The highly desirable characteristics of ternary mixtures of ionic liquids, organic solvents, and metal salts make them a promising candidate for use in various electrothermal energy storage and conversion systems. In this study, using large-scale classical molecular dynamics simulations, we looked into 10 different ternary electrolyte mixtures using combinations of [EMIM]+, [BMIM]+, and [OMIM]+ cations with [NO3]-, [BF4]-, [PF6]-, [ClO4]-, [TFO]-, and [NTf2]- anions, tetraglyme, and Li salt to study the effect of ionic liquid composition on the phase behavior of ternary electrolyte mixtures. We uncovered that in these electrolytes, phase separation is mainly a function of pairwise binding energy of the constituents of the mixture. To corroborate this theory, several simulations are performed at various temperatures ranging from 260 to 500 K for each mixture, followed by calculating the binding energy of ionic liquid pairs using density functional theory. Our results verify that the transition temperature for the phase separation of each system is indeed a function of the pairwise binding energy of its ionic liquid pairs. It is also found that in some cases, the diffusion coefficient of the Li+ ions decreased even with the increase in the temperature, an effect that is attributed to the presence of condensed ionic domains in the electrolyte. This study provides a new insight for the design of multicomponent electrolyte mixtures for a wide range of energy applications.