Polysiloxane-graft-PEG/Phosphonium Ionomer Morphology and Ion Transport

A series of random polysiloxane-based copolymer single ion conductors with phosphonium and polyethylene glycol side chains have been synthesized at various compositions and counterions. Morphology is investigated via X-ray scattering, and reveals microphase separation on extremely small length scales. Despite the low molecular weight of the PEG side chain, polysiloxane and PEG assemble into microdomains with covalently bound phosphonium cations at the interface. Exceptionally low glass transition temperatures in these microphase separated ionomers allow for high ionic mobility for both bulky, charge delocalized counterions as well as small, electronegative counterions. Morphology interpretation is complemented by measurement of ion transport properties via dielectric relaxation spectroscopy.