Some thermodynamic and transport properties of lithium salts in mixed aprotic solvents and the effect of water on such properties

In a continuing study on the optimization of the electrolyte medium for high-energy lithium batteries, volumes, heat capacities, and specific conductivities of LiClO 4 and LiBr were measured in mixtures of γ-butyrolactone (BUTY) and 1,2-dimethoxyethane (DME) and of propylene carbonate (PC) and BUTY. These results are compared with those of the electrolytes in the pure solvents. Phase diagrams are also reported when appropriate. The effect of addition of water to these binary and ternary systems was investigated with the same techniques. The mixtures DME–BUTY, PC–DME, DME–H 2 O, and BUTY–H 2 O are typical of mixtures of aprotic solvents and mixtures of aprotic solvents and water. The electrolytes at high concentrations in aprotic solvents of low dielectric constants are largely associated. The medium still conducts electrolytically since the ion pairs are in a state that resembles to a large extent that of a molten salt. With some systems at high concentration, stable solvates persist in the solution medium, as evidenced mostly by heat capacities, and are in equilibrium with either the excess solvent or unsolvated molten salts. In mixed solvents, the properties of electrolytes can largely be predicted from the binary systems and by the coexistence of these solvates. The properties of water in DME, BUTY, or mixtures of the two solvents are modified significantly in the presence of LiBr but only slightly with LiClO 4 . These specific interactions, which affect the heat capacities much more than the volumes and which are especially large with the system LiBr–DME, could be responsible for the decrease in reactivity of water with lithium metal in an aprotic medium in the presence of certain electrolytes. Key words: LiClO 4 , LiBr, γ-butyrolactone, dimethoxyethane, propylene carbonate, lithium battery, aprotic solvent, water, association, solvates, solid–liquid phase diagrams, volumes, heat capacities, specific conductivities.