The dielectric properties of polymers play a pivotal role in the development of advanced materials for energy storage, electronics, and insulation. This review comprehensively explores the critical relationship between polymer chain conformation, nanostructure, and dielectric properties, focusing on parameters such as dielectric constant, dielectric loss, and dielectric breakdown strength. It highlights how factors like chain rigidity, free volume, molecular alignment, and interfacial effects significantly influence dielectric performance. Special emphasis is placed on the impact of nanofillers, molecular weight, crystallinity, and multilayer structures in optimizing these properties. By synthesizing findings from recent experimental and theoretical studies, this review identifies strategies to enhance energy efficiency, reliability, and mechanical stability of polymer-based dielectrics. We also delve into techniques such as electrostatic force microscopy (EFM) and focused ion beam (FIB) milling for characterizing breakdown mechanisms, offering insights into molecular design for next-generation high-performance polymers. Despite considerable progress, critical challenges such as achieving an optimal balance between dielectric permittivity and breakdown strength, understanding nanoscale interfacial phenomena, and scaling these materials for industrial applications persist. These gaps can be addressed by systematic structure-property relations, advanced processing techniques, and environmental studies.
Keywords: breakdown strength; chain conformation; dielectric constant/permittivity; dielectric loss; dielectric polymers; energy density; nanocomposites; nanofillers; nanostructure.