Advances in Polymer Dielectrics with High Energy Storage Performance by Designing Electric Charge Trap Structures.

Dielectric capacitors have been developed for nearly a century, and all-polymer film capacitors are currently the most popular. Much effort has been devoted to studying polymer dielectric capacitors and improving their capacitive performance, but their high conductivity and capacitance losses under high electric fields or elevated temperatures are still significant challenges. Although many review articles have reported various strategies to address these problems, to the best of current knowledge, no review article has summarized the recent progress in the high-energy storage performance of polymer-based dielectric films with electric charge trap structures. Therefore, this paper first reviews the charge trap characterization methods for polymeric dielectrics and discusses their strengths and weaknesses. The research progress on the design of charge trap structures in polymer dielectric films, including molecular chain optimization, organic doping, blending modification, inorganic doping, multilayered structures, and the mechanisms of the charge trap-induced enhancement of the capacitive performance of polymers are systematically reviewed. Finally, a summary and outlook on the fundamental theory of charge trap regulation, performance characterization, numerical calculations, and engineering applications are presented. This review provides a valuable reference for improving the insulation and energy storage performance of dielectric capacitive films.

Prediction of Energy Storage Performance in Polymer Composites Using High-Throughput Stochastic Breakdown Simulation and Machine Learning.

Polymer dielectric capacitors are widely utilized in pulse power devices owing to their high power density. Because of the low dielectric constants of pure polymers, inorganic fillers are needed to improve their properties. The size and dielectric properties of fillers will affect the dielectric breakdown of polymer-based composites. However, the effect of fillers on breakdown strength cannot be completely obtained through experiments alone. In this paper, three of the most important variables affecting the breakdown strength of polymer-based composites are considered: the filler dielectric constants, filler sizes, and filler contents. High-throughput stochastic breakdown simulation is performed on 504 groups of data, and the simulation results are used as the machine learning database to obtain the breakdown strength prediction of polymer-based composites. Combined with the classical dielectric prediction formula, the energy storage density prediction of polymer-based composites is obtained. The accuracy of the prediction is verified by the directional experiments, including dielectric constant and breakdown strength. This work provides insight into the design and fabrication of polymer-based composites with high energy density for capacitive energy storage applications.

Polymer dielectric films exhibiting superior high-temperature capacitive performance by utilizing an inorganic insulation interlayer.

With the rapid development of next-generation electrical power equipment and microelectronics, there is an urgent demand for dielectric capacitor films which can work efficiently under extreme conditions. However, sharply increased electrical conduction and drastically degrading electric breakdown strength are inevitable at elevated temperatures. Herein, a facile but effective method is proposed to improve high temperature capacitive performance. We report that utilizing an inorganic insulation interlayer can significantly increase the discharge energy density with a high efficiency above 90% at 150 °C, i.e., a discharged energy density of 4.13 J cm-3 and an efficiency of >90% measured at 150 °C, which is superior to the state-of-the-art dielectric polymers. Combining the experimental results and computational simulations reveals that the remarkable improvement in energy storage performance at high temperature is attributed to the blocking effects that reduce the leakage current and maintain the breakdown strength. The proposed facile method provides great inspiration for developing polymer dielectric films with high capacitive performance under extreme environments.

Intumescent flame retardants inspired template-assistant synthesis of N/P dual-doped three-dimensional porous carbons for high-performance supercapacitors.

Heteroatom-doped three-dimensional (3D) porous carbons possess great potential as promising electrodes for high-performance supercapacitors. Inspired by the inherent features of intumescent flame retardants (IFRs) with universal availability, rich heteroatoms and easy thermal-carbonization to form porous carbons, herein we proposed a self-assembling and template self-activation strategy to produce N/P dual-doped 3D porous carbons by nano-CaCO3 template-assistant carbonization of IFRs. The IFRs-derived carbon exhibited large specific surface area, well-balanced hierarchical porosity, high N/P contents and interconnected 3D skeleton. Benefitting from these predominant characteristics on structure and composition, the assembled supercapacitive electrodes exhibited outstanding electrochemical performances. In three-electrode 6 M KOH system, it delivered high specific capacitances of 407 F g-1 at 0.5 A g-1, and good rate capability of 61.2% capacitance retention at 20 A g-1. In two-electrode organic EMIMBF4/PC system, its displayed high energy density of 62.8 Wh kg-1 at a power density of 748.4 W kg-1, meanwhile it had excellent cycling stability with 84.7% capacitance retention after 10,000 cycles. To our best knowledge, it is the first example to synthesize porous carbon from IFRs precursor. Thus, the current work paved a novel and low-cost way for the production of high-valued carbon material, and expanded its application for high-performance energy storage devices.

Conjugated Conductive Polymer Materials and its Applications: A Mini-Review.

Since their discovery 50 years ago, conjugated conducting polymers have received increasing attention owing to their unique conductive properties and potential applications in energy storage, sensors, coatings, and electronic devices such as organic field-effect transistors, photovoltaic cells, and light-emitting devices. Recently, these materials have played a key role in providing a more comfortable environment for humans. Consequently, the development of novel, high-performance conjugated conductive materials is crucial. In this mini-review, the progress of conjugated conductive materials in various applications and the relationship between the chemical structures and their performances is reviewed. This can aid in the molecular design and development of novel high-performance conjugated polymer materials.

Recent Advances in Multilayer-Structure Dielectrics for Energy Storage Application.

An electrostatic capacitor has been widely used in many fields (such as high pulsed power technology, new energy vehicles, etc.) due to its ultrahigh discharge power density. Remarkable progress has been made over the past 10 years by doping ferroelectric ceramics into polymers because the dielectric constant is positively correlated with the energy storage density. However, this method often leads to an increase in dielectric loss and a decrease in energy storage efficiency. Therefore, the way of using a multilayer structure to improve the energy storage density of the dielectric has attracted the attention of researchers. Although research on energy storage properties using multilayer dielectric is just beginning, it shows the excellent effect and huge potential. In this review, the main physical mechanisms of polarization, breakdown and energy storage in multilayer structure dielectric are introduced, the theoretical simulation and experimental results are systematically summarized, and the preparation methods and design ideas of multilayer structure dielectrics are mainly described. This article covers not only an overview of the state-of-the-art advances of multilayer structure energy storage dielectric but also the prospects that may open another window to tune the electrical performance of the electrostatic capacitor via designing a multilayer structure.

Charge Injection and Dielectric Characteristics of Polyethylene Terephthalate Based on Semiconductor Electrodes.

Employing a novel semiconductor electrode in comparison with the traditional semiconductor electrode made of polyethylene/ethylene-vinyl-acetate copolymer/carbon-black (PE/EVA/CB) composite, characteristic charge carriers are injected into polyethylene terephthalate (PET) as a polymer dielectric paradigm, which will be captured by specific deep traps of electrons and holes. Combined with thermal stimulation current (TSC) experiments and first-principles electronic-state calculations, the injected charges from the novel electrode are characterized, and the corresponding dielectric behavior is elucidated through DC conductance, electrical breakdown and dielectric spectrum tests. TSC experiments with novel and traditional semiconductor electrodes can distinguish the trapping characteristics between hole and electron traps in polymer dielectrics. The observable discrepancy in space charge-limited conductance and the stable dielectric breakdown strength demonstrate that the electron injection into PET film specimen is restricted by using the novel semiconductor electrode. Attributed to the favorable suppression on the inevitable electron injections from metal electrodes, adopting novel i-electrode can avoid the evident abatement of dipole orientation polarization caused by space charge clamp, but will engender the accessional high-frequency dielectric loss from dielectric relaxations of interface charges at i-electrodes.

Excellent Energy Storage Performance of Ferroconcrete-like All-Organic Linear/Ferroelectric Polymer Films Utilizing Interface Engineering.

Ferroelectric polymers are regarded as the preferred material in dielectric energy storage devices because of their high dielectric constant. However, their relatively low breakdown strength and efficiency restrict their practical application. This work combines coaxial spinning and hot pressing to compound the highly insulating linear poly(methyl methacrylate) (PMMA) and ferroelectric poly(vinylidene fluoride) (PVDF) to obtain a PMMA/PVDF all-organic film with a ferroconcrete-like structure. Further, improvements in the energy storage performance over those of the pristine polymer were achieved via modulation of the PMMA to PVDF ratio. The 45% PMMA/PVDF film had an energy storage density of 17.7 J/cm3 and an energy efficiency of 73% at 640 kV/mm. Moreover, 51% PMMA/PVDF exhibited the best energy storage density (U = 20.7 J/cm3, η = 63% at 630 kV/mm). This work, therefore, provides a new idea for the design of all-organic polymer films for the field of energy storage.

Improved Energy Storage Performance of All-Organic Composite Dielectric via Constructing Sandwich Structure.

Improving the energy storage density of dielectrics without sacrificing charge-discharge energy storage efficiency and reliability is crucial to the performance improvement of modern electrical and electronic systems, but traditional methods of doping high-dielectric ceramics cannot achieve high energy storage densities without sacrificing reliability and storage efficiency. Here, an all-organic energy storage dielectric composed of ferroelectric and linear polymer with a sandwich structure is proposed and successfully prepared by the electrostatic spinning method. Additionally, the effect of the ferroelectric/linear volume ratio on the dielectric properties, breakdown, and energy storage is systematically studied. The results show that the structure has good energy storage characteristics with a high energy storage density (9.7 J/cm3) and a high energy storage efficiency (78%). In addition, the energy storage density of the composite dielectric under high energy storage efficiency (90%) is effectively improved (25%). This result provides theoretical analysis and experience for the preparation of multilayer energy storage dielectrics which will promote the development and application of energy storage dielectrics.

Synthesis of a Novel Semi-Conductive Composites Doping with La0.8Sr0.2MnO3 for Excellent Electric Performance for HVDC Cable.

The semi-conductive layer located between the wire core and the insulation layer in high voltage direct current (HVDC) cable plays a vital role in uniform electric field and affecting space charges behaviors. In this work, the research idea of adding ionic conductive particles to semi-conductive materials to improve the conductive network and reduce the energy of the moving charge inside it and to suppress charge injection was proposed. Semi-conductive composites doped with different La0.8Sr0.2MnO3 (LSM) contents were prepared. Resistivity at different temperatures was measured to investigate the positive temperature coefficient (PTC) effect. Pulse electro-acoustic (PEA) method and thermal-stimulation depolarization currents (TSDC) tests of the insulation layers were carried out. From the results, space charge distribution and TSDC currents in the insulation samples were analyzed to evaluate the inhibitory effect on space charge injection. When LSM content is 6 wt. %, the experimental results show that the PTC effect of the specimen and charge injection are both being suppressed significantly. The maximum resistivity of it is decreased by 53.3% and the insulation sample has the smallest charge amount, 1.85 × 10-7 C under 10 kV/mm-decreased by 40%, 3.6 × 10-7 C under 20 kV/mm-decreased by 45%, and 6.42 × 10-7 C under 30 kV/mm-decreased by 26%. When the LSM content reaches 10 wt. %, the suppression effect on the PTC effect and the charge injection are both weakened, owing to the agglomeration of the conductive particles inside the composites which leads to the interface electric field distortion and results in charge injection enhancement.

Investigation of the Space Charge and DC Breakdown Behavior of XLPE/α-Al2O3 Nanocomposites.

This paper describes the effects of α-Al2O3 nanosheets on the direct current voltage breakdown strength and space charge accumulation in crosslinked polyethylene/α-Al2O3 nanocomposites. The α-Al2O3 nanosheets with a uniform size and high aspect ratio were synthesized, surface-modified, and characterized. The α-Al2O3 nanosheets were uniformly distributed into a crosslinked polyethylene matrix by mechanical blending and hot-press crosslinking. Direct current breakdown testing, electrical conductivity tests, and measurements of space charge indicated that the addition of α-Al2O3 nanosheets introduced a large number of deep traps, blocked the charge injection, and decreased the charge carrier mobility, thereby significantly reducing the conductivity (from 3.25 × 10-13 S/m to 1.04 × 10-13 S/m), improving the direct current breakdown strength (from 220 to 320 kV/mm) and suppressing the space charge accumulation in the crosslinked polyethylene matrix. Besides, the results of direct current breakdown testing and electrical conductivity tests also showed that the surface modification of α-Al2O3 nanosheets effectively improved the direct current breakdown strength and reduced the conductivity of crosslinked polyethylene/α-Al2O3 nanocomposites.

Effect of Semi-Conductive Layer Modified by Magnetic Particle SrFe12O19 on Charge Injection Characteristics of HVDC Cable.

For high voltage direct current (HVDC) cable, a semi-conductive layer lies between the conductor and the insulation layer; as the charge migrates the path from the conductor to the insulation material, it will affect space charge injection. In this work, the research idea of changing the injection path of moving charges within semi-conductive layer by magnetic particles was proposed. Semi-conductive composites with different SrFe12O19 contents of 1 wt.%, 5 wt.%, 10 wt.%, 20 wt.%, and 30 wt.% were prepared, and the amount of injected charges in the insulation sample was characterized by space charge distribution, polarization current, and thermally-stimulated depolarization current. The experimental results show that a small amount of SrFe12O19 can significantly reduce charge injection in the insulation sample, owing to the deflection of the charge migration path, and only part of the electrons can enter the insulation sample. When the content is 5 wt.%, the insulation sample has the smallest charge amount, 0.89 × 10-7 C, decreasing by 37%, and the steady-state current is 6.01 × 10-10 A, decreasing by 22%. When SrFe12O19 content exceeds 10 wt.%, the charge suppression effect is not obvious and even leads to the increase of charge amount in the insulation sample, owing to the secondary injection of charges. Most moving charges will deflect towards the horizontal direction and cannot direct access to the insulation sample, resulting in a large number of charges accumulation in the semi-conductive layer. These charges will seriously enhance the interface electric field near the insulation sample, leading to the secondary injection of charges, which are easier to inject into the insulation sample.

Charge Injection Characteristics of Semi-Conductive Composites with Carbon Black-Polymer for HVDC Cable.

Semi-conductive composites composed of carbon black-polymer play an important role in uniform electric field in high voltage direct current (HVDC) cable. They also affect space charge behaviors in the insulation material. However, the charge injection characteristics of semi-conductive composites are not detailed. In this work, the electrode structure of 'Semi-conductive composites- Insulation material- Metal bottom' (S-I-M) is proposed, and the currents formed by injected charges from semi-conductive composites are characterized by the thermally stimulated depolarization current (TSDC) method. Further, the experimental results based on the structure of S-I-M are compared with the traditional electrode structure of M-I-M (Metal upper electrode- Insulation material- Metal bottom electrode) and the simplified cable electrode structure of MS-I-M (Metal upper electrode-Semi-conductive electrode- Insulation material- Metal bottom electrode), respectively. The experimental results show that the semi-conductive composite plays an important role in the charge injection process and it presents a different tendency under different compound modes of temperature and electric field. For the low electric field (E ≤ 5 kV/mm) and the low temperature (T ≤ 50 °C), the current caused by the accumulated charges follows the rule, IS > IMS > IM. For the low electric field and high temperature (T > 50 °C), the current caused by the injected charges follows the rule, IMS > IM > IS. This phenomenon is closely related to the interface characterization and contact barrier.

Fabrication of superhydrophobic composite coating based on fluorosilicone resin and silica nanoparticles.

Composite superhydrophobic coating built with film former and filler is attracting much attention for its facile and convenient fabrication, but significant limitations and disadvantages still remain. In this paper, a composite superhydrophobic coating is introduced which can be cured at room temperature and made by dispersing modified silica nanoparticles with 1H, 1H, 2H, 2H-perfluorooctyltriethoxysilane in fluorosilicone resin. Silica content and dispersion time showed obvious influences on the morphology and topography of composite coating by reuniting dispersed nanoparticles to form peaks on the surface. Excessively large distances between these peaks would decrease water contact angle value. Increasing slope of peaks, appropriate distance between peaks and decreasing diameter size of peaks would diminish sliding angle value. Formation mechanism of the composite coating based on fluorosilicone resin and modified nanoparticles was explained using interpenetrating polymer model.

Enhanced Thermal Conductivity and Dielectric Properties of Iron Oxide/Polyethylene Nanocomposites Induced by a Magnetic Field.

Iron Oxide (Fe3O4) nanoparticles were deposited on the surface of low density polyethylene (LDPE) particles by solvothermal method. A magnetic field was introduced to the preparation of Fe3O4/LDPE composites, and the influences of the magnetic field on thermal conductivity and dielectric properties of composites were investigated systematically. The Fe3O4/LDPE composites treated by a vertical direction magnetic field exhibited a high thermal conductivity and a large dielectric constant at low filler loading. The enhancement of thermal conductivity and dielectric constant is attributed to the formation of the conductive chains of Fe3O4 in LDPE matrix under the action of the magnetic field, which can effectively enhance the heat flux and interfacial polarization of the Fe3O4/LDPE composites. Moreover, the relatively low dielectric loss and low conductivity achieved are attributed to the low volume fraction of fillers and excellent compatibility between Fe3O4 and LDPE. Of particular note is the dielectric properties of Fe3O4/LDPE composites induced by the magnetic field also retain good stability across a wide temperature range, and this contributes to the stability and lifespan of polymer capacitors. All the above-mentioned properties along with the simplicity and scalability of the preparation for the polymer nanocomposites make them promising for the electronics industry.

Enhanced dielectric properties of poly(vinylidene fluoride) composites filled with nano iron oxide-deposited barium titanate hybrid particles.

We report enhancement of the dielectric permittivity of poly(vinylidene fluoride) (PVDF) generated by depositing magnetic iron oxide (Fe3O4) nanoparticles on the surface of barium titanate (BT) to fabricate BT-Fe3O4/PVDF composites. This process introduced an external magnetic field and the influences of external magnetic field on dielectric properties of composites were investigated systematically. The composites subjected to magnetic field treatment for 30 min at 60 °C exhibited the largest dielectric permittivity (385 at 100 Hz) when the BT-Fe3O4 concentration is approximately 33 vol.%. The BT-Fe3O4 suppressed the formation of a conducting path in the composite and induced low dielectric loss (0.3) and low conductivity (4.12 × 10(-9) S/cm) in the composite. Series-parallel model suggested that the enhanced dielectric permittivity of BT-Fe3O4/PVDF composites should arise from the ultrahigh permittivity of BT-Fe3O4 hybrid particles. However, the experimental results of the BT-Fe3O4/PVDF composites treated by magnetic field agree with percolation theory, which indicates that the enhanced dielectric properties of the BT-Fe3O4/PVDF composites originate from the interfacial polarization induced by the external magnetic field. This work provides a simple and effective way for preparing nanocomposites with enhanced dielectric properties for use in the electronics industry.

The application of low frequency dielectric spectroscopy to analyze the electrorheological behavior of monodisperse yolk-shell SiO2/TiO2 nanospheres.

Monodisperse SiO2/TiO2 yolk-shell nanospheres (YSNSs) with different SiO2 core sizes were fabricated and adopted as dispersing materials for electrorheological (ER) fluids to investigate the influence of the gradual structural change of disperse particles on ER properties. The results showed that the ER performance of the YSNS-based ER fluid prominently enhanced with the decrease of SiO2 core size, which was attributed to the enhancement of electric field force between YSNSs. Combined with the analysis of dielectric spectroscopy, it was found that the increase of permittivity at low frequency (10(-2)-10(0) Hz) was due to the increase of polarized charges caused by secondary polarization (Psp). Moreover, the number of Psp closely related to the distributing change of polarized particles in ER fluid was a critical factor to assess the ER performance. Additionally, a parameter K (the absolute value of the slope of permittivity curves at 0.01 Hz) could be utilized to characterize the efficiency of structural evolution of polarized particles in ER fluid. Compared with the ER performance, it could be concluded that the value of Δε(100Hz-100kHz)' just demonstrated the initial intensity of the interface polarization in the ER fluid as the electric field was applied, which ignored the distributing evolution of polarized disperse particles in ER fluid. The polarizability Δε(0.01Hz-100kHz)' obtained in the frequency range of 10(-2)-10(5) Hz should be more suitable for analyzing the system of ER fluid. The relationships between polarizability of disperse particles, parameter K and ER properties were discussed in detail.

Enhanced Electrorheological Performance of Nb-Doped TiO2 Microspheres Based Suspensions and Their Behavior Characteristics in Low-Frequency Dielectric Spectroscopy.

Titanium dioxide and Nb-doped titanium dioxide microspheres with the same size were fabricated by a simple sol-gel method, and the formation mechanism of Nb-doped titanium dioxide microspheres was proposed. Titanium dioxide and Nb-doped titanium dioxide microspheres were adopted as dispersed materials for electrorheological (ER) fluids to investigate the influence of the charge increase introduced by Nb doping on the ER activity. The results showed that Nb doping could effectively enhance the ER performance. Combining with the analysis of dielectric spectroscopy, it was found that the interface polarization of Nb-doped TiO2 ER fluid was larger than that of TiO2 ER fluid, which might be caused by more surface charges in Nb-TiO2 microspheres due to Nb(5+) doping and resulting in enhancement of electric field force and strengthening of fibrous structure. In addition, by comparing and analyzing the permittivity curves of Nb-TiO2/LDPE solid composite and Nb-TiO2/silicone-oil fluid composite, it could be concluded that the enhancement of permittivity at low frequency resulted from the increase of the order degree of dispersed particles in ER fluid rather than from the quasi-dc (QDC) behavior. Moreover, the absolute value of slope of permittivity curves (K) at 0.01 Hz could be utilized as the standard for judging the ability to maintain the chainlike structure. The relationships between polarizability of dispersed particles, dielectric spectrum, parameter K, and ER properties were discussed in detail.

Bipolar high-repetition-rate high-voltage nanosecond pulser.

The pulser designed is mainly used for producing corona plasma in waste water treatment system. Also its application in study of dielectric electrical properties will be discussed. The pulser consists of a variable dc power source for high-voltage supply, two graded capacitors for energy storage, and the rotating spark gap switch. The key part is the multielectrode rotating spark gap switch (MER-SGS), which can ensure wider range modulation of pulse repetition rate, longer pulse width, shorter pulse rise time, remarkable electrical field distortion, and greatly favors recovery of the gap insulation strength, insulation design, the life of the switch, etc. The voltage of the output pulses switched by the MER-SGS is in the order of 3-50 kV with pulse rise time of less than 10 ns and pulse repetition rate of 1-3 kHz. An energy of 1.25-125 J per pulse and an average power of up to 10-50 kW are attainable. The highest pulse repetition rate is determined by the driver motor revolution and the electrode number of MER-SGS. Even higher voltage and energy can be switched by adjusting the gas pressure or employing N(2) as the insulation gas or enlarging the size of MER-SGS to guarantee enough insulation level.