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Origin of voltage decay in high-capacity layered oxide electrodes

Nature Materials volume 14, pages 230–238 (2015)Cite this article

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Abstract

Although Li-rich layered oxides (Li1+xNiyCozMn1−x−y−zO2 > 250 mAh g−1) are attractive electrode materials providing energy densities more than 15% higher than today’s commercial Li-ion cells, they suffer from voltage decay on cycling. To elucidate the origin of this phenomenon, we employ chemical substitution in structurally related Li2RuO3 compounds. Li-rich layered Li2Ru1−yTiyO3 phases with capacities of ~240 mAh g−1 exhibit the characteristic voltage decay on cycling. A combination of transmission electron microscopy and X-ray photoelectron spectroscopy studies reveals that the migration of cations between metal layers and Li layers is an intrinsic feature of the charge–discharge process that increases the trapping of metal ions in interstitial tetrahedral sites. A correlation between these trapped ions and the voltage decay is established by expanding the study to both Li2Ru1−ySnyO3 and Li2RuO3; the slowest decay occurs for the cations with the largest ionic radii. This effect is robust, and the finding provides insights into new chemistry to be explored for developing high-capacity layered electrodes that evade voltage decay.

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Figure 1: Structural and electrochemical aspects of Li2Ru0.75Ti0.25O3.
Figure 2: Cycling behaviour of Li2Ru1−yMyO3 (M = Ru/Sn/Ti) in the view towards voltage decay.
Figure 3: Li-driven structural changes of Li2Ru0.75M0.25O3 (M = Sn/Ti).
Figure 4: XPS of Li2Ru0.75Ti0.25O3.
Figure 5: HAADF-STEM images of Li2Ru0.75Ti0.25O3 electrodes.
Figure 6: Comparison of HAADF-STEM images of Li2Ru0.75M0.25O3 (M = Sn/ Ti) on long cycling.

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Acknowledgements

The authors acknowledge both ALISTORE-ERI and RS2E institutions for fully supporting this work. G.V.T. acknowledges the European Research Council, ERC grant No. 246791–COUNTATOMS. The research leading to these results has received funding from the European Union Seventh Framework Programme under Grant Agreement 312483-ESTEEM2 (Integrated Infrastructure Initiative–I3). C.P.L. thanks the CSIR, New Delhi for granting a Senior Research Fellowship. Use of the APS (Advanced Photon Source) at Argonne National Laboratory (ANL) supported by the US Department of Energy under Contract No. DE-AC02-06CH11357 is greatly acknowledged. J. Kurzman is acknowledged for support in editing the manuscript.

Author information

Authors and Affiliations

  1. FRE 3677 ‘Chimie du Solide et de l’Energie’, Collège de France, 11, Place Marcelin Berthelot 75231 Paris, France,

    M. Sathiya, G. Rousse, A. S. Prakash & J-M. Tarascon

  2. LRCS, CNRS UMR 7314, Université de Picardie Jules Verne, 80039 Amiens, France

    M. Sathiya

  3. ALISTORE-European Research Institute, 80039 Amiens, France

    M. Sathiya, D. Foix, M. Saubanère, M. L. Doublet, D. Gonbeau & J-M. Tarascon

  4. EMAT, University of Antwerp, Groenenborgerlaan 171 B-2020 Antwerp, Belgium,

    A. M. Abakumov & G. VanTendeloo

  5. IPREM/ECP (UMR 5254), University of Pau, 2 av. Pierre Angot 64053 Pau Cedex 9, France,

    D. Foix & D. Gonbeau

  6. Réseau sur le Stockage Electrochimique de l’Energie (RS2E), FR CNRS 3459, France

    D. Foix, G. Rousse, M. Saubanère, M. L. Doublet, D. Gonbeau & J-M. Tarascon

  7. Sorbonne Universités UPMC Univ Paris 06, 4 place Jussieu 75252 Paris Cedex 05, France,

    G. Rousse

  8. CSIR- CECRI- Chennai Centre, CSIR Campus, Taramani, Chennai-600 113, India

    K. Ramesha, C. P. Laisa & A. S. Prakash

  9. Institut Charles Gerhardt, CNRS UMR5253, Université Montpellier 2, 34 095 Montpellier, France

    M. Saubanère & M. L. Doublet

  10. Univ. Lille Nord de France, CNRS, UMR 8516 – LASIR, Univ. Lille 1, F-59655 Villeneuve d’Ascq, France

    H. Vezin

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Contributions

M.Sathiya, K.R., C.P.L. and A.S.P. carried out the synthesis, M.Sathiya, and J-M.T. conducted the electrochemical work and J-M.T. designed the research approach; G.R. analysed the crystal structures and diffraction patterns; A.M.A. and G.V.T. carried out, analysed and exploited the electron diffraction and HAADF-STEM studies; D.F. and D.G. collected and analysed the XPS spectra; M.Saubanère and M.L.D. conducted the DFT calculations and developed the theoretical framework; M.Sathiya, A.M.A. and J-M.T. wrote the manuscript and all authors discussed the experiments and final manuscript.

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Correspondence to J-M. Tarascon.

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Sathiya, M., Abakumov, A., Foix, D. et al. Origin of voltage decay in high-capacity layered oxide electrodes. Nature Mater 14, 230–238 (2015). https://doi.org/10.1038/nmat4137

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