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Chemical factors controlling the behaviour of oxide cathodes in batteries

Nature Energy (2026)Cite this article

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Abstract

Oxide cathodes enable high-energy lithium-ion and sodium-ion batteries, with their performances fundamentally governed by three interrelated chemical factors: electronic configuration, chemical bonding and chemical reactivity. Here we illustrate how these factors dictate the redox energy, structural stability, ionic and electronic transport, and interfacial behaviour in both layered oxide and polyanion oxide cathodes. We discuss how crystal field effects and octahedral-site stabilization energies influence cation migration, and how inductive effects tune bond covalency and operating voltages. We also explain how chemical bonding governs thermal stability, gas evolution and first-cycle capacity loss, and how alignment of the transition metal redox band with the oxygen 2p band determines electrolyte reactivity. A comparison between lithium and sodium layered oxides further reveals how differences in Li–O and Na–O bond ionicity affect chemical reactivity. Finally, we outline strategies, including compositional tuning, surface doping and electrolyte optimization, for the development of new materials with improved performance, and emphasize how high-throughput, data-driven approaches can offer guidance for the design of next-generation oxide cathodes.

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Fig. 1: Battery performance metrics and influencing factors.
Fig. 2: Influence of electronic configuration on the oxide cathode performance.
Fig. 3: Influence of chemical bonding on the oxide cathode performance.
Fig. 4: Influence of chemical reactivity on the oxide cathode performance.
Fig. 5: Comparison between lithium and sodium layered oxide cathodes.

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Acknowledgements

This work was supported by the US Department of Energy, Office of Basic Energy Sciences, Division of Materials Science and Engineering under award number DE-SC0005397 and the Assistant Secretary for Energy Efficiency and Renewable Energy (EERE), Office of Vehicle Technologies of the US Department of Energy through the Advanced Battery Materials Research (BMR) Program (Battery500 Consortium) award number DE-AC05-76RLO1830.

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  1. Walker Department of Mechanical Engineering, The University of Texas at Austin, Austin, TX, USA

    Arumugam Manthiram & Zehao Cui

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  1. Arumugam Manthiram
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A.M. and Z.C. conceived the idea and wrote the paper. A.M. supervised the work.

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Correspondence to Arumugam Manthiram.

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Competing interests

A.M. is a co-founder of TexPower EV Technologies, a company focusing on cobalt-free cathode materials for lithium-based batteries. Z.C. declares no competing interests.

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Nature Energy thanks Gui-Liang Xu, Lin Gu and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Manthiram, A., Cui, Z. Chemical factors controlling the behaviour of oxide cathodes in batteries. Nat Energy (2026). https://doi.org/10.1038/s41560-025-01963-x

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