Thermal and dielectric properties of PEO/EC/Pr₄N⁺I⁻ polymer electrolytes for possible applications in photo-electro chemical solar cells

Abstract

The anion-conducting polymer electrolyte polyethylene oxide (PEO)/ethylene carbonate (EC)/Pr₄N⁺I⁻/I₂ is a candidate material for fabricating photo-electrochemical (PEC) solar cells. Relatively high ionic conductivity values are obtained for the plasticized electrolytes; at room temperature, the conductivity increases from 7.6 × 10⁻⁹ to 9.5 × 10⁻⁵ S cm⁻¹ when the amount of EC plasticizer increases from 0% to 50% by weight. An abrupt conductivity enhancement occurs at the melting of the polymer; above the melting temperature, the conductivity can reach values of the order of 10⁻³ S cm⁻¹. The melting temperature decreases from 66.1 to 45.1 °C when the EC mass fraction is increased from 0% to 50%, and there is a corresponding reduction in the glass transition temperature from −57.6 to −70.9 °C with the incorporation of the plasticizer. The static dielectric constant values, $\varepsilon _{\text{s}}^\prime$, increase with the mass fraction of plasticizer, from 3.3 for the unplasticized sample to 17.5 for the 50% EC sample. The dielectric results show only small traces of ion-pair relaxations, indicating that the amount of ion association is low. Thus, the iodide ion is well dissociated, and despite its large size and relatively low concentration in these samples, the iodide ion to ether oxygen ratio is 1:68, a relatively efficient charge carrier. A further enhancement of the ionic conductivity, especially at lower temperatures, is however desired for these applications.