Selective Control of Ion Transport by Nanoconfinement: Ionic Liquid in Mesoporous Resorcinol-Formaldehyde Monolith

Thermal and dynamic properties of ionic liquid (IL)-based electrolytic solution (Li⁺TFSI^- in Pyr13⁺TFSI^-; 1-methyl-1-propylpyrrolidinium bis(trifluoromethylsulfonyl)imide = Pyr13⁺TFSI^-) confined in nanoporous polymer hosts were investigated with respect to the pore size/porosity and the surface chemistry of the polymer host. As host material, mesoporous resorcinol-formaldehyde (RF) polymer monoliths with three-dimensionally connected pore structure were prepared, with precise control of the pore size ranging from ca. 7 to 60 nm. Thermal analysis of RF polymer-ionic liquid composites showed stability up to almost 400 °C and a melting point depression proportional to the inverse of the pore diameter. Good ionic conductivity comparable to that of a commercial separator is obtained, which is dependent on the porosity (i.e., pore volume) of the confining host material (i.e., the number of charge carriers available in the system). Further pulsed field gradient (PFG) NMR experiments revealed that the diffusion coefficient of Pyr13⁺ cation becomes smaller than that of TFSI^- anion inside RF pores, which is contradictory to the bulk IL system. This change in the ionic motion is due to electrostatic attraction between the pore walls and Pyr13⁺ cations, resulting in a layer structure composed of a Pyr13⁺ cation-rich layer adsorbed at the pore wall surface and a TFSI^- anion-enriched bulklike layer at the pore center. Our study suggests that transport characteristics of the ions of interest can be controlled by optimizing the surface chemistry of the host framework and their motion can be separately monitored by PFG NMR spectroscopy.