The confinement and anion type effect on the physicochemical properties of ionic liquid/halloysite nanoclay ionogels

Abstract

This work is the first attempt to study the physicochemical properties of ionogels - quasi-solid hybrid materials formed by ionic liquids (ILs) − 1-butyl-3-methylimidazolium (BMIm+) salts with dicyanamide- (DCA−), bis(trifluoromethylsulfonyl)imide- (TFSI−), and trifluoromethanesulfonate- (Otf−) anions - and halloysite, a powdered clay filler with nanotube particles (at the IL:Hal molar ratio of 2:1) in order to find possible new applications of ionic liquids and industrial minerals. The electron microscopy, TG, and DSC analysis, FTIR spectroscopy, X-ray diffraction analysis, conductometry and cyclic voltammetry methods are used to investigate the anion effect on the IL interaction with halloysite. It has, for the first time, been found that the distinguishing feature of halloysite interaction with an IL determining the structural changes in the clay mineral and electrochemical characteristics of the ionogels is partial dehydration of the clay and absorption of the released water by the ionic liquid. It is shown that the halloysite dehydration effect depends on the IL hydrophilicity determined by the anion type, corresponds to the series: BMImDCA > BMImOtf > BMImTFSI. The electrochemical and thermal behaviour of ILs confined within a halloysite matrix differs from that of bulk ILs and is controlled by the anion type. Temperature dependences of the structural resistance of the halloysite filler are radically different for the ILs with high and low hydrophilicity. The effects resulting from the formation of halloysite-based ionogels can be of interest to those who develop quasi-solid ionic conductors that can work within a wide temperature range.

Keywords

• Ionogels
• Halloysite
• Ionic liquids
• Structural characteristics
• Thermal destruction
• Ionic conductivity