Unravelling structural ambiguities in lithium- and manganese-rich transition metal oxides

Shukla, A. K., Ramasse, Q. M., Ophus, C., Duncan, H., Hage, F. and Chen, G. (2015) Unravelling structural ambiguities in lithium- and manganese-rich transition metal oxides. Nature Communications, 6, 8711. (doi: 10.1038/ncomms9711) (PMID:26510508) (PMCID:PMC4846316)

Abstract

Although Li- and Mn-rich transition metal oxides have been extensively studied as high-capacity cathode materials for Li-ion batteries, the crystal structure of these materials in their pristine state is not yet fully understood. Here we apply complementary electron microscopy and spectroscopy techniques at multi-length scale on well-formed Li1.2(Ni0.13Mn0.54Co0.13)O2 crystals with two different morphologies as well as two commercially available materials with similar compositions, and unambiguously describe the structural make-up of these samples. Systematically observing the entire primary particles along multiple zone axes reveals that they are consistently made up of a single phase, save for rare localized defects and a thin surface layer on certain crystallographic facets. More specifically, we show the bulk of the oxides can be described as an aperiodic crystal consisting of randomly stacked domains that correspond to three variants of monoclinic structure, while the surface is composed of a Co- and/or Ni-rich spinel with antisite defects.

• Item Type: Articles
• Additional Information: This work was supported by the Assistant Secretary for Energy Efficiency and Renewable Energy, Office of Vehicle Technologies of the US Department of Energy under Contract DE-AC02-05CH11231 under the Batteries for Advanced Transportation Technologies (BATT) Program. Work at the Molecular Foundry was supported by the Office of Science, Office of Basic Energy Sciences, of the US Department of Energy under Contract No. DE-AC02-05CH11231.
• Status: Published
• Refereed: Yes
• Glasgow Author(s) Enlighten ID: Hage, Dr Fredrik Sydow
• Authors: Shukla, A. K., Ramasse, Q. M., Ophus, C., Duncan, H., Hage, F., and Chen, G.
• College/School: College of Science and Engineering > School of Physics and Astronomy
• Journal Name: Nature Communications
• Publisher: Nature Publishing Group
• ISSN: 2041-1723
• ISSN (Online): 2041-1723
• Copyright Holders: Copyright © 2015 The Authors
• First Published: First published in Nature Communications 6: 8711
• Publisher Policy: Reproduced under a Creative Commons License