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A near dimensionally invariable high-capacity positive electrode material

Abstract

Delivering inherently stable lithium-ion batteries is a key challenge. Electrochemical lithium insertion and extraction often severely alters the electrode crystal chemistry, and this contributes to degradation with electrochemical cycling. Moreover, electrodes do not act in isolation, and this can be difficult to manage, especially in all-solid-state batteries. Therefore, discovering materials that can reversibly insert and extract large quantities of the charge carrier (Li+), that is, high capacity, with inherent stability during electrochemical cycles is necessary. Here lithium-excess vanadium oxides with a disordered rocksalt structure are examined as high-capacity and long-life positive electrode materials. Nanosized Li8/7Ti2/7V4/7O2 in optimized liquid electrolytes deliver a large reversible capacity of over 300 mAh g−1 with two-electron V3+/V5+ cationic redox, reaching 750 Wh kg−1 versus metallic lithium. Critically, highly reversible Li storage and no capacity fading for 400 cycles were observed in all-solid-state batteries with a sulfide-based solid electrolyte. Operando synchrotron X-ray diffraction combined with high-precision dilatometry reveals excellent reversibility and a near dimensionally invariable character during electrochemical cycling, which is associated with reversible vanadium migration on lithiation and delithiation. This work demonstrates an example of an electrode/electrolyte couple that produces high-capacity and long-life batteries enabled by multi-electron transition metal redox with a structure that is near invariant during cycling.

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Fig. 1: Structural and electrochemical characterization of xLi2TiO3–(1−x)LiVO2 binary system.
Fig. 2: Synthesis and electrochemical properties of ‘nanosized’ Li8/7Ti2/7V4/7O2.
Fig. 3: Structural characterization for nanosized Li8/7−yTi2/7V4/7O2.
Fig. 4: Dimensional stability of nanosized Li8/7−yTi2/7V4/7O2.
Fig. 5: Correlation between Li-excess contents in the host structures and unit-cell volume changes for Li-excess V oxides.
Fig. 6: Evaluation of Li8/7Ti2/7V4/7O2 with sulfide-based solid electrolyte.

Data availability

All relevant experimental and theoretical data within the article will be provided by the corresponding author on reasonable request.

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Acknowledgements

N.Y. acknowledges the partial support from JSPS, Grant-in-Aid for Scientific Research (grant numbers 19H05816 and 21H04698), and MEXT programme ‘Elements Strategy Initiative to Form Core Research Center (JPMXP0112101003)’, MEXT; Ministry of Education Culture, Sports, Science and Technology, Japan. This work was partially supported by JST, CREST grant number JPMJCR21O6, Japan. N.S. and D.G. acknowledge the support from the Australian Research Council (ARC) through the projects DP200100959, FT200100707 and the Research Training Program (RTP). K.O. thanks the support from JSPS, Grant-in-Aid for Scientific Research (grant number 19H05814). This study was partially supported by the SOLiD-EV project (JPNP18003) of NEDO. The synchrotron X-ray absorption work was done under the approval of the Photon Factory Program Advisory Committee (proposal number 2019G033). The synchrotron radiation experiments were performed at the BL19B2 and BL04B2 of SPring-8 with the approval of the Japan Synchrotron Radiation Research Institute (JASRI) (proposal numbers 2019B1685 and 2020A2135) and on the powder diffraction beamline at the Australian Synchrotron operated by the Australian Nuclear Science and Technology Organisation (ANSTO). The ND experiments at the Materials and Life Science Experimental Facility of the J-PARC were performed under a user program (proposal number 2019PM2004). We thank the beamline scientists and support staff at these facilities. N.Y. thanks A. Nakao for the fruitful discussion about photoelectron spectroscopy.

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N.Y. conceived the basic idea for this project and led the research. I.K. performed the material synthesis, electrochemical testing and structural/spectroscopic characterization including, XRD, ND, XAS and thermal analysis. D.G. and N.S. conducted operando XRD study and contributed to the interpretation of the results. T.M. performed the dilatometry study. T.M. and Y.Y conducted the electrochemical testing with solid-state electrolyte. S.H. and K.O. conducted total X-ray scattering study and PDF analysis and discussed the interpretation of the results. Y.M. performed XPS study. H.B.R. conducted electrochemical characterization. T.I. performed ND measurement. I.K., N.S. and N.Y. discussed fundamental ideas for the overall study. I.K., N.S. and N.Y. wrote the paper.

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Correspondence to Naoaki Yabuuchi.

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Konuma, I., Goonetilleke, D., Sharma, N. et al. A near dimensionally invariable high-capacity positive electrode material. Nat. Mater. 22, 225–234 (2023). https://doi.org/10.1038/s41563-022-01421-z

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