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Nanoscale mapping of ion diffusion in a lithium-ion battery cathode

Nature Nanotechnology volume 5, pages 749–754 (2010)Cite this article

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Abstract

The movement of lithium ions into and out of electrodes is central to the operation of lithium-ion batteries. Although this process has been extensively studied at the device level, it remains insufficiently characterized at the nanoscale level of grain clusters, single grains and defects. Here, we probe the spatial variation of lithium-ion diffusion times in the battery-cathode material LiCoO2 at a resolution of ∼100 nm by using an atomic force microscope to both redistribute lithium ions and measure the resulting cathode deformation. The relationship between diffusion and single grains and grain boundaries is observed, revealing that the diffusion coefficient increases for certain grain orientations and single-grain boundaries. This knowledge provides feedback to improve understanding of the nanoscale mechanisms underpinning lithium-ion battery operation.

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Figure 1: Characterizing the LiCoO2 cathode layer and redistributing lithium ions with constant voltages (low-frequency pulses).
Figure 2: Mapping local lithium flow with high-frequency bias.
Figure 3: Local probing of lithium diffusion times by varying pulse frequency and amplitude.
Figure 4: Lithium intercalation map in LiCoO2.

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Acknowledgements

Research was sponsored as part of the Fluid Interface Reactions, Structures and Transport (FIRST) Center, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences under Award Number ERKCC61 (N.B., L.A., N.D., S.V.K.) and part of the Scientific User Facilities Division, Office of Basic Energy Sciences, U.S. Department of Energy in the projects CNMS2010-098 and CNMS2010-099 (N.B., S.J., I.N.I.). N.B. also acknowledges the Alexander von Humboldt foundation. R.E.G. and D.W.C. are grateful for the support provided by NSF grant CMMI 0856491.

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Authors and Affiliations

  1. The Center for Nanophase Materials Science, Oak Ridge National Laboratory, Oak Ridge, 37831, Tennessee, USA

    N. Balke, S. Jesse & S. V. Kalinin

  2. Institute of Semiconductor Physics, National Academy of Science of Ukraine, Ukraine 41, pr. Nauki, Kiev, 03028, Ukraine

    A. N. Morozovska

  3. Institute for Problems of Materials Science, National Academy of Science of Ukraine, Ukraine 3, Krjijanovskogo, Kiev, 03142, Ukraine

    E. Eliseev

  4. School of Materials Engineering, Purdue University, West Lafayette, 47907, Illinois, USA

    D. W. Chung & R. E. García

  5. Materials Sciences and Technology Division, Oak Ridge National Laboratory, Oak Ridge, 37831, Tennessee, USA

    Y. Kim, L. Adamczyk, N. Dudney & S. V. Kalinin

Authors
  1. N. Balke
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  10. S. V. Kalinin
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Contributions

Y.K., L.A. and N.D. prepared the thin-film devices and N.B. conducted the experiments. S.J. developed the spectroscopic measurement technique and analysis tools. The semi-analytical calculations were provided by A.N.M. and E.E. and the object oriented finite element analysis calculations were carried out by D.W.C. and R.E.G. N.B. and S.V.K. wrote the article. All authors discussed the results and commented on the manuscript.

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Correspondence to N. Balke or S. V. Kalinin.

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The authors declare no competing financial interests.

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Balke, N., Jesse, S., Morozovska, A. et al. Nanoscale mapping of ion diffusion in a lithium-ion battery cathode. Nature Nanotech 5, 749–754 (2010). https://doi.org/10.1038/nnano.2010.174

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