Thermally Stable Poly(vinylidene fluoride) for High-Performance Printable Piezoelectric Devices

Piezoelectric polymers, such as poly(vinylidene fluoride) (PVDF) and its copolymers, can achieve large strains and high work density under external electrical fields. These materials are highly desirable in the development of electronic devices and intelligent structures. Here, we demonstrate that dehydrofluorination (DHF) can provide a versatile chemical modification of the PVDF homopolymer that yields thermally stable ferroelectricity. The DHF process significantly increases the fraction of planar chain conformation in the PVDF and results in higher piezoelectric coupling with a wider processing temperature range, compared to traditionally processed PVDF. The efficacy of DHF in promoting planar chain conformation is demonstrated through molecular simulation and further proven by experimental characterization. The induced piezoelectric phases by DHF were able to be preserved through high temperature treatments up to 200 °C. The dehydrofluorinated PVDF exhibits improved electromechanical coupling with a high piezoelectric strain coefficient of d₃₁ = 25.12 ± 1.13 pC/N, which can be further improved to 35.12 ± 0.69 pC/N by common mechanical drawing. This high piezoelectric voltage coefficient leads to an excellent actuation and energy harvesting behavior with a power density of 21.96 mW/cm³ in a flexible undrawn PVDF energy harvester, which is 3.13 times higher than conventionally drawn PVDF. The versatile and scalable method for preparing PVDF polymers with high piezoelectric coupling will enable new manufacturing processes not currently compatible with PVDF homopolymers.