Interfacial Charge Dynamics and Polarization Coupling in Ferroelectric Nematic Liquid Crystal Tailored PVDF Composite Films for High‐Performance Organic Triboelectric Nanogenerator‐Based Electromechanical Energy Harvesting

Developing soft and conformable materials with enhanced charge generation and retention capabilities remains a critical barrier for next‐generation flexible triboelectric nanogenerators (TENGs). Here, we report a polarization‐coupled tribo‐negative film fabricated by integrating a room‐temperature ferroelectric nematic liquid crystal (FNLC) material (FNLC‐1571) into an electrospun poly(vinylidene fluoride) (PVDF) mat. In contrast to traditional rigid fillers, the optimally engineered ferroelectric nematic phase (N F ) of FNLC‐1571 microdomains assists spontaneous soft polar ordering in the nanofibrous PVDF matrix. This facilitates the integration of dipolar interactions with the fluorinated ends of PVDF, thereby synergistically promoting the crystallization of the electroactive β‐phase, enhancing dielectric behavior, modulating surface potential, improving interfacial charge‐trapping ability, and increasing contact area for superior charge generation while maintaining mechanical flexibility. When paired with a polyethylenimine (PEI)‐coated polyamide‐6 (PA‐6) tribo‐positive counter layer, the optimized 1 wt.% FNLC/PVDF‐based TENG delivers stable electrical output under low‐amplitude mechanical periodic contact‐separation excitation (8N, 10 Hz), with a peak‐to‐peak open‐circuit voltage of ∼395 V, a short‐circuit current of ∼40 µA, and a transferred charge of ∼167 nC. Finally, the optimally engineered all‐organic TENG assemblies were employed for various practical applications by demonstrating efficient capacitor charging, LED illumination, accurate biomechanical‐motion sensing, and real‐time IoT‐enabled monitoring through wireless interfacing.