Adding free volume to PEG based anhydrous proton conducting electrolytes with bulky copolymers

We have synthesized several H+ conducting siloxane copolymers with a methyl polyethylene glycol siloxane (MePEGnSiO1.5; n = 3, 7, 12, 16) and diphenyl siloxane, isobutyl siloxane, and 3,3,3-trifluoropropyl siloxane copolymers. These copolymers where prepared to test if copolymerization with bulky groups can add free volume to our MePEGn polymer, and thus affect ion transport properties. We also found that the fractional free volume (FFV) could be increased in short MePEGn copolymers with the diphenyl and isobutyl copolymers, while with longer MePEGn groups (n = 12, 16), the pure (MePEGn–SiO3)m polymer already has a large free volume and that the added copolymers only dilute that already maximized free volume. The increase in FFV did not correspond to an increase in ionic conductivity. Ionic conductivity appears to be more a function of the volume fraction of PEG (Vf,PEG) than FFV.