Synergistic waste-derived fillers induce polar phase transformation for high-performance fluorinated polymer

This manuscript reports a scalable, solution-cast strategy to upcycle waste-derived functional fillers into electroactive poly(vinylidene fluoride) (PVDF) hybrid membranes for promising dielectric/piezoelectric applications. Carbon-doped recycled ZnO (Rc-ZnO) microspheres are synthesized from spent zinc-carbon batteries and combined with graphene oxide (GO) to fabricate PVDF/Rc-ZnO, PVDF/GO, and ternary PVDF/Rc-ZnO/GO films at a fixed total loading of 10 wt% (5 wt% Rc-ZnO/5 wt% GO in the ternary system) using DMF/acetone casting and controlled thermal drying. Structural and spectroscopic analyses (XRD/FT-IR/SEM) confirm a filler-driven α → β transformation, where GO defect sites act as nucleation centers and the dual-filler system increases the β-phase fractions alongside a morphology evolution toward a more interconnected porous architecture. Dielectric spectroscopy shows that co-doping delivers the most favorable electrical response, with AC conductivity increasing with frequency and temperature due to synergistic charge-carrier generation by ZnO and conductive pathways provided by GO. Density-functional-theory calculations (B3LYP/DGDZVP2) further rationalize these trends by revealing a strong reduction in the electronic gap upon interfacial hybridization (PVDF: 9.251 eV; GO/PVDF/ZnO: 1.595 eV; d-GO/PVDF/ZnO: 0.833 eV), supporting enhanced interfacial polarization and charge transport.