Intrinsic Elastification of Ferroelectric Poly(vinylidene fluoride) Homopolymers

ABSTRACT Elastic ferroelectrics, distinguished by their softness, stretchability, and ferroelectric and piezoelectric responses, are promising candidates in next‐generation wearable electronics. Currently, the intrinsic elastification of ferroelectric polymers has been achieved through a “slight crosslinking” strategy, which relies on costly poly(vinylidene fluoride) (PVDF)‐based copolymers with low Curie temperatures, thereby limiting their operation at high temperatures. In contrast, PVDF homopolymers are low‐cost and possess an inherently high Curie temperature, while their high modulus has long hindered elasticity. Here, we overcome these limitations by introducing highly reactive, soft long‐chain crosslinkers into PVDF homopolymers, enabling simultaneous low cost, high thermal stability, and intrinsic elasticity. By tuning the crosslinking density, intrinsically elastic ferroelectrics based on PVDF homopolymer were obtained with over 80% elastic recovery under 60% strain. Remarkably, the materials retain a high remanent polarization ( P r ) of 7.00 µC/cm 2 at 110°C. The materials maintain stable ferroelectric responses even under strains up to 70%. This study resolves the long‐standing challenge of elastifying high‐modulus PVDF homopolymers and develops a low‐cost, thermally robust, intrinsically elastic ferroelectric. These advances outline a promising pathway toward next‐generation wearable electronics that demand both high elasticity and high‐temperature operation.