Multi-Level In Situ Surface Modification of Electrospun Tetragonal BaTiO₃ Nanofibers for High-Performance Flexible...

The practical application of inorganic ferroelectric fillers in flexible piezoelectric composites is critically constrained by low polarization efficiency and severe interfacial incompatibility with polymer matrices. Herein, we report a multi-level in situ surface modification strategy that simultaneously addresses both limitations. High-purity one-dimensional tetragonal barium titanate nanofibers (BTO NFs) are first synthesized via sol-gel electrospinning combined with a two-step gradient annealing process, which precisely controls phase evolution and preserves structural continuity. To overcome the detrimental acid-induced degradation of BTO NFs during functionalization, a polydopamine (PDA) buffer layer is first conformally coated, followed by the liquid-phase deposition of a conductive polypyrrole (PPy) shell, forming a robust core-shell PPy@PBT NFs architecture. Incorporating only 4 wt% of these multifunctional fillers into a poly(vinylidene fluoride) (PVDF) matrix yields a dramatic enhancement in electromechanical performance. The resulting flexible piezoelectric energy harvesters achieve a piezoelectric coefficient (d₃₃) of 28.7 pC/N, an output voltage of 13 V, and an output current of 0.7 μA, representing substantial improvements over unmodified filler systems. This synergistic enhancement originates from the PDA-mediated interfacial stress transfer and the PPy-induced Maxwell-Wagner polarization intensification, establishing a robust and generalizable paradigm for high-performance flexible piezoelectric composites in self-powered wearable electronics.