Theory of Phase Separation and Polarization for Pure Ionic Liquids

Room temperature ionic liquids are attractive to numerous applications and particularly, to renewable energy devices. As solvent free electrolytes, they demonstrate a paramount connection between the material morphology and Coulombic interactions: the electrode/RTIL interface is believed to be a product of both polarization and spatiotemporal bulk properties. Yet, theoretical studies have dealt almost exclusively with independent models of morphology and electrokinetics. Introduction of a distinct Cahn-Hilliard-Poisson type mean-field framework for pure molten salts (i.e., in the absence of any neutral component), allows a systematic coupling between morphological evolution and the electrokinetic phenomena, such as transient currents. Specifically, linear analysis shows that spatially periodic patterns form via a finite wavenumber instability and numerical simulations demonstrate that while labyrinthine type patterns develop in the bulk, lamellar structures are favored near charged surfaces. The results demonstrate a qualitative phenomenology that is observed empirically and thus, provide a physically consistent methodology to incorporate phase separation properties into an electrochemical framework.