Investigation of the free volume characteristics of PEO based solid state polymer electrolyte by means of positron annihilation spectroscopy

Ion conduction in poly (ethylene oxide), PEO, based electrolytes are explained considering the ion movement coupled with polymer segmental motions or free volume. Herein, we describe the application of positron annihilation spectroscopy to investigate the free volume structure of PEO-LiTFSI solid state electrolyte with varying electrolyte concentration. Addition of LiTFSI indicates plasticization effect through the increase in free volume size of polymer matrix. Depth dependent Doppler broadening measurements have shown a decrease in positron/positronium diffusion length and S-parameter value on addition of electrolyte. The observed decrease in S-parameter and positronium intensity could not be ascribed to positronium reaction (inhibition) with dissociated ions or salt aggregates as the variation does not follow the established inhibition expression. The SW correlation curves indicate that the chemical environment at positron/positronium annihilation sites in PEO-LiTFSI is similar to pristine PEO. It again confirms that reduction in positronium intensity and S-parameter cannot be attributed to positronium inhibition. The present study shows that resultant positron/positronium annihilation parameters can be directly attributed to the change in molecular packing or free volume structure of the solid state electrolytes.