Effect of the electric field on the free volume investigated from positron annihilation lifetime and dielectric properties of sulfonated PVC/PMMA

Polymer electrolyte membranes (PEMs) play a vital role in electrochemical devices, facilitating ion conduction while blocking gases and electrons. Their effectiveness is closely linked to their microstructural properties, especially the free volume, which impacts ionic conductivity, mechanical strength, and overall device performance. This study examines the behavior of PVC/PMMA/SSA blends under electric fields, using Positron Annihilation Lifetime Spectroscopy (PALS) to assess free volume and dielectric properties. The study involved preparing and characterizing membranes through x‐ray diffraction (XRD), thermogravimetric analysis (TGA), and PALS. XRD results indicated semi‐crystalline structures with changes in intensity due to temperature variations, while TGA highlighted changes in thermal stability under different electric fields. PALS measurements showed that free volume varied with temperature and electric field strength, influencing the material's dielectric and mechanical characteristics. The results revealed that higher electric fields reduced free volume while enhancing dielectric properties. The dielectric constant and loss were found to depend on frequency, which was affected by the polar SO3H groups. Impedance spectroscopy provided further insights into the electrical properties, showing increased dc conductivity with stronger electric fields. A correlation between the free volume investigated from PAL and the electrical properties was observed. This study emphasizes the significance of free volume and external electric field in optimizing PEMs for advanced energy applications.