2O5.
Fig. 4: Structural evolution characterized by operando synchrotron powder XRD.
Fig. 5: Migration barriers in pre-intercalated compounds.

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All data supporting this study are available within this article and its Supplementary Information. Any additional relevant data are available upon request. Source data are provided with this paper.

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Acknowledgements

This study is based on work supported by the National Science Foundation (NSF) under DMR 1809866 (S.B.). This research used resources of the Advanced Photon Source by Argonne National Laboratory under contract number DE-AC02-06CH11357. Argonne National Laboratory is operated for the US Department of Energy Office of Science by UChicago Argonne. We thank K. Wiaderek and A. Yakovenko for their support at beamline 17-BM of the Advanced Photon Source. Use of the TAMU Materials Characterization Facility and the Texas A&M Microscopy and Imaging Center is acknowledged. M.P. acknowledges the support of National Science Foundation (NSF) under DMR 1944674. T.D. and S.C. acknowledge HRI Allahabad and DST-SERB (SRG/2020/001707) for the infrastructure and funding. Computational work for this study was carried out at the cluster computing facility at Harish-Chandra Research Institute (http://www.hri.res.in/cluster).

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  1. These authors contributed equally: Yuting Luo, Joseph V. Handy, Tisita Das, John D. Ponis.

Authors and Affiliations

  1. Department of Chemistry, Texas A&M University, College Station, TX, USA

    Yuting Luo, Joseph V. Handy, John D. Ponis, Ryan Albers, Yu-Hsiang Chiang & Sarbajit Banerjee

  2. Department of Materials Science and Engineering, Texas A&M University, College Station, TX, USA

    Yuting Luo, Joseph V. Handy, John D. Ponis, Ryan Albers, Yu-Hsiang Chiang & Sarbajit Banerjee

  3. Harish-Chandra Research Institute (HRI) Allahabad, a Constituent Institution of Homi Bhabha National Institute (HBNI), Prayagraj (Allahabad), India

    Tisita Das & Sudip Chakraborty

  4. Department of Mechanical Engineering, Texas A&M University, College Station, TX, USA

    Matt Pharr

  5. Dimien Inc., Buffalo, NY, USA

    Brian J. Schultz, Leonardo Gobbato & Dean C. Brown

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Contributions

Y.L. conceptualized the project under the supervision of S.B. The powder materials were designed, synthesized and characterized and electrochemically tested by Y.L. The operando experiment was conducted by Y.L. with the help of J.V.H. The single-crystal materials were designed, synthesized and characterized by J.V.H., J.D.P. and R.A. The DFT simulations were performed by T.D. under the supervision of S.C. Galvanostatic intermittent titration technique data were acquired by Y.-H.C. Long-term electrochemical cycling was conducted by B.J.S., L.G and D.C.B. Coin cell assembly resources and advice were provided by M.P. The paper was written by Y.L. and revised by S.B., J.V.H. and J.D.P. with the help of all other authors. All authors contributed to discussions and writing—review and editing.

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Correspondence to Sudip Chakraborty or Sarbajit Banerjee.

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A provisional patent has been filed related to new compositions of lithiated β-Na0.25V2O5/β-K0.22V2O5 by the Texas A&M University System.

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Supplementary Figs. 1–13 and Tables 1–20.

Supplementary Video 1

Single-crystal structure of lithiated sodium vanadium oxide.

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Luo, Y., Handy, J.V., Das, T. et al. Effect of pre-intercalation on Li-ion diffusion mapped by topochemical single-crystal transformation and operando investigation. Nat. Mater. (2024). https://doi.org/10.1038/s41563-024-01842-y

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