Intermolecular Interactions and Electrochemical Studies on Highly Concentrated Acetate-Based Water-in-Salt and Ionic Liquid Electrolytes

Abstract

Water-in-salt electrolytes constitute a new class of materials that have distinct properties relative to lower-concentration solutions. A recent approach to further increase the salt concentration and decrease the water content includes the addition of an ionic liquid to a highly concentrated aqueous solution. However, the physicochemical and electrochemical properties of aqueous lithium acetate-1-ethyl-3-methylimidazolium acetate solutions as well as the molecular interactions between electrolyte species have not been characterized. Here, we investigate these properties by evaluation of the ionic conductivity, viscosity, and thermal properties as well as the electrochemical behavior of various electrodes in these electrolytes. The intermolecular interactions are probed by nuclear magnetic resonance and infrared spectroscopies. We find that the addition of the ionic liquid increases the solubility limit of lithium acetate and that with an increase in both acetate salt and ionic liquid concentration in the electrolyte and decrease in water concentration, a strong acetate-water network is formed. The electrochemical stability window increases upon addition of the ionic liquid and reaches a value larger than 5 V for a set of negative Al and positive Ti electrodes in the highest acetate salt/ionic liquid concentration. Preliminary electrochemical charge storage performance measurements of a symmetric device based on two porous carbon electrodes cycled at a current density of 25 mA g-1 delivered a specific capacitance of 20 F g-1 with a Coulombic efficiency higher than 99% using a 1.8 V voltage window.