화학공학소재연구정보센터
Journal of Physical Chemistry B, Vol.122, No.35, 8469-8476, 2018
Fully-Zwitterionic Polymer-Supported lonogel Electrolytes Featuring a Hydrophobic Ionic Liquid
In this report, fully-zwitterionic (ZI) copolymer scaffolds for ionogel electrolytes have been synthesized via in situ photo-polymerization using various molar ratios of 2-methacryloyloxyethyl phosphorylcholine (MPC) and sulfobetaine vinylimidazole (SBVI) within the hydrophobic ionic liquid 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (EMI TFSI). Depending on the chemical composition of the ZI scaffold, ionogel room temperature ionic conductivities are found to vary between 2.5 and 6.7 mS cm(-1) at a fixed 20 mol % total polymer content. Compressive elastic moduli also exhibit a strong dependence on the co-monomer ratio, with values between 23 kPa and 11 MPa observed because of different degrees of ZI physical cross-linking. These results, together with NMR chemical shift analysis, suggest that the phosphorylcholine ZI group of MPC interacts more strongly with EMI TFSI, while SBVI prefers to self-aggregate and form dipole-dipole cross-links in the ionic liquid (IL). Self-diffusivity measurements of the EMI+ cations and TFSI- anions in both ionogel and ZI solution samples confirm that slower ion diffusion in MPC-containing systems is due to attractive zwitterion/IL interactions, and not merely reduced mobility in the presence of a polymeric scaffold. This work highlights the importance of relative zwitterion/IL and ZI dipole-dipole interactions on the properties of a novel class of fully-ZI polymer-supported ionogel electrolytes containing a hydrophobic IL suitable for future electrical energy storage applications.