Interface‐Strengthened Polymer Nanocomposites with Reduced Dielectric Relaxation Exhibit High Energy Density at Elevated Temperatures Utilizing a Facile Dual Crosslinked Network

High‐temperature ceramic/polymer nanocomposites with large energy density as the reinforcement exhibit great potential for energy storage applications in modern electronic and electrical power systems. Yet, a general drawback is that the increased dielectric constant is usually achieved at the cost of decreased breakdown strength, thus leading to moderate improvement of energy density and even displaying a marked deterioration under high temperatures and high electric fields. Herein, a new strategy is reported to simultaneously improve breakdown strength and discharged energy density by a step‐by‐step, controllable dual crosslinking process, which constructs a strengthened interface as well as reduces molecular chains relaxation under elevated temperatures. Great breakdown strength and discharged energy density is achieved in the dual crosslinked network BT‐BCB@DPAES nanocomposites at elevated temperatures when compared to noninterfacial‐strengthened, BT/DPAES composites, i.e., an enhanced breakdown strength and a discharged energy density of 442 MV m^?1 and 3.1 J cm^?3, increasing by 66% and 162%, and a stable cyclic performance over 10 000 cycles is demonstrated at 150 °C. Moreover, the enhancement through the synergy of two crosslinked networks is rationalized via a comprehensive phase‐field model for the composites. This work offers a strategy to enhance the electric storage performances of composites at high temperatures.     

Scalable Polymer Nanocomposites with Record High‐Temperature Capacitive Performance Enabled by Rationally Designed Nanostructured Inorganic Fillers

Next‐generation microelectronics and electrical power systems call for high‐energy‐density dielectric polymeric materials that can operate efficiently under elevated temperatures. However, the currently available polymer dielectrics are limited to relatively low working temperatures. Here, the solution‐processable polymer nanocomposites consisting of readily prepared Al₂O₃ fillers with systematically varied morphologies including nanoparticles, nanowires, and nanoplates are reported. The field‐dependent electrical conduction of the polymer nanocomposites at elevated temperatures is investigated. A strong dependence of the conduction behavior and breakdown strength of the polymer composites on the filler morphology is revealed experimentally and is further rationalized via computations. The polymer composites containing Al₂O₃ nanoplates display a record capacitive performance, e.g., a discharged energy density of 3.31 J cm^?3 and a charge–discharge efficiency of >90% measured at 450 MV m^?1 and 150 °C, significantly outperforming the state‐of‐the‐art dielectric polymers and nanocomposites that are typically prepared via tedious, low‐yield approaches.     

高储能陶瓷/聚偏氟乙烯复合电介质的研究进展

介电电容器作为间歇产生的可持续能源的高效存储转换设备,在新能源领域发挥着不可替代的作用。而电介质电容器的核心是具有高储能密度的电介质材料。聚合物电介质材料由于具有击穿场强高、放电速度快、能长时间使用并可自修复等特点,成为高性能电容器的潜力候选材料,但聚合物本身较低的介电常数限制了其储能密度。通过将具有高介电常数的陶瓷填料与聚偏氟乙烯(PVDF)聚合物复合,制备新型陶瓷/PVDF复合电介质,在提高电介质材料的介电性能和储能密度方面取得了重要进展。本文介绍了电介质材料的基本原理,综述了不同类型的陶瓷/PVDF复合电介质的结构、储能机制及介电储能性能,并对其未来发展趋势进行了展望。      

Improved polymer nanocomposite dielectric breakdown performance through barium titanate to epoxy interface control

A composite approach to dielectric design has the potential to provide improved permittivity as well as high breakdown strength and thus afford greater electrical energy storage density. Interfacial coupling is an effective approach to improve the polymer-particle composite dielectric film resistance to charge flow and dielectric breakdown. A bi-functional interfacial coupling agent added to the inorganic oxide particles’ surface assists dispersion into the thermosetting epoxy polymer matrix and upon composite cure reacts covalently with the polymer matrix. The composite then retains the glass transition temperature of pure polymer, provides a reduced Maxwell-Wagner relaxation of the polymer-particle composite, and attains a reduced sensitivity to dielectric breakdown compared to particle epoxy composites that lack interfacial coupling between the composite filler and polymer matrix. Besides an improved permittivity, the breakdown strength and thus energy density of a covalent interface nanoparticle barium titanate in epoxy composite dielectric film, at a 5 vol.% particle concentration, was significantly improved compared to a pure polymer dielectric film. The interfacially bonded, dielectric composite film had a permittivity ∼6.3 and at a 30 μm thickness achieved a calculated energy density of 4.6 J/cm³.     

Low-content core–shell-structured TiO2 nanobelts@SiO2 doped with poly(vinylidene fluoride) composites to achieve high-energy storage density

Polymer film capacitors have a high power density and great application potential in high-power electronic devices; however, high-energy storage density of polymer composites is usually obtained via doping high-content ceramic filler. An efficient approach to solve this issue is to dope polymers with an ultralow-content ceramic filler to improve their energy storage density. In this work, one-dimensional (1D) TiO₂ nanobelts@SiO₂ (TO nb@SO) are prepared via the hydrothermal reaction, muffle calcination, and hydrolysis. Extremely low-content TO nb@SO/poly(vinylidene fluoride) (TO nb@SO/PVDF) composites are prepared. The microstructure, crystalline structure, dielectric properties, electric breakdown strength, and discharge energy density are systematically investigated. The results show that the nanobelts have a width of 250 nm, a length of 1–2 μm, and a uniform shell layer at the edge with a thickness of ～25 nm. The relative dielectric constant of the composites is significantly enhanced; it reaches 11 for PVDF at 100 Hz, and 12.03 for 0.5 wt% TO nb@SO/PVDF. The theoretical dielectric constant is calculated based on a mathematical model and compared with the measured value. 1D materials with a large aspect ratio are beneficial in the improvement of the dielectric properties. The Weibull breakdown field strength is 381.3 MV/m for 0.5 wt% TO nb@SO/PVDF. A discharge energy density of 8.86 J/cm³ is obtained at 390 MV/m, while a high charge/discharge efficiency of 66.28% is achieved. To conclude, this work provides a valuable method for increasing the energy storage density and charge/discharge efficiency of dielectric capacitors.

     

High‐Performance Polymers Sandwiched with Chemical Vapor Deposited Hexagonal Boron Nitrides as Scalable High‐Temperature Dielectric Materials

Polymer dielectrics are the preferred materials of choice for power electronics and pulsed power applications. However, their relatively low operating temperatures significantly limit their uses in harsh‐environment energy storage devices, e.g., automobile and aerospace power systems. Herein, hexagonal boron nitride (h ‐BN) films are prepared from chemical vapor deposition (CVD) and readily transferred onto polyetherimide (PEI) films. Greatly improved performance in terms of discharged energy density and charge–discharge efficiency is achieved in the PEI sandwiched with CVD‐grown h ‐BN films at elevated temperatures when compared to neat PEI films and other high‐temperature polymer and nanocomposite dielectrics. Notably, the h ‐BN‐coated PEI films are capable of operating with >90% charge–discharge efficiencies and delivering high energy densities, i.e., 1.2 J cm^?3, even at a temperature close to the glass transition temperature of polymer (i.e., 217 °C) where pristine PEI almost fails. Outstanding cyclability and dielectric stability over a straight 55 000 charge–discharge cycles are demonstrated in the h ‐BN‐coated PEI at high temperatures. The work demonstrates a general and scalable pathway to enable the high‐temperature capacitive energy applications of a wide range of engineering polymers and also offers an efficient method for the synthesis and transfer of 2D nanomaterials at the scale demanded for applications.     

Bioinspired Polymer Nanocomposites Exhibit Giant Energy Density and High Efficiency at High Temperature

Polymer dielectrics are ubiquitous in advanced electric energy storage systems. However, the relatively low operating temperature significantly menaces their widespread application at high temperatures, such as for hybrid vehicles and aerospace power electronics. Spider silk, a natural nanocomposite comprised of biopolymer chains and crystal protein nanosheets combined by multiple interfacial interactions, exhibits excellent mechanical properties even at elevated temperatures. Inspired by the hierarchical nanostructure of spider silk, poly(aryl ether sulfone) is anchored to the surface of wide bandgap artificial nanosheets to prepare the nanocomposites with nanoconfinement effect. The bioinspired strategy successfully improves the mechanical and electrical performances of the nanocomposite. Owing to the structural‐enabled enhancements, the nanocomposites exhibit excellent breakdown strength and electrical energy storage performance at high temperatures. In detail, giant discharged energy density (2.7 J cm^?3) and high charge–discharge efficiency (>90%) are simultaneously achieved at 150 °C and 400 MV m^?1. Notably, under 500 MV m^?1, the discharged energy density reaches 4.2 J cm^?3, which is the record high discharged energy density among polymer‐based dielectrics at 150 °C. This work demonstrates a viable strategy to design high‐temperature polymer dielectrics by constructing nanoconfinement in the nanocomposites.     

Superior Energy Storage Capability and Stability in Lead-Free Relaxors for Dielectric Capacitors Utilizing Nanoscale Polarization Heterogeneous Regions

The development of high-performance lead-free dielectric ceramic capacitors is essential in the field of advanced electronics and electrical power systems. A huge challenge, however, is how to simultaneously realize large recoverable energy density (W_rec), ultrahigh efficiency (η), and satisfactory temperature stability to effectuate next-generation high/pulsed power capacitors applications. Here, a strategy of utilizing nanoscale polarization heterogeneous regions is demonstrated for high-performance dielectric capacitors, showing comprehensive properties of large W_rec (≈6.39 J cm⁻³) and ultrahigh η (≈94.4%) at 700 kV cm⁻¹ accompanied by excellent thermal endurance (20–160 °C), frequency stability (5–200 Hz), cycling reliability (1–105 cycles) at 500 kV cm⁻¹, and superior charging-discharging performance (discharge rate t_0.9 ≈ 28.4 ns, power density PD ≈161.3 MW cm⁻³). The observations reveal that constructing the polarization heterogeneous regions in a linear dielectric to form novel relaxor ferroelectrics produces favorable microstructural characters, including extremely small polar nanoregions with high dynamics and multiphase coexistence and stable local structure symmetry, which enables large breakdown strength and ultralow polarization switching hysteresis, hence synergistically contributing to high-efficient capacitive energy storage. This study thus opens up a novel strategy to design lead-free dielectrics with comprehensive high-efficient energy storage performance for advanced pulsed power capacitors applications.     

Alkali-free glass as a high energy density dielectric material

One of the greatest challenges in the development of new high energy density materials is to increase dielectric permittivity while maintaining high breakdown strength. The dielectric breakdown behavior of an alkali-free barium boroaluminosilicate glass is shown to have remarkably high DC dielectric breakdown strength (12 MV/cm) and reasonably high permittivity (~ 6), equating to energy densities in excess of 35 J/cm³. This behavior is attributed to highly polarizable Ba ions enhancing the real part of complex permittivity, the low loss due to the alkali-free composition, and the substantially defect-free quality of the glass and its surfaces. To our knowledge, this is the highest breakdown strength reported for a bulk glass, and rivals the breakdown strength more typically observed in pristine thin films of SiO₂. These findings indicate that alkali-free multicomponent glasses may be strong candidates for next-generation high energy density storage capacitors for portable or pulsed power applications.     

Improved Capacitive Energy Storage Nanocomposites at High Temperature Utilizing Ultralow Loading of Bimetallic MOF

It is urgent to develop high-temperature dielectrics with high energy density and high energy efficiency for next-generation capacitor demands. Metal-organic frameworks (MOFs) have been widely used due to their structural diversity and functionally adaptable properties. Doping of metal nodes in MOFs is an effective strategy to change the band gap and band edge positions of the original MOFs, which helps to improve their ability to bind charges as traps. In this work, the incorporation of ultralow loading (<1.5 wt%) of novel bimetallic MOFs (ZIF 8–67) into the polyetherimide (PEI) polymer matrix is exhibited. With the addition of ZIF 8–67, the breakdown strength and energy storage capacity of ZIF 8–67/PEI nanocomposites are significantly improved, especially at high temperatures (200 °C). For example, the energy densitiy of the 0.5 wt% ZIF 8–67/PEI nanocomposite is up to 2.96 J cm⁻³, with an efficiency (η) > 90% at 150 °C. At 200 °C, the discharge energy density of 0.25 wt% ZIF 8–67/PEI nanocomposites can still reach 1.84 J cm⁻³ with a η > 90%, which is nine times higher than that of pure PEI (0.21 J cm⁻³) under the same conditions, and it is the largest improvement compared with the previous reports.     

Negatively Charged Nanosheets Significantly Enhance the Energy-Storage Capability of Polymer-Based Nanocomposites

Polymer-based dielectric materials play a key role in advanced electronic devices and electric power systems. Although extensive research has been devoted to improve their energy-storage performances, it is a great challenge to increase the breakdown strength of polymer nanocomposites in terms of achieving high energy density and good reliability under high voltages. Here, a general strategy is proposed to significantly improve their breakdown strength and energy storage by adding negatively charged Ca₂Nb₃O₁₀ nanosheets. A dramatically enhanced breakdown strength (792 MV m⁻¹) and the highest energy density (36.2 J cm⁻³) among all flexible polymer-based dielectrics are observed in poly(vinylidene fluoride)-based nanocomposite capacitors. The strategy generalizability is verified by the similar substantial enhancements of breakdown strength and energy density in polystyrene-based nanocomposites. Phase-field simulations demonstrate that the further enhanced breakdown strength is ascribed to the local electric field, produced by the negatively charged Ca₂Nb₃O₁₀ nanosheets sandwiched with the positively charged polyethyleneimine, which suppresses the secondary impact-ionized electrons and blocks the breakdown path in nanocomposites. The results demonstrate a new horizon of high-energy-density flexible capacitors.     

Enhanced dielectric properties and energy storage density of surface engineered BCZT/PVDF-HFP nanodielectrics

Polymer nanocomposites have proved to be promising energy storage devices for modern power electronic systems. In this work we have studied the dielectric properties and dielectric energy storage densities of 0–3 type BCZT/PVDF-HFP polymer nanocomposites with different filler volume concentrations. BCZT nanopowder was synthesized by solgel method through citrate precursor method. The structural and morphological features of the BCZT nanopowder were examined by X-ray diffraction and transmission electron microscopy. For better polymer ceramic interface coupling, BCZT was surface functionalized with extended aromatic ligand, naphthyl phosphate (NPh). The surface functionalization was validated and quantified by thermogravimetric analysis and X-ray photoelectron spectroscopy. The dielectric constant of surface passivated BCZT nanoparticles was estimated to be ~?155 using slurry technique, while the dielectric permittivity of pristine BCZT nanopowder could not be assessed due to high innate surface conductivity. BCZT/PVDF-HFP polymer nanocomposite thin films were fabricated using solution casting technique. The dispersion quality of the ceramic fillers in the polymer matrix was examined by scanning electron microscopy. Due to better polymer ceramic interface, At 5 vol% filler concentration, NPh modified nanoBCZT/PVDF-HFP films showed enhanced dielectric breakdown strength and energy storage density than untreated nanoBCZT/PVDF-HFP and even pure polymer films. Maximum energy storage density of 8.5 J cm^?3 was obtained at an optimum filler concentration of 10 vol% for surface functionalized BCZT/PVDF-HFP composite films of 10 μm thickness.     

Effects of sintering temperature on the microstructure and dielectric properties of titanium dioxide ceramics

Nanostructured (~200 nm grain size) titanium dioxide (TiO₂) ceramics were densified at temperature as low as 800 °C by pressureless sintering in a pure oxygen atmosphere. Phase transition and microstructural development of sintered samples were studied by X-ray diffraction (XRD) and scanning electron microscopy (SEM). Dielectric properties including d.c. conductivity, dielectric constant, loss tangent, and dielectric breakdown strength (BDS) were determined for samples sintered at various temperatures. The influence of sintering temperature on the microstructural development, defect chemistry, and dielectric properties of TiO₂ is discussed. Nanostructured TiO₂ ceramics with high sintering density (>98%) lead to improved dielectric properties; high BDS (~1800 kV/cm), low electrical conductivity (~5 × 10⁻¹⁵ S/cm), high dielectric constant (~130), and low loss tangent (~0.09% at 1 kHz), which is promising for application in high energy density capacitors.     

Lead‐Free Antiferroelectric Silver Niobate Tantalate with High Energy Storage Performance

Antiferroelectric materials that display double ferroelectric hysteresis loops are receiving increasing attention for their superior energy storage density compared to their ferroelectric counterparts. Despite the good properties obtained in antiferroelectric La‐doped Pb(Zr,Ti)O₃‐based ceramics, lead‐free alternatives are highly desired due to the environmental concerns, and AgNbO₃ has been highlighted as a ferrielectric/antiferroelectric perovskite for energy storage applications. Enhanced energy storage performance, with recoverable energy density of 4.2 J cm^?3 and high thermal stability of the energy storage density (with minimal variation of ≤±5%) over 20–120 °C, can be achieved in Ta‐modified AgNbO₃ ceramics. It is revealed that the incorporation of Ta to the Nb site can enhance the antiferroelectricity because of the reduced polarizability of B‐site cations, which is confirmed by the polarization hysteresis, dielectric tunability, and selected‐area electron diffraction measurements. Additionally, Ta addition in AgNbO₃ leads to decreased grain size and increased bulk density, increasing the dielectric breakdown strength, up to 240 kV cm^?1 versus 175 kV cm^?1 for the pure counterpart, together with the enhanced antiferroelectricity, accounting for the high energy storage density.     

Achieving low dielectric loss and high energy density of polyimide composite dielectric film: inhibiting the formation of conductive path in both macro–microscales

Polyimide (PI) possesses high heat resistance and low dielectric loss, but exhibits low dielectric constant (k) and energy storage density, which constrains its further application in the field of high-temperature energy storage dielectric. The compounding of high-k filler and PI can greatly improve the dielectric constant of polymer-based dielectric composites, but it is often accompanied by the increase of dielectric loss and deterioration of breakdown strength. This issue can be effectively solved by the fabrication of dielectric filler with core–shell structure and construction of a layered structure. Therefore, in this research, a new SiC@polydopamine (PDA)@Ag nanoparticles (AgNPs)/PI flexible composite film with a sandwich structure (SSP) was prepared by a step-by-step casting method, in which the insulating layer (pristine PI) was intercalated between two polarization layers (SiC@PDA@Ag/PI composites). Pristine PI in the middle layer effectively hinders the transmission of carriers in the middle layer of the composite multilayer film. The SSP shows the highest energy storage density (1.35 J cm^?3 under 273.4 kV mm^?1), and the tanδ is as low as 0.0057. Additionally, SSP also shows excellent thermal stability and moisture resistance.

Graphical abstract

     

Strawberry‐like Core–Shell Ag@Polydopamine@BaTiO3 Hybrid Nanoparticles for High‐k Polymer Nanocomposites with High Energy Density and Low Dielectric Loss

Flexible nanocomposites comprising of polymer and high‐dielectric‐constant (high‐k) ceramic nanoparticles are becoming increasingly attractive for dielectric and energy storage applications in modern electronic and electric industry. However, a huge challenge still remains. Namely, the increase of dielectric constant usually at the cost of significant decrease of breakdown strength of the nanocomposites because of the electric field distortion and concentration induced by the high‐k filler. To address this long‐standing problem, by using nano‐Ag decorated core–shell polydopamine (PDA) coated BaTiO₃ (BT) hybrid nanoparticles, a new strategy is developed to prepare high‐k polymer nanocomposites with high breakdown strength. The strawberry‐like BT‐PDA‐Ag based ferroelectric polymer [i.e., poly(vinylideneflyoride‐co‐hexafluroro propylene), P(VDF‐HFP)] nanocomposites exhibit greatly enhanced energy density and significantly suppressed dielectric loss as well as leakage current density in comparison with the nanocomposites with the core–shell structured BT‐PDA. Coulomb‐blockade effect of super‐small nano‐Ag is used to explain the observed performance enhancement of the nanocomposites. The simplicity and scalability of the described approach provide a promising route to polymer nanocomposites for dielectric and energy storage applications.     

Sandwiched Polymer Nanocomposites Reinforced by Two-Dimensional Interface Nanocoating for Ultrahigh Energy Storage Performance at Elevated Temperatures

Polymer-based dielectrics are essential components in electrical and power electronic systems for high power density storage and conversion. A mounting challenge for polymer dielectrics is how to maintain their electrical insulation at not only high electric fields but also elevated temperatures, in order to meet the growing needs for renewable energies and grand electrifications. Here, a sandwiched barium titanate/polyamideimide nanocomposite with reinforced interfaces via two-dimensional nanocoatings is presented. It is demonstrated that boron nitride and montmorillonite nanocoatings can block and dissipate injected charges, respectively, to present a synergetic effect on the suppression of conduction loss and the enhancement of breakdown strength. Ultrahigh energy densities of 2.6, 1.8, and 1.0 J cm⁻³ are obtained at 150 °C, 200 °C, and 250 °C, respectively, with a charge-discharge efficiency >90%, far outperforming the state-of-the-art high-temperature polymer dielectrics. Cyclic charge-discharge tests up to 10 000 times verify the excellent lifetime of the interface-reinforced sandwiched polymer nanocomposite. This work provides a new pathway to design high-performance polymer dielectrics for high-temperature energy storage via interfacial engineering.     

Dielectric breakdown studies of Teflon perfluoroalkoxy at high temperature

Teflon^® perfluoroalkoxy (PFA) was evaluated for use as a dielectric material in high-temperature high-voltage capacitors for space applications. The properties that were characterized included the d.c. dielectric strength at temperatures up to 250 °C and the permittivity and dielectric loss as a function of frequency, temperature and voltage. To understand the breakdown mechanism taking place at high temperatures, the pre-breakdown discharge and conduction currents, and the dependence of dielectric strength on thickness of the film were determined. Confocal laser microscopy was performed to diagnose for microimperfections within the film structure. The results obtained show a significant decrease in the dielectric strength and an increase in dielectric loss with an increase in temperature, suggesting that impulse thermal breakdown could be a responsible mechanism in PFA film at temperatures above 150 °C.     

Optimized energy storage properties of BaTiO3-based ceramics with enhanced grain boundary effect

Energy storage dielectric ceramics play a more and more important role in power or electronics systems as a pulse power material, and the development of new technologies has put forward higher requirements for energy storage properties. Here, the sol-gel method was used to synthetize the 0.9BaTiO₃-0.1Bi(Mg_1/2Zr_1/2)O₃ (0.9BT–0.1BMZ) precursor powder and 0.9BT-0.1BMZ ceramics with pseudocubic phase was obtained. The 0.9BT-0.1BMZ dielectric ceramics possessed a strong relaxation behavior with 1.64 relaxation degree (g) and 0.15 eV relaxation activation energy (E_a) fitted by modified Curie–Weiss law and Vogel-Fulcher formulas, respectively. The most important was that by controlling the grain size to be reduced, the discharge energy storage density had been improved to 2.0 J/cm³ with high breakdown strength (325 kV/cm). In addition, the comprehensive analysis of electric field distributions, breakdown paths, and impedance spectra was illustrated the enhanced grain boundary effect can improve the energy storage performance obviously.

     

Dielectric and thermal properties of a machinable glass—ceramic at low temperatures

Measurements of the dielectric properties (2–300 K), specific heat (2–20 K), and thermal conductivity (2–22 K) are reported for a mica-containing glass-ceramic which has a machinability in the range from brass to low-carbon steel. The dielectric constant increases with increasing temperature and is field independent for field strengths up to at least 70 kV cm^?1 at low temperatures. Power-supply-limited attempts to measure the dielectric breakdown strength at low temperatures are consistent with the reported strength at room temperature (1.4 MV cm^?1). The thermal properties are similar to fused SiO₂ with two exceptions: the thermal conductivity does not show the ‘knee’ at ～ 10 K typical of amorphous materials, and the specific heat deviates strongly from a T³ law below 3.5 K