Engineering the Dielectric Constants of Polymers: From Molecular to Mesoscopic Scales.

Polymers are essential components of modern-day materials and are widely used in various fields. The dielectric constant, a key physical parameter, plays a fundamental role in the light-, electricity-, and magnetism-related applications of polymers, such as dielectric and electrical insulation, battery and photovoltaic fabrication, sensing and electrical contact, and signal transmission and communication. Over the past few decades, numerous efforts have been devoted to engineering the intrinsic dielectric constant of polymers, particularly by tailoring the induced and orientational polarization modes and ferroelectric domain engineering. Investigations into these methods have guided the rational design and on-demand preparation of polymers with desired dielectric constants. This review article exhaustively summarizes the dielectric constant engineering of polymers from molecular to mesoscopic scales, with emphasis on application-driven design and on-demand polymer synthesis rooted in polymer chemistry principles. Additionally, it explores the key polymer applications that can benefit from dielectric constant regulation and outlines the future prospects of this field.

Aromatic-Free Polymers Based All-Organic Dielectrics with Breakdown Self-Healing for High-Temperature Capacitive Energy Storage.

High-temperature dielectric polymers are becoming increasingly desirable for capacitive energy storage in renewable energy utilization, electrified transportation, and pulse power systems. Current dielectric polymers typically require robust aromatic molecular frameworks to ensure structural thermal stability at elevated temperatures. Nevertheless, the introduction of aromatic units compromises electrical insulation owing to pronounced π─π interactions that facilitate electron transport and eliminate the breakdown self-healing property owing to their high carbon content. Herein, an aromatic-free polynorborne copolymer exhibiting electrical conductivity-two orders of magnitude lower than that of state-of-the-art polyetherimide-at elevated temperatures and high electric fields owing to its large bandgap (≈4.64 eV) and short hopping conduction distance (≈0.63 nm) is described. Density functional theory calculations demonstrate that the copolymer can effectively suppress the excitation of high-field valence electrons. Furthermore, the incorporation of trace semiconductors results in high discharge density (3.73 J cm-3 ) and charge-discharge efficiency (95% at 150 °C), outperforming existing high-temperature dielectric polymers. The excellent electrical breakdown self-healing capability of the copolymer film at elevated temperatures further demonstrates its potential for use in dielectric capacitors capable of continuous operation under extreme conditions.