This review provides a detailed overview of the latest developments using nanoscale strategies in the field of polymeric and polymer nanocomposite materials for emerging dielectric capacitor-based energy storage applications. Among the various energy storage devices, solid-state dielectric capacitors possess the advantage of high-power density which makes them highly attractive for pulsed power applications. Polymers are particularly suitable for dielectric energy storage applications because of their high breakdown strength, low dielectric loss, formability, self-healing capability, flexibility, solvent processability, and graceful breakdown failure. Strategies to enhance the dielectric breakdown strength of polymeric dielectric capacitors are emphasized in this review. General background on breakdown mechanism, breakdown characteristics, and factors influencing polymer dielectrics breakdown are introduced. Given that polymers have low permittivity, strategies to substantially enhance dipole mobility and hence the permittivity, are highlighted. We discuss strategies to address permittivity contrast between nanofillers and the polymer matrix including the potential for developing gradient permittivity structured nanofillers. To improve the compatibility of nanofiller with polymer and minimize nanofiller aggregation, different routes to surface functionalize nanoparticles are presented. An outlook and future perspectives section are provided for the design of high energy density polymer film capacitors.

Designing high energy density dielectric capacitors for advanced energy storage systems needs nanocomposite-based dielectric materials, which can utilize the properties of both inorganic and polymeric materials. Polymer-grafted nanoparticle (PGNP)-based nanocomposites alleviate the problems of poor nanocomposite properties by providing synergistic control over nanoparticle and polymer properties. Here, we synthesize "core-shell" barium titanate-poly(methyl methacrylate) (BaTiO₃-PMMA) grafted PGNPs using surface-initiated atom transfer polymerization (SI-ATRP) with variable grafting densities of (0.303 to 0.929) chains/nm² and high molecular masses (97700 g/mL to 130000 g/mol) and observe that low grafted density and high molecular mass based PGNP show high permittivity, high dielectric strength, and hence higher energy densities (≈ 5.2 J/cm³) as compared to the higher grafted density PGNPs, presumably due to their "star-polymer"-like conformations with higher chain-end densities that are known to enhance breakdown. Nonetheless, these energy densities are an order of magnitude higher than their nanocomposite blend counterparts. We expect that these PGNPs can be readily used as commercial dielectric capacitors, and these findings can serve as guiding principles for developing tunable high energy density energy storage devices using PGNP systems.