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Origin of additional capacities in metal oxide lithium-ion battery electrodes

Nature Materials volume 12, pages 1130–1136 (2013)Cite this article

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Abstract

Metal fluorides/oxides (MFx/MxOy) are promising electrodes for lithium-ion batteries that operate through conversion reactions. These reactions are associated with much higher energy densities than intercalation reactions. The fluorides/oxides also exhibit additional reversible capacity beyond their theoretical capacity through mechanisms that are still poorly understood, in part owing to the difficulty in characterizing structure at the nanoscale, particularly at buried interfaces. This study employs high-resolution multinuclear/multidimensional solid-state NMR techniques, with in situ synchrotron-based techniques, to study the prototype conversion material RuO2. The experiments, together with theoretical calculations, show that a major contribution to the extra capacity in this system is due to the generation of LiOH and its subsequent reversible reaction with Li to form Li2O and LiH. The research demonstrates a protocol for studying the structure and spatial proximities of nanostructures formed in this system, including the amorphous solid electrolyte interphase that grows on battery electrodes.

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Figure 1: In situ PDF analyses of the RuO2/Li system reveal the changes in phase composition following battery discharge.
Figure 2: In situ XAS analyses of the RuO2/Li system reveal the changes in the average oxidation state of ruthenium, phase composition and bond lengths.
Figure 3: Tracking the evolution of different chemical species at different states of charge in the RuO2/Li battery system.
Figure 4: Summary of the reaction pathway, evolution of phase distribution and relevant experimental evidence of the RuO2/Li battery system.

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Acknowledgements

This research was supported as part of the North Eastern Center for Chemical Energy Storage, an Energy Frontier Research Center funded by the US Department of Energy, Office of Science, and Office of Basic Energy Sciences under Award Number DE-SC0001294. Work done at Argonne and use of the Advanced Photon Source, an Office of Science User Facility operated for the US Department of Energy (DOE) Office of Science by Argonne National Laboratory, was supported by the US DOE under Contract No. DE-AC02-06CH11357. Use of the National Synchrotron Light Source, Brookhaven National Laboratory, was supported by the US DOE, Office of Science, Office of Basic Energy Sciences, under Contract No. DE-AC02-98CH10886. Y-Y.H. acknowledges support from a Newton International Fellowship from the Royal Society and a Marie Curie International Incoming Fellowship (PIIF-GA-2011_299341). We thank A. Van der Ven (University of Michigan) and M. Leskes (University of Cambridge) for constructive discussions.

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Authors and Affiliations

  1. Department of Chemistry, University of Cambridge, Lensfield Road, Cambridge CB2 1EW, UK

    Yan-Yan Hu, Zigeng Liu, Jun Cheng, Xiao Hua, Matthew T. Dunstan & Clare P. Grey

  2. Chemistry Department, Brookhaven National Laboratory, New York 11973, USA

    Kyung-Wan Nam, Xiqian Yu & Xiao-Qing Yang

  3. X-ray Science Division, Advanced Photon Source, Argonne National Laboratory, Illinois 60439, USA

    Olaf J. Borkiewicz, Kamila M. Wiaderek, Karena W. Chapman & Peter J. Chupas

  4. Department of Chemistry, Stony Brook University, New York 11794-3400, USA

    Lin-Shu Du & Clare P. Grey

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Contributions

C.P.G. and Y-Y.H. proposed the concepts and designed the experiments. Y-Y.H., Z.L., K-W.N., O.J.B., X.H., J.C., K.M.W., L-S.D. and X.Y. carried out the experiments, C.P.G., Y-Y.H., K-W.N., O.J.B., X.H., J.C., M.T.D., K.W.C., P.J.C., X.Y. and X-Q.Y. performed the analysis. C.P.G. and Y-Y.H. wrote the manuscript with help from all the co-authors.

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Correspondence to Clare P. Grey.

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Hu, YY., Liu, Z., Nam, KW. et al. Origin of additional capacities in metal oxide lithium-ion battery electrodes. Nature Mater 12, 1130–1136 (2013). https://doi.org/10.1038/nmat3784

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