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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References
Cohen, Y. S. & Aurbach, D. Surface films phenomena on vanadium-pentoxide cathodes for Li and Li-ion batteries: in situ AFM imaging. Electrochem. Commun. 6, 536–542 (2004).
Doi, T. et al. Electrochemical AFM study of LiMn2O4 thin film electrodes exposed to elevated temperatures. J. Power Sources 180, 539–545 (2008).
Beaulieu, L. Y., Cumyn, V. K., Eberman, K. W., Kraus, L. J. & Dahn, J. R. A system for performing simultaneous in situ atomic force microscopy/optical microscopy measurements on electrode materials for lithium-ion batteries. Rev. Sci. Instrum. 72, 3313–3319 (2001).
Beaulieu, L. Y., Hatchard, T. D., Bonakdarpour, A., Fleischauer, M. D. & Dahn, J. R. Reaction of Li with alloy thin films studied by in situ AFM. J. Electrochem. Soc. 150, A1457–A1464 (2003).
Lewis, R. B., Timmons, A., Mar, R. E. & Dahn, J. R. In situ AFM measurements of the expansion and contraction of amorphous Sn–Co–C films reacting with lithium. J. Electrochem. Soc. 154, A213–A216 (2007).
Tian, Y., Timmons, A. & Dahn, J. R. In situ AFM measurements of the expansion of nanostructured Sn–Co–C films reacting with lithium. J. Electrochem. Soc. 156, A187–A191 (2009).
Matsui, M., Dokko, K. & Kanamura, K. J. Dynamic behavior of surface film on LiCoO2 thin film electrode. J. Power Sources 177, 184–193 (2008).
Clemencon, A., Appapillai, A. T., Kumar, S. & Shao-Horn, Y. Atomic force microscopy studies of surface and dimensional changes in LixCoO2 crystals during lithium de-intercalation. Electrochem. Acta 52, 4572–4580 (2007).
Semenov, A. E., Borodina, I. N. & Garofalini, S. H. In situ deposition and ultrahigh vacuum STM/AFM study of V2O5/Li3PO4 interface in a rechargeable lithium-ion battery. J. Electrochem. Soc. 148, A1239–A1246 (2001).
Kuriyama, K., Onoue, A., Yuasa, Y. & Kushida, K. Atomic force microscopy study of surface morphology change in spinel LiMn2O4: possibility of direct observation of Jahn–Teller instability. Surf. Sci. 601, 2256–2259 (2007).
Huggins, R. A. Advanced Batteries: Materials Science Aspects (Springer, 2008).
García, R. E., Chiang, Y. M., Carter, W. C., Limthongkul, P. & Bishop, C. M. Microstructural modeling and design of rechargeable lithium-ion batteries. J. Electrochem. Soc. 152, A255–A263 (2005).
Nazri, G. A. & Pistoia, G. (eds) Lithium Batteries: Science and Technology (Springer, 2009).
Amatucci, G. G., Tarascon, J. M. & Klein, L. C. CoO2, the end member of the LixCoO2 solid solution. J. Electrochem. Soc. 143, 1114–1123 (1996).
Mizushima, K., Jones, P. C., Wiseman, P. J. & Goodenough, J. B. LixCoO2 (0 < x ≤ 1)—a new cathode material for batteries of high-energy density. Mater. Res. Bull. 15, 783–789 (1980).
Hart, F. X. & Bates, J. B. Lattice model calculation of the strain energy density and other properties of crystalline LiCoO2 . J. Appl. Phys. 83, 7560–7566 (1998).
Bouwman, P. J., Boukamp, B. A., Bouwmeester, H. J. M., Wondergem, H. J. & Notten, P. H. L. Structural analysis of submicrometer LiCoO2 films. J. Electrochem. Soc. 148, A311–A317 (2001).
Gruverman, A. & Kholkin, A. Nanoscale ferroelectrics: processing, characterization and future trends. Rep. Prog. Phys. 69, 2443–2474 (2006).
Morozovska, A. N., Eliseev, E. A. & Kalinin, S. V. Electromechanical probing of ionic currents in energy storage materials. Appl. Phys. Lett. 96, 222906 (2010).
Jesse, S., Kalinin, S. V., Proksch, R., Baddorf, A. P. & Rodriguez, B. J. The band excitation method in scanning probe microscopy for rapid mapping of energy dissipation on the nanoscale. Nanotechnology 18, 435503 (2007).
Zienkiewicz, O. C., Taylor, R. L. & Zhu. J. Z. The Finite Element Method Vol. 1 (McGraw-Hill, 2005).
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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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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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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DOI: https://doi.org/10.1038/nnano.2010.174
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