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Unveiling the impact of residual Li conversion and cation ordering on electrochemical performance of Co-free Ni-rich cathodes

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Abstract

The residual Li and Li+/Ni2+ cation mixing play essential roles in the electrochemical properties of Ni-rich cathodes. However, a general relationship between the residual Li conversion, cation mixing, and their effects on the Li+ kinetics and structural stability has yet to be established, due to the presence of cobalt in the cathode. Here, we explore the synergistic impact of the residual Li conversion and cation ordering on a Co-free Ni-rich cathode (i.e., LiNi0.95Mn0.05O2). It discloses that the rate capability is mainly affected by residual Li contents and operating voltage. Specifically, residual Li can be electrochemically converted to cathode electrolyte interphase (CEI) below 4.3 V, thus inducing high interphase resistance, and decomposes to produce CO2-dominated gas at 4.5 V, causing temporary enhancement of Li+ diffusivity but severe surface degradation during cycling. Moreover, the cycling performance of Co-free Ni-rich cathode is not only determined by Li+/Ni2+ cation-ordered superlattice, which enhances the structural stability as it functions as the pillar to impede lattice collapse at a highly charged state, but also by the robust CEI layers which protect the bulk from electrolyte attack under 4.3 V. These findings promote an in-depth understanding of residual Li conversion and Li+/Ni2+ cation ordering on Co-free Ni-rich cathode.

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Acknowledgement

This work was financially supported by the National Natural Science Foundation of China (No. 51774051), the Science and Technology Planning Project of Hunan Province (No. 2019RS2034), the Hunan High-tech Industry Science and Technology Innovation Leading Plan (No. 2020GK2072), and the Changsha City Fund for Distinguished and Innovative Young Scholars (No. KQ1707014).

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Authors and Affiliations

  1. School of Materials Science and Engineering, Changsha University of Science and Technology, Changsha, 410114, China

    Chu Wang, Hongling Yi, Zixiang Zhao & Lingjun Li

  2. School of Energy and Power Engineering, Changsha University of Science and Technology, Changsha, 410114, China

    Lei Tan

  3. School of Metallurgy and Environment, Central South University, Changsha, 410083, China

    **aoli Yi, Junchao Zheng & Jiexi Wang

  4. Hunan Changyuan Lico Co., Ltd., Changsha, 410205, China

    Youyuan Zhou

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  1. Chu Wang
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Correspondence to Lingjun Li.

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12274_2022_4889_MOESM1_ESM.pdf

Unveiling the impact of residual Li conversion and cation ordering on electrochemical performance of Co-free Ni-rich cathodes

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Wang, C., Tan, L., Yi, H. et al. Unveiling the impact of residual Li conversion and cation ordering on electrochemical performance of Co-free Ni-rich cathodes. Nano Res. 15, 9038–9046 (2022). https://doi.org/10.1007/s12274-022-4889-0

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