表面技術
Online ISSN : 1884-3409
Print ISSN : 0915-1869
ISSN-L : 0915-1869
研究論文
イオン液体-Grignard試薬混合電解液におけるマグネシウムレドックス特性の経時変化
北田 敦姜 唯宇深見 一弘邑瀬 邦明
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2019 年 70 巻 4 号 p. 210-214

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For use in room-temperature electrodeposition of magnesium(Mg)metal, aging variation was studied to assess the electrochemical properties of a mixed system: an ionic liquid(IL)and a Grignard reagent. Cyclic voltammograms of a mixture of an IL, i.e. trimethylhexylammonium bis(trifluoromethylsulfonyl)amide(TMHA-Tf2N; Tf=CF3SO2), and a Grignard reagent, i.e., ethylmagnesium bromide(EtMgBr)in tetrahydrofuran(THF), showed redox currents for Mg metal deposition and dissolution. Similarly to other IL-Grignard mixed electrolyte solutions, the mixture examined in this study was found to have larger redox current than neat Grignard electrolyte solutions. Voltammograms for one-day-aged TMHA-Tf2N-EtMgBr-in-THF mixtures showed smaller or almost no redox current. Furthermore, adding a Grignard reagent to the one-day-aged IL-Grignard mixture did not improve the electrochemical properties. Therefore, redox property deterioration was not attributable to a sizable decrease in the electrochemically active species or a shift of the Schlenk equilibrium in 2EtMgBr ↔ Et2Mg+MgBr2. From our results, we speculate that Lewis acidic IL cations and Lewis basic Grignard species reacted gradually to form redox-inactive species or inhibitor(s)for the electrochemical deposition of Mg.

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