Volume fraction of ether is a significant factor in controlling conductivity in proton conducting polyether based polymer sol-gel electrolytes.

We have synthesized several copolymers of methyl polyethylene glycol siloxane (MePEG7SiO3)m and methyl polypropylene glycol siloxane (MePPGnSiO3)m as hydrogen ion (H(+)) conducting polymer electrolytes. These copolymers were prepared by a sol-gel polymerization of mixtures of the MePEG and MePPG monomers. We synthesized these H(+) conducting polymer electrolytes in order to study the relationship between observed ionic conductivity and structural properties such as viscosity, fractional free volume, and volume fraction of ether. We found that viscosity increased as the fraction of the smaller comonomer increased. For the MePPG2/MePPG3 copolymer, an increase in fractional free volume increased the fluidity. The heterogeneous copolymers (PEG/PPG copolymers) obeyed the Doolittle equation, while the homogeneous (PEG/PEG and PPG/PPG) copolymers did not. The increase of FFV did not, however, correspond to an increase in conductivity, as would have been predicted by the Forsythe equation. The conductivity data did correspond to a modified Forsythe equation substituting Volume Fraction of Ether (V(f,ether)) for FFV. We conclude that the proton conductivity of MePEG copolymers is more dependent on the volume fraction of ether than on the fractional free volume.

Star-shaped MePEGn polymers as H+ conducting electrolytes.

Proton conducting electrolytes composed of a mixture of MePEG(7)SO(3)H acid and a four-armed, PEG-based, star molecule were prepared. Four MePEG(n) (n = 3, 7, 12) arms were attached to a pentaerythritol or tetrakis(dimethylsilyl) orthosilicate core to form the star molecules. We have examined the structure of these star electrolytes to observe how the structure of an electrolyte affects the observed ionic conductivity. In terms of structural parameters, these star electrolytes showed large volume fractions of PEG, high fluidities, and large fractional free volumes, all of which predict larger ionic conductivities. Through a comparison of the conductivity and structural parameters in a variety of different star electrolytes, we have shown that each of these three structural parameters are important and can strongly affect the observed ionic conductivity. Walden plots indicated a large extent of ion-pairing in our star electrolytes and that MePEG(7)SO(3)H acid was a weak acid in our star electrolytes.