Synthesis of High‐Performance Polyvinylidene Fluoride Composites via Hydroxyl Anchoring Effect and Directional Freeze‐Drying Method

Abstract

Polyvinylidene fluoride (PVDF) and its copolymers present extensive application prospects, especially in the field of wearable electronics. However, utilizing nanofillers for enhanced β‐phase and piezoelectric properties faces challenges like noncontinuous interfaces, poor compatibility between nanofillers and PVDF matrix, and the requirement of high‐voltage polarization, hindering extensive domain alignment on a large scale. Herein, a method is proposed to synthesize high‐performance PVDF composites by introducing hydroxylated barium titanate (H@BTO) nanoparticles and a directional freeze‐drying method to enhance β‐phase content and piezoelectric properties without polarization. Molecular dynamics simulations reveal robust binding interactions between Ba and F atoms along with OH surface terminations on H@BTO, facilitating hydrogen bonding within the PVDF matrix, resulting in dipole alignment and increased spontaneous polarization. The composite film achieves an 86.69% β phase content and a piezoelectric coefficient of ≈14.49 pm V−1 without electric polarization. The freeze‐drying PVDF‐H@BTO composite film paired with a PA6 membrane is used to fabricate triboelectric nanogenerator, demonstrating a current density of ≈107.5 mA m−2 and an output voltage of ≈832 V. Results demonstrate that the utilization of strong binding interactions between various atoms, the hydroxyl anchoring effect, and directional freeze‐drying method as a strategy holds promising prospects for synthesizing high‐performance piezoelectric composites.