Phase-Engineered Electrospun Poly(vinylidene fluoride) Nanofibers with Enhanced Piezoelectricity

Poly(vinylidene fluoride) (PVDF) nanofibers have emerged as promising materials for flexible piezoelectric sensors, yet their performance is fundamentally constrained by the limited formation and alignment of the electroactive β-phase. In this study, we report a phase-engineering strategy that integrates ionic functionalization, inorganic nanofiller incorporation, and post-fabrication corona poling to achieve enhanced crystalline ordering and electromechanical coupling in electrospun PVDF nanofibers. Tetrabutylammonium perchlorate increases solution conductivity, enabling uniform, bead-free fiber formation, while barium titanate nanoparticles act as nucleation centers that promote β-phase crystallization at the expense of the non-polar α-phase. Subsequent corona poling further aligns molecular dipoles and strengthens remnant polarization within both the PVDF matrix and embedded nanoparticles. Structural analyses confirm the synergistic evolution of crystalline phases, and piezoelectric measurements demonstrate a substantial increase in peak-to-peak output voltage under dynamic loading conditions. This combined phase-engineering approach provides a simple and scalable route to high-performance PVDF-based piezoelectric sensors and highlights the importance of coupling crystallization control with dipole alignment in designing next-generation wearable electromechanical materials.