Polyvinylidene Fluoride Based Piezoelectric Composites with Strong Interfacial Adhesion via Click Chemistry for Self‐Powered Flexible Sensors

Abstract Achieving relatively uniform dispersion in organic–inorganic composites with overwhelming differences in surface energy is a perennial challenge. Herein, novel eliminated polyvinylidene fluoride (EPVDF)/EPVDF functionalized barium titanate nanoparticles (EPVDF@BT) flexible piezoelectric nanogenerators (PENGs) with strong interfacial adhesion are developed via thermal stretching following sequential click chemistry. Thanks to the strong interfacial adhesion, the optimal PENGs containing ultra‐high β ‐phase content (97.2%) exhibit not only optimized mechanical and dielectric behaviors but also excellent piezoelectric properties with high piezoelectric output ( V = 10.7 V, I = 216 nA), reliable durability (8000 cycles), ultrafast response time (20 ms), and good sensitivity (2.09 nA kPa −1 ), far outperforming most reported PVDF‐based composites. Furthermore, COMSOL finite element simulations (FEM) confirm that the elevated stress transfer efficiency induced by the strong interfacial adhesion is the main driving force for enhanced piezoelectric performances. For practical applications, self‐powered PENGs can simply but stably capture mechanical energy, drive tiny electronic devices, and serve as potential multifunctional and durable sensors for detecting human physiological motions. This work opens a pioneering avenue to break the trade‐offs between piezoelectric and other properties, which is of great importance for developing self‐powered flexible sensors.