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离子液体作为电化学双层电容器的电解质:优化比能量的结构。

Ionic Liquids as Electrolytes for Electrochemical Double-Layer Capacitors: Structures that Optimize Specific Energy.

机构信息

Department of Chemistry, University of Minnesota , 207 Pleasant Street S.E., Minneapolis, Minnesota 55455, United States.

Department of Theory and Bio-Systems, Max Planck Institute of Colloids and Interfaces , Science Park, Potsdam 14476, Germany.

出版信息

ACS Appl Mater Interfaces. 2016 Feb 10;8(5):3396-406. doi: 10.1021/acsami.5b11353. Epub 2016 Jan 27.

Abstract

Key parameters that influence the specific energy of electrochemical double-layer capacitors (EDLCs) are the double-layer capacitance and the operating potential of the cell. The operating potential of the cell is generally limited by the electrochemical window of the electrolyte solution, that is, the range of applied voltages within which the electrolyte or solvent is not reduced or oxidized. Ionic liquids are of interest as electrolytes for EDLCs because they offer relatively wide potential windows. Here, we provide a systematic study of the influence of the physical properties of ionic liquid electrolytes on the electrochemical stability and electrochemical performance (double-layer capacitance, specific energy) of EDLCs that employ a mesoporous carbon model electrode with uniform, highly interconnected mesopores (3DOm carbon). Several ionic liquids with structurally diverse anions (tetrafluoroborate, trifluoromethanesulfonate, trifluoromethanesulfonimide) and cations (imidazolium, ammonium, pyridinium, piperidinium, and pyrrolidinium) were investigated. We show that the cation size has a significant effect on the electrolyte viscosity and conductivity, as well as the capacitance of EDLCs. Imidazolium- and pyridinium-based ionic liquids provide the highest cell capacitance, and ammonium-based ionic liquids offer potential windows much larger than imidazolium and pyridinium ionic liquids. Increasing the chain length of the alkyl substituents in 1-alkyl-3-methylimidazolium trifluoromethanesulfonimide does not widen the potential window of the ionic liquid. We identified the ionic liquids that maximize the specific energies of EDLCs through the combined effects of their potential windows and the double-layer capacitance. The highest specific energies are obtained with ionic liquid electrolytes that possess moderate electrochemical stability, small ionic volumes, low viscosity, and hence high conductivity, the best performing ionic liquid tested being 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide.

摘要

影响电化学双层电容器 (EDLC) 比能的关键参数是双电层电容和电池的工作电位。电池的工作电位通常受电解质溶液电化学窗口的限制,即施加电压的范围在该范围内电解质或溶剂不会被还原或氧化。离子液体作为 EDLC 的电解质很有吸引力,因为它们提供了相对较宽的电位窗口。在这里,我们系统地研究了离子液体电解质的物理性质对采用具有均匀、高度互连介孔(3DOm 碳)的介孔碳模型电极的 EDLC 的电化学稳定性和电化学性能(双电层电容、比能)的影响。研究了几种具有结构不同的阴离子(四氟硼酸根、三氟甲烷磺酸根、三氟甲烷磺酰亚胺)和阳离子(咪唑鎓、铵、吡啶鎓、哌啶鎓、吡咯烷鎓)的离子液体。我们表明,阳离子大小对电解质的粘度和电导率以及 EDLC 的电容有显著影响。基于咪唑鎓和吡啶鎓的离子液体提供了最高的电池电容,而基于铵的离子液体提供的电位窗口比咪唑鎓和吡啶鎓离子液体大得多。增加 1-烷基-3-甲基咪唑鎓三氟甲烷磺酰亚胺中烷基取代基的链长不会拓宽离子液体的电位窗口。我们通过综合考虑其电位窗口和双电层电容,确定了使 EDLC 比能最大化的离子液体。通过使用具有中等电化学稳定性、较小离子体积、低粘度和高电导率的离子液体电解质,获得了最高的比能,测试性能最佳的离子液体是 1-乙基-3-甲基咪唑鎓双(三氟甲基磺酰基)亚胺。

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