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Article Dans Une Revue Journal of The Electrochemical Society Année : 2021

Evolution of Oxygen Ligands upon Large Redox Swings of Li 3 IrO 4

Résumé

The limits of intercalation electrochemistry continue to be tested in the quest for ever increasing gains in the storage capability of Li-ion cathodes. The subsequent push for multi-electron reactivity has led to the recognition of the extremely versatile role of oxide ligands in charge compensation when there is a large redox swing. Li 3 IrO 4 is a unique model of such activity because it can reversibly cycle between Li 1 IrO 4 and Li 4.7 IrO 4. Here, X-ray spectroscopy, magnetic measurements and computational simulations uncover the evolution of O states in the different steps, compared to the involvement of Ir. While the process between Li 1 IrO 4 and Li 3 IrO 4 is dominated by the unconventional lattice oxygen redox, the process between Li 3 IrO 4 and Li 4.7 IrO 4 involves a conventional change of the formal oxidation state of Ir, which affects O due to the high covalency. The O states of Li 3 IrO 4 exhibit a very high reversibility after the whole 3.7-electron process, completely restoring the pristine state.
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Dates et versions

hal-03835068 , version 1 (31-10-2022)

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Haifeng Li, Arnaud J Perez, Beata Taudul, Teak D Boyko, John W Freeland, et al.. Evolution of Oxygen Ligands upon Large Redox Swings of Li 3 IrO 4. Journal of The Electrochemical Society, 2021, 168 (6), pp.060541. ⟨10.1149/1945-7111/ac0ad4⟩. ⟨hal-03835068⟩
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