Fluorination‐Driven Homogeneous Strategy for High‐Performance Tribo‐Piezoelectric Hybrid Nanogenerators

ABSTRACT Electrospun PVDF‐based tribo‐piezoelectric hybrid nanogenerators (TPHGs) exhibit potential in the domain of self‐powered sensing, owing to their high output performance and flexibility. However, simultaneously optimizing both piezoelectric and triboelectric outputs remains a persistent challenge. In this work, we propose a fluorination‐driven homogeneous strategy to construct F‐BTO/PVDF‐HFP fiber‐based TPHG, achieving simultaneous enhancement of triboelectric and piezoelectric responses by maintaining high fluorine content and optimizing piezo‐dipole through interfacial compatibility. The TPHG device achieved an output voltage of 353.5 ± 3.9 V and a current of 2.94 ± 0.09 µA, which represents a sevenfold improvement over PVDF‐HFP devices. Density functional theory (DFT) calculations reveal that the resulting piezoelectric field dynamically regulates interfacial electron movement, enabling directional triboelectric charge transfer and establishing tribo‐piezoelectric coupling mechanism. Benefiting from its excellent output and high sensitivity (4.14 V kPa − 1 ), the device is further integrated into an ultralight (8.56 g) wearable knee patch for monitoring mobility risks in older adults, achieving a recognition accuracy of 98.74% with machine learning assistance. This work provides general design principles and mechanistic insight for high‐performance self‐powered wearable sensing systems.