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The structural and chemical origin of the oxygen redox activity in layered and cation-disordered Li-excess cathode materials

Nature Chemistry volume 8, pages 692–697 (2016)Cite this article

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Abstract

Lithium-ion batteries are now reaching the energy density limits set by their electrode materials, requiring new paradigms for Li+ and electron hosting in solid-state electrodes. Reversible oxygen redox in the solid state in particular has the potential to enable high energy density as it can deliver excess capacity beyond the theoretical transition-metal redox-capacity at a high voltage. Nevertheless, the structural and chemical origin of the process is not understood, preventing the rational design of better cathode materials. Here, we demonstrate how very specific local Li-excess environments around oxygen atoms necessarily lead to labile oxygen electrons that can be more easily extracted and participate in the practical capacity of cathodes. The identification of the local structural components that create oxygen redox sets a new direction for the design of high-energy-density cathode materials.

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Figure 1: Effect of local atomic environments on the electronic states of O ions in cation-mixed layered LiNiO2.
Figure 2: Effect of Li–O–Li configurations on the electronic states of O ions in Li2MnO3.
Figure 3: Illustrations of preferred oxygen oxidation along the Li–O–Li configuration in various Li-excess materials.
Figure 4: Structural and chemical origin of the preferred oxygen oxidation along the Li–O–Li configuration.

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Acknowledgements

This work was supported by Robert Bosch Corporation and Umicore Specialty Oxides and Chemicals, and by the Assistant Secretary for Energy Efficiency and Renewable Energy, Office of Vehicle Technologies of the US Department of Energy under contract no. DE-AC02–05CH11231, under the Batteries for Advanced Transportation Technologies (BATT) Program subcontract no. 7056411. This work used the Extreme Science and Engineering Discovery Environment (XSEDE), which is supported by National Science Foundation grant no. ACI-1053575, and resources of the National Energy Research Scientific Computing Center (NERSC), a DOE Office of Science User Facility supported by the Office of Science of the US Department of Energy under contract no. DE-C02-05CH11231. D.-H.S. acknowledges support from the Basic Science Research Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Education (2014R1A6A3A03056034). J.L. acknowledges financial support from a Samsung Scholarship.

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Author notes

  1. Dong-Hwa Seo and Jinhyuk Lee: These authors contributed equally to this work

Authors and Affiliations

  1. Department of Materials Science and Engineering, Massachusetts Institute of Technology, Cambridge, 02139, Massachusetts, USA

    Dong-Hwa Seo, Jinhyuk Lee, Rahul Malik, ShinYoung Kang & Gerbrand Ceder

  2. Department of Materials Science and Engineering, UC Berkeley, Berkeley, 94720, California, USA

    Dong-Hwa Seo, Jinhyuk Lee, Alexander Urban & Gerbrand Ceder

  3. Materials Science Division, Lawrence Berkeley National Laboratory, Berkeley, 94720, California, USA

    Gerbrand Ceder

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Contributions

G.C. planned the project, supervised all aspects of the research, contributed to the main theory and to writing the manuscript. D.-H.S. and J.L. conceived and designed project details. D.-H.S. performed DFT calculations. D.-H.S. and J.L. analysed the data. J.L. and D.-H.S. developed the main theory and authored the manuscript. D.-H.S and J.L. contributed equally to this work. A.U. and S.Y.K. performed preliminary DFT calculations. A.U. and R.M. assisted in data analysis and in writing the manuscript.

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Correspondence to Gerbrand Ceder.

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Seo, DH., Lee, J., Urban, A. et al. The structural and chemical origin of the oxygen redox activity in layered and cation-disordered Li-excess cathode materials. Nature Chem 8, 692–697 (2016). https://doi.org/10.1038/nchem.2524

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