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Decoupling the roles of Ni and Co in anionic redox activity of Li-rich NMC cathodes

Nature Materials volume 22, pages 1370–1379 (2023)Cite this article

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Abstract

Li[LixNiyMnzCo1−x−y−z]O2 (lithium-rich NMCs) are benchmark cathode materials receiving considerable attention due to the abnormally high capacities resulting from their anionic redox chemistry. Although their anionic redox mechanisms have been much investigated, the roles of cationic redox processes remain underexplored, hindering further performance improvement. Here we decoupled the effects of nickel and cobalt in lithium-rich NMCs via a comprehensive study of two typical compounds, Li1.2Ni0.2Mn0.6O2 and Li1.2Co0.4Mn0.4O2. We discovered that both Ni3+/4+ and Co4+, generated during cationic redox processes, are actually intermediate species for triggering oxygen redox through a ligand-to-metal charge-transfer process. However, cobalt is better than nickel in mediating the kinetics of ligand-to-metal charge transfer by favouring more transition metal migration, leading to less cationic redox but more oxygen redox, more O2 release, poorer cycling performance and more severe voltage decay. Our work highlights a compositional optimization pathway for lithium-rich NMCs by deviating from using cobalt to using nickel, providing valuable guidelines for future high-capacity cathode design.

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Fig. 1: Decomposing Li1.2Ni0.13Mn0.54Co0.13O2 as a linear combination of LNMO and LCMO.
Fig. 2: Redox mechanism of LNMO.
Fig. 3: Redox mechanism of LCMO.
Fig. 4: Operando X-ray diffraction of LNMO and LCMO.
Fig. 5: Electrochemical analysis of the LMCT process.

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Source data are provided with this paper. All data supporting the findings of this Article and its Supplementary Information will be made available upon reasonable request to the authors. Source data are provided with this paper.

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Acknowledgements

This research used resources of the Advanced Photon Source, a US Department of Energy (DOE) Office of Science User Facility, operated for the DOE Office of Science by Argonne National Laboratory under contract number DE-AC02-06CH11357, and resources of the Advanced Light Source, which is a DOE Office of Science User Facility under contract no. DE-AC02-05CH11231. Hard XAS experiments were performed on the ROCK beamline at the SOLEIL Synchrotron. We appreciate help from S. Mariyappan with performing the TGA and DSC experiments. A.V.M. and A.M.A. are grateful to the Russian Science Foundation for financial support (grant 23-73- 30003). J.-M.T and B.L. acknowledge funding from the European Research Council (ERC) (FP/2014)/ERC Grant-Project 670116-ARPEMA. We dedicate this article to J.B. Goodenough, as it deals with the layered oxides and fundamentals of electronic structure and redox chemistry in solid state that were so dear to the heart of John, the inspirer of so many of us.

Author information

Author notes

  1. Biao Li

    Present address: School of Materials Science and Engineering, Peking University, Beijing, P.R. China

Authors and Affiliations

  1. Chimie du Solide-Energie, UMR 8260, Collège de France, Paris, France

    Biao Li, Xu Gao & Jean-Marie Tarascon

  2. Réseau sur le Stockage Electrochimique de l’Energie (RS2E), FR CNRS 3459, Amiens, France

    Biao Li, Antonella Iadecola, Xu Gao & Jean-Marie Tarascon

  3. Advanced Light Source, Lawrence Berkeley National Laboratory, Berkeley, CA, USA

    Zengqing Zhuo, Jinghua Guo & Wanli Yang

  4. Department of Chemistry – Ångström Laboratory, Uppsala University, Uppsala, Sweden

    Leiting Zhang

  5. Skolkovo Institute of Science and Technology, Moscow, Russia

    Anatolii V. Morozov & Artem M. Abakumov

  6. Sorbonne Université, Paris, France

    Jean-Marie Tarascon

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Contributions

B.L. and J.-M.T. planned the project and designed the experiments. B.L. carried out the synthesis, structural characterization and electrochemical analysis. X.G. prepared some of the samples for RIXS and performed the operando XRD experiment of LNMCO compound. Z.Z., J.G. and W.Y. collected and analysed the RIXS and soft XAS data. A.I. collected and processed the hard XAS data. A.V.M. and A.M.A. performed TEM experiments and did the analysis. L.Z. performed the OEMS experiments and data analysis. B.L., J.-M.T. and A.M.A. discussed the results and wrote the paper with the contributions from all other authors.

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Correspondence to Jean-Marie Tarascon.

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Nature Materials thanks Valerie Pralong and Naoaki Yabuuchi for their contribution to the peer review of this work.

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Extended data

Extended Data Fig. 1 OEMS results of LNMO and LCMO.

OEMS results for (a–c) LNMO and (d–f) LCMO. The cells were cycled at a current density of 15 mA g-1. The amount of O2 and CO2 release were indicated. The loss of O was calculated as percentage of O in the formula and shown as the loss of stoichiometry. ‘P1’ and ‘P2’ label the CO2 release peaks corresponding to different originations but with different intensities in LNMO and LCMO. The first peak P1 starts at ~4 V and normally can be attributed to the chemical/electrochemical decomposition of surface Li2CO3 residue, and their evolution rates depend on the amount of surface carbonate residuals after synthesis. The second peak P2 at the end of charge generally originates from electrolyte decomposition, and can be partially related to the singlet O species generated during oxygen release that can react with electrolyte to form CO2. The smaller amount of CO2 release in LNMO can hence be explained by its smaller oxygen release or less oxidized oxygen (shorter 4.5 V plateau) compared with that of LCMO.

Extended Data Fig. 2 TEM results of LNMO and LCMO after 40 cycles.

TEM images of LNMO and LCMO before and after 40 cycles. (a) [010] and (b) [\(\bar{1}10\)] HAADF-STEM images and corresponding SAED patterns of discharged LNMO after 40 cycles. Main reflections in the SAED patterns can be indexed in the parent O3-trigonal structure (space group: R\(\bar{3}\)m), whereas additional h ± 1/2 0 l and h ± 1/2 k ± 1/2 l reflections appear in both [010] and [\(\bar{1}10\)] SAED patterns of cycled LNMO. These extra spots indicate a formation of a tetragonally distorted I41/amd spinel structure aroused from TM migration from their initial positions (3a) towards both empty Li sites (3b) and tetrahedrally coordinated interstices in FCC oxygen lattice. An interlayer migration of the TM cations to Li layers is also directly evidenced in HAADF-STEM images, since extra HAADF intensity is observed between the (Li,TM)O2 layers. Besides interlayer, pronounced irreversible intra-layer TM cation migration is clearly seen in (b) [\(\bar{1}10\)] HAADF-STEM, that is a typical sign of structure densification. However, in LNMO material the densified layer is confined to near surface area and does not exceed few nm in thickness, while the diffuse intensity lines (marked with white arrowheads) are recognizable in [\(\bar{1}10\)] SAED pattern as well as double-dot contrast typical for Li/TM ‘honeycomb’ ordering is preserved in a bulk part of LNMO. (c) [010] and (d) [\(\bar{1}10\)] HAADF-STEM images and corresponding SAED patterns of the discharged LСMO after 40 cycles. A large fraction of the TM cations moves to Li layers and tetrahedral voids forming spinel-like nano domains clearly visible in [010] HAADF-STEM image. The ‘honeycomb’ Li/M ordering is completely suppressed in cycled LCMO: no diffuse intensity is observed in [\(\bar{1}10\)] SAED patterns and the dots in Li/TM layers are uniformly spaced and have similar brightness in [\(\bar{1}10\)] HAADF-STEM image. Altogether, such significant structural degradation indicates much higher degree of ‘densification’ of LCMO, where it propagates through all observed area compared to LNMO where it is confined to the near-surface layer. The scale bar is 2 nm.

Supplementary information

Supplementary Information

Supplementary Figs. 1–29, Note I and Tables 1–7.

Source data

Source Data Fig. 1

Source data of electrochemical profiles and XRD refinements.

Source Data Fig. 2

Source data of electrochemistry and XAS.

Source Data Fig. 3

Source data of electrochemistry and XAS.

Source Data Fig. 4

Source data of electrochemistry and in situ XRD.

Source Data Fig. 5

Source data of electrochemistry.

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Li, B., Zhuo, Z., Zhang, L. et al. Decoupling the roles of Ni and Co in anionic redox activity of Li-rich NMC cathodes. Nat. Mater. 22, 1370–1379 (2023). https://doi.org/10.1038/s41563-023-01679-x

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