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Quantitative characterization of local ionic mobility and concentration in Li-battery cathodes via Low Frequency Electrochemical Strain Microscopy

Abstract

Recently discovered Electrochemical Strain Microscopy (ESM) can provide useful information on the ionic processes in materials at the local scale. This is especially important for ever growing applications of Li-batteries which performance is limited by the intrinsic and extrinsic degradation, involving different scales from microns to a few nanometers. However, ESM method used so far was only qualitative due to multiple contributions to the apparent ESM signal. In this work, we provide a viable approach for the local probing of ionic concentration and diffusion coefficients based on the frequency dependence of the ESM signal. Theoretical basis considering the dynamic behavior of ion migration and change of ion concentration profiles under the action of electric field of ESM tip is developed. We argue that several parasitic contributions to the ESM signal discussed in the literature can be thus eliminated and the values of Li concentration and diffusion coefficients can be extracted with the nanoscale resolution. The analysis of ESM maps using the proposed approach allows to make far reaching conclusion on the lithiation-delithiation processes in ionic conductors. The results are validated on Li-battery cathodes (LiMn2O4) extracted from commercial Li-batteries and provide novel possibilities for their development and further insight into the mechanisms of their degradation.

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Publication details

The article was received on 27 Oct 2017, accepted on 15 Dec 2017 and first published on 15 Dec 2017


Article type: Paper
DOI: 10.1039/C7NR08001H
Citation: Nanoscale, 2017, Accepted Manuscript
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    Quantitative characterization of local ionic mobility and concentration in Li-battery cathodes via Low Frequency Electrochemical Strain Microscopy

    D. Alikin, K. Romanyuk, B. Slautin, D. Rosato, V. Shur and A. Kholkin, Nanoscale, 2017, Accepted Manuscript , DOI: 10.1039/C7NR08001H

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