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Capturing dynamic ligand-to-metal charge transfer with a long-lived cationic intermediate for anionic redox

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Abstract

Reversible anionic redox reactions represent a transformational change for creating advanced high-energy-density positive-electrode materials for lithium-ion batteries. The activation mechanism of these reactions is frequently linked to ligand-to-metal charge transfer (LMCT) processes, which have not been fully validated experimentally due to the lack of suitable model materials. Here we show that the activation of anionic redox in cation-disordered rock-salt Li1.17Ti0.58Ni0.25O2 involves a long-lived intermediate Ni3+/4+ species, which can fully evolve to Ni2+ during relaxation. Combining electrochemical analysis and spectroscopic techniques, we quantitatively identified that the reduction of this Ni3+/4+ species goes through a dynamic LMCT process (Ni3+/4+–O2− → Ni2+–On). Our findings provide experimental validation of previous theoretical hypotheses and help to rationalize several peculiarities associated with anionic redox, such as cationic–anionic redox inversion and voltage hysteresis. This work also provides additional guidance for designing high-capacity electrodes by screening appropriate cationic species for mediating LMCT.

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Fig. 1: Structure and electrochemistry of xLi2TiO3·(1 − x)LiTi0.5Ni0.5O2 (0 < x < 1).
Fig. 2: Redox mechanism of 0.4LTO–0.6LTNO studied by ex situ XAS and DFT calculations.
Fig. 3: In situ X-ray diffraction patterns for 0.4LTO–0.6LTNO.
Fig. 4: Quantifying the LMCT process by electrochemical titration.
Fig. 5: LMCT characterized by HAXPES with an  = 10 keV photon energy and structural analysis.
Fig. 6: Rationalizing redox inversion and voltage hysteresis.

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All data supporting the findings of this article and its Supplementary Information will be made available upon reasonable request to the authors. Source data are provided with this paper.

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Acknowledgements

This research used resources of the Advanced Photon Source, a US Department of Energy (DOE) Office of Science User Facility, operated for the DOE Office of Science by Argonne National Laboratory under contract number DE-AC02-06CH11357. We are grateful to J. Freeland, T. Wu and G. Sterbinsky for their help during mail-in XAS measurements at the Advanced Photon Source. J.C. and I.R. acknowledge support from the National Science Foundation, under grant number DMR-1809372. K.K. acknowledges support from the National Science Foundation, under grant number CBET-1800357. A.M.A. and A.V.M. are grateful to the Russian Science Foundation for financial support (grant 20-13-00233). Access to TEM facilities was granted by the Advance Imaging Core Facility of Skoltech. HAXPES experiments (proposal no. 99210184) were performed on the GALAXIES beamline at the SOLEIL Synchrotron, France. The Ni K-edge XAS was collected on the ROCK beamline at the SOLEIL Synchrotron through a rapid access for urgent need. We are grateful to J. Sottmann and J.-P. Rueff for their assistance during the HAXPES experiments. J.-M.T and B.L. acknowledge funding from the European Research Council (ERC) (FP/2014)/ERC Grant-Project 670116-ARPEMA.

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B.L. and J.-M.T. conceived the idea and designed the experiments. B.L. carried out the synthesis, structural characterization, electrochemical analysis and DFT calculations. R.D. collected and analysed the HAXPES data. K.K., I.R. and J.C. collected the XAS data and carried out the analysis. A.V.M., O.V.E. and A.M.A. performed TEM experiments and did the analysis. L.Z. performed the OEMS experiments and data analysis. S.B. collected the Ni K-edge XAS data during relaxation. T.K. did the protocol and assembling of ASSB cells. B.L. and J.-M.T. wrote the manuscript with the contributions from all the authors.

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Correspondence to Jean-Marie Tarascon.

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Nature Materials thanks Kisuk Kang and Zhaoxiang Wang for their contribution to the peer review of this work.

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Li, B., Kumar, K., Roy, I. et al. Capturing dynamic ligand-to-metal charge transfer with a long-lived cationic intermediate for anionic redox. Nat. Mater. (2022). https://doi.org/10.1038/s41563-022-01278-2

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