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Local degradation pathways in lithium-rich manganese–nickel–cobalt oxide epitaxial thin films

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Abstract

The electrochemical performance and microstructure of positive electrodes are intimately linked. As such, developing batteries resistance to capacity and voltage fade requires understanding these underlying structure–property relationships and their evolution with operation. Epitaxial films of a Li-rich manganese–nickel–cobalt oxide cathode material were deposited on (100)- and (111)-oriented SrRuO3/SrTiO3 substrates. Cyclic voltammetry and impedance spectroscopy tracked the response of these positive electrode materials, while the microstructure of the pristine and cycled films was characterized using transmission electron microscopy. Energy-dispersive X-ray spectroscopy identifies compositional fluctuations in as-deposited films. Phase transformations and dissolution were observed after electrochemical testing. There is a correlation between both local composition and substrate orientation (i.e., surface faceting) and what degradation pathways are active. Regions with comparatively higher concentrations of Ni and Co were more resistant to dissolution and unfavorable phase transformations than those with relatively more Mn. As such, a global composition metric may not be an accurate predictor of degradation and performance. Rather possessing the synthetic ability to engineer the chemical profile as well as characterizing it, pose a challenge and opportunity.

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Acknowledgements

We thank Bryant J. Polzin and Andrew N. Jansen (Argonne National Laboratory) for providing the HE5050 powder. This research was performed, while A.C.J.-P. held a National Research Council Research Associateship Award at the National Institute of Standards and Technology. S.T. acknowledges support from the US Department of Commerce, National Institute of Standards and Technology, under financial assistance Award 70NANB16H107.

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Author notes

  1. Saya Takeuchi

    Present address: Physical Measurement Laboratory, National Institute of Standards and Technology, Gaithersburg, MD, 20899, USA

  2. K. Kamala Bharathi

    Present address: Department of Physics and Nanotechnology, SRM University, Kattankulathur, Chennai, 603203, India

  3. Aaron C. Johnston-Peck and Saya Takeuchi have contributed equally to this work.

Authors and Affiliations

  1. Material Measurement Laboratory, National Institute of Standards and Technology, Gaithersburg, MD, 20899, USA

    Aaron C. Johnston-Peck, Saya Takeuchi, K. Kamala Bharathi, Andrew. A. Herzing & Leonid A. Bendersky

  2. Theiss Research, La Jolla, CA, 92037, USA

    Saya Takeuchi

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  1. Aaron C. Johnston-Peck
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Disclaimer Certain commercial equipment and materials are identified in this paper in order to specify adequately the experimental procedure. In no case does such identification imply recommendations by the National Institute of Standards and Technology nor does it imply that the material or equipment identified is necessarily the best available for this purpose.

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Johnston-Peck, A.C., Takeuchi, S., Bharathi, K.K. et al. Local degradation pathways in lithium-rich manganese–nickel–cobalt oxide epitaxial thin films. J Mater Sci 53, 1365–1379 (2018). https://doi.org/10.1007/s10853-017-1593-5

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