Progress in Multilayer PVDF‐Based Composite for Dielectric Energy Storage

Abstract Poly(vinylidene fluoride) (PVDF)‐based polymers stand out for their high dielectric constant and breakdown strength, offering potential for advanced film capacitors. However, inherent drawbacks such as high leakage current, poor interfacial compatibility restrict their application. Multilayer composite designs provide a promising strategy by enhancing electric field distribution and interfacial polarization, thereby improving energy density without sacrificing flexibility or processability. Tailoring filler types and morphologies further refines key property trade‐offs. Despite these advancements, challenges remain, including interfacial defect accumulation and the inverse relationship between dielectric constant and breakdown strength. This review presents a comprehensive overview of recent progress in PVDF‐based multilayer composite films, emphasizing three critical aspects: layer configuration, filler design, and functional layer integration, and also identifies current bottlenecks and offers insights into future directions for high‐performance PVDF and copolymer‐based capacitors in energy storage applications.