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The lithium intercalation process in the low-voltage lithium battery anode Li1+xV1−xO2

Nature Materials volume 10, pages 223–229 (2011)Cite this article

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Abstract

Lithium can be reversibly intercalated into layered Li1+xV1−xO2 (LiCoO2 structure) at ∼0.1 V, but only if x>0. The low voltage combined with a higher density than graphite results in a higher theoretical volumetric energy density; important for future applications in portable electronics and electric vehicles. Here we investigate the crucial question, why Li cannot intercalate into LiVO2 but Li-rich compositions switch on intercalation at an unprecedented low voltage for an oxide? We show that Li+ intercalated into tetrahedral sites are energetically more stable for Li-rich compositions, as they share a face with Li+ on the V site in the transition metal layers. Li incorporation triggers shearing of the oxide layers from cubic to hexagonal packing because the Li2VO2 structure can accommodate two Li per formula unit in tetrahedral sites without face sharing. Such understanding is important for the future design and optimization of low-voltage intercalation anodes for lithium batteries.

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Figure 1: Structural characterization of as-prepared Li1+xV1−xO2.
Figure 2: Variation of potential (versus Li+[1 M]/Li) with state of charge for Li1+xV1−xO2.
Figure 3: Expanded regions of the powder neutron diffraction patterns collected at various states of charge for Li1.07V0.93O2.
Figure 4: Schematic representation of the structure of Li2VO2.
Figure 5: Configurations of 2VV4+ and LiV+ in the vanadium layer of Li1.07V0.93O2.
Figure 6: Calculated local structures around an inserted Li+ ion in LiVO2 and Li1.07V0.93O2.

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Acknowledgements

P.G.B. and M.S.I. are indebted to the European Union and EPSRC for financial support. The computations were run on the HECToR facilities via the Materials Chemistry Consortium.

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Authors and Affiliations

  1. EaStCHEM, School of Chemistry, University of St Andrews, St. Andrews, Fife, KY16 9ST, UK

    A. Robert Armstrong, Christopher Lyness & Peter G. Bruce

  2. Department of Chemistry, University of Bath, Bath, BA2 7AY, UK

    Pooja M. Panchmatia & M. Saiful Islam

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A.R.A. and C.L. carried out the experimental work and data analysis, P.M.P. the modelling, M.S.I. and P.G.B. conceived and directed the project.

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Correspondence to M. Saiful Islam or Peter G. Bruce.

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Armstrong, A., Lyness, C., Panchmatia, P. et al. The lithium intercalation process in the low-voltage lithium battery anode Li1+xV1−xO2. Nature Mater 10, 223–229 (2011). https://doi.org/10.1038/nmat2967

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