Conductivity of Ionic Liquids In the Bulk and during Infiltration in Nanopores

The conductivity of ionic liquids (ILs) in nanopores is essential when considering their application as materials for energy. However, no consensus has been reached about the influence of confinement on the mobility of the ions. A series of ILs bearing the same cation, 1-butyl-3-methylimidazolium ([BMIM]⁺), and six different anions ([Cl]^-, [Br]^-, [I]^-, [BF₄]^-, [PF₆]^-, and [TFSI]^-) with radii from 0.168 to 0.326 nm were investigated with respect to their self-assembly, the thermodynamics, and the ionic conductivity in the bulk, during flow and under confinement in cylindrical nanopores with sizes in the range from 400 to 25 nm. In the bulk, the [BMIM]⁺[X]^- exhibits weak ordering as a result of cation-anion correlations (charge alteration peak), and nanophase separation of polar/apolar groups. Liquid-to-glass temperatures were found to differ by ∼50 K, their viscosities by a factor of ∼270, and their conductivities by a factor of 24 (all at a temperature of 303 K). Electrostatic interactions were largely responsible for variations in the glass temperature, the viscosity, and the conductivity. Confined ILs behave differently from the bulk. The majority of ILs in the bulk were prone to crystallization during heating but were unable to crystallize in the smaller pores. Changes in dc-conductivity were used as markers of the phase state. This allowed the construction of the effective phase diagrams under confinement. The ILs penetrate the pores with an effective viscosity of the order of their viscosity in their bulk state. However, within the pores the dc-conductivity was reduced relative to bulk, indicating the immobilization of ions at the pore walls. Hydrophobization of the pore walls by hexamethyldisilazane could partially restore the conductivity. ILs are model systems where the phase state and ion mobility can be controlled by confinement.