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Surface Degradation of Lithium–Manganese Spinel in Contact with Lithium-Hexafluorophosphate-Containing Electrolyte Solution

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Abstract

A set of computational and experimental methods is used in the study of chemical side interactions in the LiMn2O4-based lithium-ion cathodic half-cell over the 25–60°C temperature range. The degradation of LiMn2O4-spinel-based electrodes is shown to start upon the LiMn2O4 granules contacting the standard (basic) electrolyte solution (1 m LiPF6 in a mixture of ethylene carbonate and dimethyl carbonate (1 : 1, by wt)). It is established that under current-less conditions, the degradation of the LiMn2O4-based electrode is caused by the mutual thermodynamic instability between LiMn2O4 and the LiPF6 lithium salt. The equilibrium interaction products are determined, and the mechanism of the critical temperature influence on the degradation of lithium-ion batteries with lithium–manganese spinel is refined. A model is proposed for the primary surface layer at the LiMn2O4/electrolyte interface formation and evolution, which explains the distinctive features of the degradation processes in this system.

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Funding

This work is performed under the State Contract of the Institute of Solid State Chemistry, Ural Branch, RAS, according to the topic no. 124020600047-4) and the Federal Research Center of Problems of Chemical Physics and Medicinal Chemistry, RAS, according to the topic no. 124013000692-4).

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  1. Institute of Solid State Chemistry, Ural Branch, Russian Academy of Sciences, Yekaterinburg, Russia

    A. A. Koshkina, T. V. Yaroslavtseva, M. V. Kuznetsov, V. T. Surikov & O. V. Bushkova

  2. Federal Research Center of Problems of Chemical Physics and Medicinal Chemistry, Russian Academy of Sciences, Chernogolovka, Russia

    A. E. Ukshe

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  1. A. A. Koshkina
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Koshkina, A.A., Yaroslavtseva, T.V., Ukshe, A.E. et al. Surface Degradation of Lithium–Manganese Spinel in Contact with Lithium-Hexafluorophosphate-Containing Electrolyte Solution. Russ J Electrochem 60, 263–282 (2024). https://doi.org/10.1134/S1023193524040049

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