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Operando Br K-edge dispersive X-ray absorption fine structure analysis for Br$$^{-}$$/Br$$_{3}$$$$^{-}$$ redox mediator for Li-Air batteries

臭素K吸収端のオペランド分散型XAFS測定によるリチウム空気電池の臭素酸化還元反応の解析

伊藤 仁彦*; 松村 大樹   ; Song, C.*; 久保 佳美*

Ito, Kimihiko*; Matsumura, Daiju; Song, C.*; Kubo, Yoshimi*

The behavior of Br$$^{-}$$/Br$$_{3}^{-}$$ redox mediator (RM), which has been shown to suppress charging overpotential in lithium-air batteries, has been detected for the first time using operando Br K-edge dispersive X-ray absorption fine structure. Br$$_{3}^{-}$$ ions in the electrolyte increase monotonically after $$sim$$ 30% charging, which indicates that a part of Br$$_{3}^{-}$$ formed via the oxidation of Br$$^{-}$$ during charging does not oxidize Li$$_{2}$$O$$_{2}$$ as RM but gets accumulated in the cell. Consistent with this result, the O$$_{2}$$ evolution efficiency gradually decreases from the initial 100% as the charging progresses, and CO$$_{2}$$ is emitted at the end of the charging. All these results clearly show that the Br$$^{-}$$/Br$$_{3}^{-}$$ RM functions effectively at the beginning of charging but gradually loses its function as charging proceeds.

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パーセンタイル:31.35

分野:Chemistry, Physical

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