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Ferroelectric polymers are a family of crystalline polymers with reversible remanent polarization originating from their unique chemical structures and molecular packing. As an important ferroelectric polymer, poly(vinylidene fluoride) (PVDF) and its copolymers have been exploited for various applications, including nonvolatile memories, energy harvesters, and piezoelectric/pyroelectric sensors. To achieve better performance in PVDF-based devices, crystallization manipulation and controllable nanostructure formation are unavoidable and are of crucial importance. For this review, recent exploitation of the control of PVDF ferroelectric polymer crystallization at the nanoscale was specifically examined and summarized to provide insight into the future development of ferroelectric polymer nanomaterials. Ferroelectric polymers, poly(vinylidene fluoride) (PVDF), and its copolymers have been exploited for various applications, including nonvolatile memories, energy harvesters, and piezoelectric/pyroelectric sensors. To achieve better performance in PVDF-based devices, crystallization manipulation and controllable nanostructure formation are unavoidable and are of crucial importance. For this review, recent exploitation of the control of PVDF ferroelectric polymer crystallization at the nanoscale was specifically examined and summarized to provide insight into the future development of ferroelectric polymer nanomaterials.

High-energy storage in polymer dielectrics is limited by two decisive factors: low-electric breakdown strength and high hysteresis under high fields. Poly(vinylidene fluoride) (PVDF), as a well-known ferroelectric polymer having a high-breakdown strength (700 MV/m) and a high dielectric constant, is suitable for use as a dielectric capacitor film, but ferroelectric hysteresis from the crystalline phase has prevented its practical application. In our previous study, the ferroelectric switching of crystalline PVDF is suppressed effectively in PVDF-based Langmuir–Blodgett (LB) nanofilms because of its large interfacial effect, even in an extremely high electric field. This study investigated the ferroelectricity and energy storage behaviors of PVDF LB nanofilms at sub-50 nm thicknesses. The ferroelectric hysteresis loops were measured using a Sawyer–Tower circuit in different electric fields. An energy density of 6.0 J/cm3 at 500 MV/m was demonstrated for the 12-nm-thick PVDF LB nanofilm device. Polar polymers with permanent dipoles such as poly(vinylidene fluoride) (PVDF) are suitable for use as high-energy storage density dielectrics because of their high permittivity. This study investigated the ferroelectricity and energy storage behaviors of PVDF Langmuir–Blodgett (LB) nanofilms at sub-50 nm thicknesses. The ferroelectric hysteresis loops were measured using a Sawyer–Tower circuit in different electric fields. An energy density of 6.0 J/cm3 at 500 MV/m was demonstrated for the 12-nm-thick PVDF LB nanofilm device.