Hydrogen Bond Reorganization‐Enabled Dielectric Pulsing Effects in Polar Polymers

Abstract Phase transition and relaxation, both essentially molecular motions, are critical mechanisms that determine the mechanical, electrical, optical, and thermal behaviors of polymer materials. For decades, hydrogen bonding has played an essential role in the modulation of molecular motions and material properties. However, in the design of stimulus‐responsive dielectric materials and the modulation of their properties, the role of hydrogen bonding has been rarely investigated, and its effect on dielectric response behavior remains elusive. Here, observations and proof that hydrogen bond reorganization is able to act as the origin of the dielectric pulsing effect in polar semicrystalline polymers by in situ testing is presented. A two‐step hydrogen bond reorganization drives molecular chain relaxation in polar semicrystalline polymers causing a strong dielectric response behavior, opening up the possibility of modulating dielectric response behavior through hydrogen bonding. Moreover, electrode polarization can synergize with interfacial and dipolar polarizations to enhance the dielectric pulsing effect. This study also provides a blow‐spinning method for preparing large‐area, flat, flexible, lightweight, and recyclable thermo‐responsive dielectric films by continuous, efficient, and low‐cost processing.