Polymer nanocomposites can be tuned to achieve exceptional dielectric properties compared to pristine dielectric polymers. To significantly enhance these properties, research has focused on modifying the structure of polymergrafted nanoparticles. However, while much attention has been given to the shell architecture of these nanoparticles, the effects of core size (near de Broglie length) and loading amount on the breakdown strength and energy density of nanocomposites remain less explored. In this study, we synthesized polystyrene grafted TiO2 nanoparticles (PSgTiO2 NPs) using surface-initiated atom transfer polymerization (SI-ATRP) with variable core sizes (15 and 40 nm). By adjusting the monomer-to-nanoparticle feed ratio, we controlled the graft density and molecular weight of the grafted chains. When dispersed in a PS matrix at various loading levels, PSgTiO2 NPs showed minimal improvement in energy density up to 5 wt%. However, significant enhancements were observed at 10 wt% and 20 wt% PSgTiO2 NPs in the PS matrix. Interestingly, for similar loading levels, the energy density and efficiency of 40 nm PSgTiO2 NPs in the PS matrix were higher compared to the 15 nm PSgTiO2 NPs. These findings on core size and nanoparticle loading amount have important implications for the design of commercial dielectric capacitors.

Structurally well-defined polymer-grafted nanoparticle hybrids are highly sought after for a variety of applications, such as antifouling, mechanical reinforcement, separations, and sensing. Herein, we report the synthesis of poly(methyl methacrylate) grafted- and poly(styrene) grafted-BaTiO3 nanoparticles using activator regeneration via electron transfer (ARGET ATRP) with a sacrificial initiator, atom transfer radical polymerization (normal ATRP), and ATRP with sacrificial initiator, to understand the role of the polymerization procedure in influencing the structure of nanoparticle hybrids. Irrespective of the polymerization procedure adopted for the synthesis of nanoparticle hybrids, we noticed PS grafted on the nanoparticles showed moderation in molecular weight and graft density (ranging from 30,400 to 83,900 g/mol and 0.122 to 0.067 chain/nm2) compared to PMMA-grafted nanoparticles (ranging from 44,620 to 230,000 g/mol and 0.071 to 0.015 chain/nm2). Reducing the polymerization time during ATRP has a significant impact on the molecular weight of polymer brushes grafted on the nanoparticles. PMMA-grafted nanoparticles synthesized using ATRP had lower graft density and considerably higher molecular weight compared to PS-grafted nanoparticles. However, the addition of a sacrificial initiator during ATRP resulted in moderation of the molecular weight and graft density of PMMA-grafted nanoparticles. The use of a sacrificial initiator along with ARGET offered the best control in achieving lower molecular weight and narrow dispersity for both PS (37,870 g/mol and PDI of 1.259) and PMMA (44,620 g/mol and PDI of 1.263) nanoparticle hybrid systems.

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.

The synthesis of polymer-grafted nanoparticles (PGNPs) or hairy nanoparticles (HNPs) by tethering of polymer chains to the surface of nanoparticles is an important technique to obtain nanostructured hybrid materials that have been widely used in the formulation of advanced polymer nanocomposites. Ceramic-based polymer nanocomposites integrate key attributes of polymer and ceramic nanomaterial to improve the dielectric properties such as breakdown strength, energy density and dielectric loss. This review describes the "grafting from" and "grafting to" approaches commonly adopted to graft polymer chains on NPs pertaining to nano-dielectrics. The article also covers various surface initiated controlled radical polymerization techniques, along with templated approaches for grafting of polymer chains onto SiO2, TiO2, BaTiO3, and Al2O3 nanomaterials. As a look towards applications, an outlook on high-performance polymer nanocomposite capacitors for the design of high energy density pulsed power thin-film capacitors is also presented.

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.

Polymer nanocomposites (PNC) have attracted enormous scientific and technological interest due to their applications in energy storage, electronics, biosensing, drug delivery, cosmetics and packaging industry. Nanomaterials (platelet, fibers, spheroids, whiskers, rods) dispersed in different types of polymer matrices constitute such PNC. The degree of dispersion of the inorganic nanomaterials in the polymer matrix, as well as the structured arrangement of the nanomaterials, are some of the key factors influencing the overall performance of the nanocomposite. To this end, the surface functionalization of the nanomaterials determines its state of dispersion within the polymer matrix. For energy storage and electronics, these nanomaterials are usually chosen for their dielectric properties for enhancing the performance of device applications. Although several reviews on surface modification of nanomaterials have been reported, a review on the surface functionalization of nanomaterials as it pertains to polymer dielectrics is currently lacking. This review summarizes the recent developments in the surface modification of important metal oxide dielectric nanomaterials including Silicon dioxide (SiO2), titanium dioxide (TiO2), barium titanate (BaTiO3), and aluminum oxide (Al2O3) by chemical agents such as silanes, phosphonic acids, and dopamine. We report the impact of chemical modification of the nanomaterial on the dielectric performance (dielectric constant, breakdown strength, and energy density) of the nanocomposite. Aside from bringing novice and experts up to speed in the area of polymer dielectric nanocomposites, this review will serve as an intellectual resource in the selection of appropriate chemical agents for functionalizing nanomaterials for use in specific polymer matrix so as to potentially tune the final performance of nanocomposite.

Designing next-generation lightweight pulsed power devices hinges on understanding the factors influencing the energy storage performance of dielectric materials. Polymer dielectric films have a quadratic dependence of energy storage on the voltage breakdown strength, and strategies to enhance the breakdown strength are expected to yield a path toward high energy storage densities. Highly stratified lamellar block copolymer (L-BCP) films of model polystyrene-b-polymethylmethacrylate (PS-b-PMMA) exhibited as much as similar to 50% enhancement in breakdown voltage (E-BD) (225% increase in stored energy density, U similar to E-BD(2)) compared to unordered as-cast L-BCP films. Such an energy density using amorphous polymer is on par with industry-standard semicrystalline biaxially oriented polypropylene (BOPP) and as such a notable development in the field. This work develops a deeper understanding of the molecular mechanisms of E-BD enhancement in L-BCP films, relating E-BD directly to molecular weight (M-n), with interpretation to effects of chain-end density and distribution, interface formation, layer thickness, and their relative contributions. As-cast disordered L-BCP films show decreasing E-BD with decreasing M-n similar to homopolymer studies because of the increase of homogeneously distributed chain ends in the film. E-BD increases significantly in parallel ordered L-BCP films because of the combination of interface formation and spatial isolation of the chain ends into segregated zones. We further confirm the role of chain ends in the breakdown process blending a low M-n L-BCP with matched M-n homopolymers to attain the same layer spacing as neat L-BCP of higher M-n. E-BD shows a significant decrease at low homopolymer fractions because of increased net chain-end density within swollen ordered L-BCP domains in wet-brush regime, followed by increased E-BD because of layer thickness increase via segregated "interphase layer" formation by excess homopolymers. Notably, E-BD of homopolymer swollen L-BCPs is always lower than that of neat L-BCPs of the same domain spacing because of overall adverse chain-end contribution from homopolymers. These findings provide important selection rules for L-BCPs for designing next-generation flexible electronics with high energy density solid-state BCP film capacitors.