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Atomic resolution of lithium ions in LiCoO2

Nature Materials volume 2, pages 464–467 (2003)Cite this article

Abstract

LiCoO2 is the most common lithium storage material for lithium rechargeable batteries, used widely to power portable electronic devices such as laptop computers1,2,3. Operation of lithium rechargeable batteries is dependent on reversible lithium insertion and extraction processes into and from the host materials of lithium storage. Ordering of lithium and vacancies3,4,5,6 has a profound effect on the physical properties of the host materials and the electrochemical performance of lithium batteries. However, probing lithium ions has been difficult when using traditional X-ray and neutron powder diffraction techniques due to lithium's relatively low scattering power when compared with those of oxygen and transition metals. In the work presented here, we have succeeded in simultaneously resolving columns of cobalt, oxygen and lithium atoms in layered LiCoO2 battery material, using experimental focal series of LiCoO2 images obtained at sub-ångstrom resolution in a mid-voltage transmission electron microscope. Lithium atoms are the smallest and lightest metal atoms, and scatter electrons only very weakly. We believe our observations of lithium to be the first by electron microscopy, and that they show promise for direct visualization of the ordering of lithium and vacancies in transition metal oxides.

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Figure 1: Models of the layered LiCoO2 structure with space group R3̄m.
Figure 2: Lighter atoms require improved resolution.
Figure 3: Visibility of Li improves with specimen thickness.
Figure 4: Experimental image of Li atom columns confirmed by simulation.

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Acknowledgements

This work was supported by National Science Foundation International Research Fellow Award INT-0000429 and the Director, Office of Science, Office of Basic Energy Sciences, Material Sciences Division, of the US Department of Energy, under contract No. DE-AC03-76SF00098. The experimental HRTEM data were collected at The National Center for Electron Microscopy, Lawrence Berkeley Laboratory, USA.

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Authors and Affiliations

  1. Department of Mechanical Engineering Massachusetts Institute of Technology, Massachusetts Institute of Technology, 77 Massachusetts Avenue, Cambridge, 02139, Massachusetts, USA

    Yang Shao-Horn

  2. Institut de Chimie de la Matière Condensée de Bordeaux-CNRS and Ecole Nationale Supérieure de Chimie et Physique de Bordeaux, Université Bordeaux I, 87 av. Dr A. Schweitzer, Pessac cedex, 33608, France

    Yang Shao-Horn, Laurence Croguennec & Claude Delmas

  3. Materials Sciences Division, Lawrence Berkeley National Laboratory, 1 Cyclotron Road, Berkeley, 94720, California, USA

    E. Chris Nelson & Michael A. O'Keefe

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  1. Yang Shao-Horn
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Correspondence to Yang Shao-Horn.

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Shao-Horn, Y., Croguennec, L., Delmas, C. et al. Atomic resolution of lithium ions in LiCoO2. Nature Mater 2, 464–467 (2003). https://doi.org/10.1038/nmat922

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