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Fundamental understanding and practical challenges of anionic redox activity in Li-ion batteries

Nature Energy volume 3, pages 373–386 (2018)Cite this article

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Abstract

Our increasing dependence on lithium-ion batteries for energy storage calls for continual improvements in the performance of their positive electrodes, which have so far relied solely on cationic redox of transition-metal ions for driving the electrochemical reactions. Great hopes have recently been placed on the emergence of anionic redox—a transformational approach for designing positive electrodes as it leads to a near-doubling of capacity. But questions have been raised about the fundamental origins of anionic redox and whether its full potential can be realized in applications. In this Review, we discuss the underlying science that triggers a reversible and stable anionic redox activity. Furthermore, we highlight its practical limitations and outline possible approaches for improving such materials and designing new ones. We also summarize their chances for market implementation in the face of the competing nickel-based layered cathodes that are prevalent today.

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Fig. 1: Crystal structures and electrochemical properties of layered oxides.
Fig. 2: Band structure of oxides and the anionic redox mechanism.
Fig. 3: Materials exploration pathway for Li-rich oxides.
Fig. 4: Practical challenges facing Li-rich cathodes.
Fig. 5: Benchmarking Li-rich NMC against NMCs.

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Acknowledgements

We thank M.-L. Doublet and M. Saubanère for valuable discussions on the theoretical aspects, and A. Grimaud, A. Abakumov, J. Vergnet, G. Rousse, A Pérez, Q. Jacquet, M. Sathiya, P. Pearce and A. Georges for sharing their knowledge and comments. J.-M.T. and G.A. acknowledge the funding from the European Research Council (ERC) (FP/2014)/ERC Grant-Project 670116-ARPEMA.

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  1. Collège de France, Chimie du Solide et de l’Energie—UMR CNRS 8260, Paris, France

    Gaurav Assat & Jean-Marie Tarascon

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

    Gaurav Assat & Jean-Marie Tarascon

  3. Sorbonne Universités, UPMC Université Paris 06, Paris, France

    Gaurav Assat & Jean-Marie Tarascon

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Assat, G., Tarascon, JM. Fundamental understanding and practical challenges of anionic redox activity in Li-ion batteries. Nat Energy 3, 373–386 (2018). https://doi.org/10.1038/s41560-018-0097-0

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