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Suppressed oxygen extraction and degradation of LiNi x Mn y Co z O2 cathodes at high charge cut-off voltages

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Abstract

The capacity degradation mechanism in lithium nickel–manganese–cobalt oxide (NMC) cathodes (LiNi1/3Mn1/3Co1/3O2 (NMC333) and LiNi0.4Mn0.4Co0.2O2 (NMC442)) during high-voltage (cut-off of 4.8 V) operation has been investigated. In contrast to NMC442, NMC333 exhibits rapid structural changes including severe micro-crack formation and phase transformation from a layered to a disordered rock-salt structure, as well as interfacial degradation during high-voltage cycling, leading to a rapid increase of the electrode resistance and fast capacity decline. The fundamental reason behind the poor structural and interfacial stability of NMC333 was found to be correlated to its high Co content and the significant overlap between the Co3+/4+ t2g and O2− 2p bands, resulting in oxygen removal and consequent structural changes at high voltages. In addition, oxidation of the electrolyte solvents by the extracted oxygen species generates acidic species, which then attack the electrode surface and form highly resistive LiF. These findings highlight that both the structural and interfacial stability should be taken into account when tailoring cathode materials for high voltage battery systems.

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Acknowledgements

This work is supported by the Assistant Secretary for Energy Efficiency and Renewable Energy, Office of Vehicle Technologies of the U.S. Department of Energy under Contract No. DE-AC02-05CH11231, Subcontract No. 18769, under the Advanced Battery Materials Research (BMR) program. The STEM/EELS/ToF-SIMS/XPS characterizations were carried out in the William R. Wiley Environmental Molecular Sciences Laboratory (EMSL), a national scientific user facility sponsored by DOE’s Office of Biological and Environmental Research and located at PNNL. PNNL is operated by Battelle for the DOE under Contract DE-AC05-76RLO1830.

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  1. Jianming Zheng and Pengfei Yan contributed equally to this work.

Authors and Affiliations

  1. Energy and Environment Directorate, Pacific Northwest National Laboratory, 902 Battelle Boulevard, Richland, WA, 99354, USA

    Jianming Zheng, Jie Xiao & Jiguang Zhang

  2. Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory, 3335 Innovation Boulevard, Richland, WA, 99354, USA

    Pengfei Yan, Jiandong Zhang, Mark H. Engelhard, Zihua Zhu & Chongmin Wang

  3. Chemical Sciences and Engineering Division, Argonne National Laboratory, 9700 South Cass Avenue, Argonne, IL, 60439, USA

    Bryant J. Polzin & Steve Trask

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  1. Jianming Zheng
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  2. Pengfei Yan
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  5. Zihua Zhu
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Correspondence to Chongmin Wang or Jiguang Zhang.

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Zheng, J., Yan, P., Zhang, J. et al. Suppressed oxygen extraction and degradation of LiNi x Mn y Co z O2 cathodes at high charge cut-off voltages. Nano Res. 10, 4221–4231 (2017). https://doi.org/10.1007/s12274-017-1761-6

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  • DOI: https://doi.org/10.1007/s12274-017-1761-6

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