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Understanding Co roles towards developing Co-free Ni-rich cathodes for rechargeable batteries

Abstract

Current bottlenecks in cobalt (Co) supply have negatively impacted commercial battery production and inspired the development of cathode materials that are less reliant on Co. However, complete Co elimination is prevented by the lack of fundamental understanding of the impact of Co on cathode capacity and structural stability, as well as the lack of effective substitute components in practice. Here we investigate the roles of Co in purposely designed systems that include both Co-rich and Mn-substituted Co-free cathodes. Our results affirmed that Co plays an undeniable role in fast capacity and/or structural degradation, and found that Co is more destructive than Ni at high potentials, which offers unexpected but encouraging perspectives for Co reduction. Moreover, Mn substitution effectively alleviates the destructive effects of Co and enables a high potential functionality. With these fundamental discoveries, we demonstrated a series of LiNiαMnβXγO2 (X = single or multiple dopants) as a promising candidate for Co-free cathodes.

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Fig. 1: Quantitative atomic occupancy analysis via HEXRD refinements and aberration-corrected high-resolution TEM.
Fig. 2: Electrochemical measurements of NC64, NMC622 and NM64.
Fig. 3: In situ synchrotron HEXRD characterization during the first charge/discharge.
Fig. 4: TM oxidation states and gas-generation measurements for three comparable samples.
Fig. 5: TEM observations of NC64 after cycling.
Fig. 6: Structure and oxygen reversibility for NC64 and NM64.
Fig. 7: Structural evolution mechanisms for Co-rich and Co-free cathodes.
Fig. 8: Prospective Co-free LiNiαMnβXγO2 cathode materials.

Data availability

All the relevant data are included in the paper and its Supplementary Information.

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Acknowledgements

We acknowledge support from the US Department of Energy (DOE), Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (VTO). This work was also supported by Clean Vehicles, US–China Clean Energy Research Centre (CERC-CVC2) under the US DOE EERE Vehicle Technologies Office. Argonne National Laboratory is operated for the DOE Office of Science by the UChicago Argonne, LLC, under contract no. DE-AC02-06CH11357. This research was partially supported by the National Key R&D Program of China (2016YFB0700600), the Guangdong Innovation Team Project (no. 2013N080), the Soft Science Research Project of Guangdong Province (no. 2017B030301013) and the Shenzhen Science and Technology Research Grants (no. ZDSYS201707281026184). T.L. thanks F.P. for the supervision and consultation on this work during his PhD study. This research used resources of the Advanced Photon Source (11-ID-C and 9-BM), a US Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under Contract no. DE-AC02-06CH11357. This work was performed including electron microscopy, in part, at the Center for Nanoscale Materials, a US Department of Energy Office of Science User Facility, and supported by the US Department of Energy, Office of Science, under Contract no. DE-AC02-06CH11357.

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Contributions

T.L., J. Lu, K.A. and F.P. conceived the idea and designed the experiments. T.L., Maofan Li and J. Liu synthesized all the materials. T.L. and Y.R. carried out the in situ and ex situ synchrotron XRD results. T.L., L.M. and T.W. performed ex situ synchrotron XAS. Z.H., J.Z. and F.P. conducted the density functional theory calculations. T.L., A.D., Matthew Li and X.B. carried out the electrochemical measurements and analysis. L.Y., D.L. and J.W. conducted the TEM measurements. T.L., A.D., J. Lu, K.A and F.P. wrote the manuscript and all the authors edited the manuscript.

Corresponding authors

Correspondence to Jun Lu or Feng Pan or Khalil Amine.

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The authors declare no competing interests.

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Peer review information Nature Energy thanks Xinping Ai and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Supplementary Information

Supplementary Figs. 1–29, Discussion and Tables 1–5.

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Liu, T., Yu, L., Liu, J. et al. Understanding Co roles towards developing Co-free Ni-rich cathodes for rechargeable batteries. Nat Energy 6, 277–286 (2021). https://doi.org/10.1038/s41560-021-00776-y

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