Influence of Water on Structure, Dynamics, and Electrostatics of Hydrophilic and Hydrophobic Ionic Liquids in Charged and Hydrophilic Confinement between Mica Surfaces.

Abstract

Water is ubiquitous in the environment and is the origin for operational constraints in ionic-liquid based electrolytes for supercapacitors. In this study, the influence of water on the interfacial behavior of hydrophilic (1-ethyl-3-methylimidazolium ethylsulfate, abbr. [EMIM][EtSO4]) and hydrophobic (1-ethyl-3-methylimidazolium tris(pentafluoroethyl)trifluorophosphate and 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, abbr. [EMIM][FAP] and [EMIM][TFSI], respectively) ionic liquids (ILs) confined between mica surfaces was investigated at separations precisely modulated by a surface force apparatus and at controlled relative humidity between 0% and 50% RH. Diffusion experiments revealed that water spontaneously invades the nanoconfined ILs above a certain humidity threshold and that the confined hydrophobic IL is completely replaced by water at sufficiently high environmental humidity (∼45% here) as a result of surface-induced phase separation. This behavior is expected to be universal for other ILs that are not fully miscible with water when they are confined in hydrophilic nanopores of a few nanometers in width. The effect of environmental humidity on interfacial structure, dynamics, and electrostatics was studied via dynamic force measurements. In the dry state, several layers of ions are immobilized on the mica surface, and the effective viscosity increases by up to 2 orders of magnitude with a decrease in film thickness from ∼10 to ∼3 nm. Based on recent work, it is proposed that nanoconfinement enhances the anion-cation association in highly concentrated electrolytes, thereby justifying the loss of fluidity of the ILs. When phase separation is excluded, water is intercalated in the layered structure of the three ILs, and it leads to a change of the layer thickness compared to the dry state. Furthermore, our results reveal that interfacial water prevents ions from being immobilized on the surface and facilitates the outflow of both hydrophilic and hydrophobic ILs by reducing their effective viscosity in the order [EMIM][FAP] < [EMIM][TFSI] < [EMIM][EtSO4]. The underlying mechanisms are evaluated by considering the roles of water in enhancing ion dissociation through screening of electrostatic interactions and solvation of the selected ILs to different extents. The discussed experimental observations support the recent discoveries made by molecular dynamic simulations and neutron scattering studies that using hydrophilic ILs coupled with water as cosolvent could lead to the enhanced power density of IL-based supercapacitors, and therefore, that water-in-(hydrophilic) ILs is a direction worth exploring as electrolytes for supercapacitors.