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Pushing the limit of 3d transition metal-based layered oxides that use both cation and anion redox for energy storage

Abstract

Intercalation chemistry has dominated electrochemical energy storage for decades, and storage capacity worldwide has now reached the terawatt-hour level. State-of-the-art intercalation cathodes for Li-ion batteries operate within the limits of transition metal cation electrochemistry, but the discovery of anion-redox processes in recent decades suggests rich opportunities for substantially increasing stored energy densities. The diversity of compounds that exhibit anion redox in the solid state has inspired the exploration of new materials for next-generation cathodes. In this Review, we outline the mechanisms proposed to contribute to anion redox and the accompanying kinetic pathways that can occur in layered transition metal oxides. We discuss the crucial role of structural changes at both the atomic and mesoscopic scales with an emphasis on their impact on electrochemical performance. We emphasize the need for an integrated approach to studying the evolution of both the bulk structure and electrode–electrolyte interphase by combining characterization with computation. Building on the fundamental understanding of electrochemical reaction mechanisms, we discuss engineering strategies such as composition design, surface protection and structural control to achieve stable anion redox for next-generation energy storage devices.

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Fig. 1: Crystal structures of different types of layered oxides.
Fig. 2: Relationship between voltage curves and Gibbs free energy.
Fig. 3: Common features of voltage curves for Li-excess layered oxides.
Fig. 4: Distinct redox mechanisms for Li-excess layered oxides.
Fig. 5: Structural evolution scenarios during or after oxygen-redox activation.
Fig. 6: Characterization tools for addressing capacity contributions and assigning the oxygen-redox mechanism.
Fig. 7: Advanced analytical electron microscopy for studying anion-redox mechanisms in Li-excess layered oxides.
Fig. 8: Impact of sample composition on reversible and stable oxygen redox in Li-excess materials.

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Acknowledgements

The authors acknowledge funding support from the NorthEast Center for Chemical Energy Storage (NECCES), an Energy Frontier Research Center funded by the US Department of Energy, Office of Science, Office of Basic Energy Sciences under Award No. DE-SC0012583. The authors thank J.-M. Doux, W. Li, H. Chung and B. Sayahpour for their help in preparing the electrochemical performance summary (Supplementary Table 2) from published papers.

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Zhang, M., Kitchaev, D.A., Lebens-Higgins, Z. et al. Pushing the limit of 3d transition metal-based layered oxides that use both cation and anion redox for energy storage. Nat Rev Mater 7, 522–540 (2022). https://doi.org/10.1038/s41578-022-00416-1

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