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残留微量水对含镁电解质疏水性离子液体电化学性能的影响

Influence of Residual Water Traces on the Electrochemical Performance of Hydrophobic Ionic Liquids for Magnesium-Containing Electrolytes.

作者信息

Elkhafif Omar W, Hassan Hagar K, Ceblin Maximilian U, Farkas Attila, Jacob Timo

机构信息

Institute of Electrochemistry, Ulm University, Albert-Einstein-Allee 47, 89081, Ulm, Germany.

Helmholtz Institute Ulm (HIU) - Electrochemical Energy Storage, Helmholtzstr. 11, D-89081, Ulm, Germany.

出版信息

ChemSusChem. 2023 Oct 6;16(19):e202300421. doi: 10.1002/cssc.202300421. Epub 2023 Jul 31.

DOI:10.1002/cssc.202300421
PMID:37338003
Abstract

A trace amount of water is typically unavoidable as an impurity in ionic liquids, which is a huge challenge for their application in Mg-ion batteries. Here, we employed molecular sieves of different pore diameters (3, 4, and 5 Å), to effectively remove the trace amounts of water from 1-methyl-1-propylpiperidinium bis(trifluoromethylsulfonyl)imide (MPPip-TFSI) and 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide (BMP-TFSI). Notably, after sieving (water content <1 mg ⋅ L ), new anodic peaks arise that are attributed to the formation of different anion-cation structures induced by minimizing the influence of hydrogen bonds. Furthermore, electrochemical impedance spectroscopy (EIS) reveals that the electrolyte resistance decreases by ∼10 % for MPPip-TFSI and by ∼28 % for BMP-TFSI after sieving. The electrochemical Mg deposition/dissolution is investigated in MPPip-TFSI/tetraglyme (1 : 1)+100 mM Mg(TFSI) +10 mM Mg(BH ) using Ag/AgCl and Mg reference electrodes. The presence of a trace amount of water leads to a considerable shift of 0.9 V vs. Mg Mg in the overpotential of Mg deposition. In contrast, drying of MPPip-TFSI enhances the reversibility of Mg deposition/dissolution and suppresses the passivation of the Mg electrode.

摘要

作为离子液体中的杂质,痕量水通常是不可避免的,这对其在镁离子电池中的应用构成了巨大挑战。在此,我们使用了不同孔径(3、4和5埃)的分子筛,以有效去除1-甲基-1-丙基哌啶双(三氟甲基磺酰)亚胺(MPPip-TFSI)和1-丁基-1-甲基吡咯烷双(三氟甲基磺酰)亚胺(BMP-TFSI)中的痕量水。值得注意的是,筛分后(水含量<1毫克·升),出现了新的阳极峰,这归因于通过最小化氢键的影响而形成的不同阴离子-阳离子结构。此外,电化学阻抗谱(EIS)显示,筛分后,MPPip-TFSI的电解质电阻降低了约10%,BMP-TFSI的电解质电阻降低了约28%。使用Ag/AgCl和Mg参比电极,在MPPip-TFSI/四甘醇二甲醚(1∶1)+100毫摩尔Mg(TFSI)+10毫摩尔Mg(BH)中研究了电化学镁沉积/溶解。痕量水的存在导致镁沉积过电位相对于Mg/Mg有0.9伏的显著偏移。相比之下,MPPip-TFSI的干燥增强了镁沉积/溶解的可逆性,并抑制了镁电极的钝化。

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