Spiral-Structured Dielectric Polymers Exhibiting Ultrahigh Energy Density and Charge-Discharge Efficiency at High Temperatures.

The growing need for high-power and compact-size energy storage in modern electronic and electrical systems demands polymer film capacitors with excellent temperature capability. However, conventional polymer dielectrics feature dramatic deterioration in capacitive performance under concurrent high temperature and electric field because the high thermal stability traditionally relies on the conjugated, planar molecular segments in the polymer chains. Herein, inspired by the stable double helix structures of deoxyribonucleic acid, spiral-structured dielectric polymers that exhibit simultaneous high thermal stability and great capacitive performance are demonstrated. Both the experimental results and computational simulations confirm that the spiral groups serve to weaken the electrostatic molecular interaction, induce proper molecular chain stacking structure, and regulate the charge transfer process by breaking the conjugated planes and introducing deep trap sites. The resultant polymer exhibits the maximum discharged energy densities of 7.29 and 6.13 J cm-3 with the charge-discharge efficiency above 90% at 150 and 200 °C, respectively, more than ten times those of the original dielectric at the same conditions. Here a completely new dimension is offered for the molecular design of polymers, giving rise to well-balanced thermal and dielectric properties, and ultimately the desired capacitive energy storage performance at high temperatures.

A Bi-Gradient Dielectric Polymer/High-Κ Nanoparticle/Molecular Semiconductor Ternary Composite for High-Temperature Capacitive Energy Storage.

Attaining compact energy storage under extreme temperature conditions is of paramount importance in the development of advanced dielectric materials. The polymer composite approach has proved effective towards this goal, and addressing the correlation between filler distribution and electrical properties is foremost in designing composite dielectrics, especially in multifiller systems. Here, the design of a bi-gradient polymer composite dielectric using an integrated framework based on the phase field model is reported. This framework can predict the charge-inhibiting behavior of composite dielectrics, which is a key factor impacting the high-temperature capacitive performance but unfortunately is ignored in conventional phase field models. It is found that due to the traps provided by the functional organic fillers, more carriers are trapped near the electrodes and weaken the electric field, thus significantly suppressing the breakdown initialization process. An interpenetrating gradient structure is designed rationally and synthesized experimentally, which exhibits concurrent high energy density (5.51 J cm-3 ) and high charge-discharge efficiency (90%) up to 200 °C. This work provides a strategy to predict the high-temperature energy storage performance of polymer composites containing charge-inhibiting components and helps broaden the scope of data-driven materials design based on phase-field modeling.

Designing tailored combinations of structural units in polymer dielectrics for high-temperature capacitive energy storage.

Many mainstream dielectric energy storage technologies in the emergent applications, such as renewable energy, electrified transportations and advanced propulsion systems, are usually required to operate under harsh-temperature conditions. However, excellent capacitive performance and thermal stability tend to be mutually exclusive in the current polymer dielectric materials and applications. Here, we report a strategy to tailor structural units for the design of high-temperature polymer dielectrics. A library of polyimide-derived polymers from diverse combinations of structural units are predicted, and 12 representative polymers are synthesized for direct experimental investigation. This study provides important insights into decisive structural factors necessary to achieve robust and stable dielectrics with high energy storage capabilities at elevated temperature. We also find that the high-temperature insulation performance would experience diminishing marginal utility as the bandgap increases beyond a critical point, which is strongly correlated to the dihedral angle between neighboring planes of conjugation in these polymers. By experimentally testing the optimized and predicted structures, an increased energy storage at temperatures up to 250 °C is observed. We discuss the possibility for this strategy to be generally applied to other polymer dielectrics to achieve further performance enhancement.

Molecular Structure Modulated Trap Distribution and Carrier Migration in Fluorinated Epoxy Resin.

Surface charge accumulation on epoxy insulators is one of the most serious problems threatening the operation safety of the direct current gas-insulated transmission line (GIL), and can be efficiently inhibited by the surface modification technology. This paper investigated the mechanisms of fluorination modulated surface charge behaviors of epoxy resin through quantum chemical calculation (QCC) analysis of the molecular structure. The results show that after fluorination, the surface charge dissipation process of the epoxy sample is accelerated by the introduced shallow trap sites, which is further clarified by the carrier mobility model. The electron distribution probability of the highest occupied molecular orbitals (HOMO) under positive charging and the lowest unoccupied molecular orbitals (LUMO) under negative charging shows distinctive patterns. It is illustrated that electrons are likely to aggregate locally around benzenes for the positively charged molecular structure, while electrons tend to distribute all along the epoxy chain under negatively charging. The calculated results verify that fluorination can modulate surface charge behaviors of epoxy resin through redesigning its molecular structure, trap distribution and charging patterns.