Enhanced dielectric response of ternary polymeric composite films via interfacial bonding between V2C MXene and wide-bandgap ZnS

Increasing the dielectric constant of polymer/sulfide ceramic composites by using wide-bandgap semiconducting sulfide ceramic fillers like ZnS is difficult because of their low interface polarization. To increase the dielectric constant, in this study, ternary polymer-based composite films were designed and fabricated using a hybrid filler consisting of shell-like ZnS particles and core-like V₂C MXene particles. First, V₂C MXene with a multi-layered structure was synthesized from the simplest raw materials followed by the in-situ hydrothermal growth of ZnS particles around the V₂C particles. Then, binary polymer/ZnS and ternary polymer/V₂C–ZnS composites were fabricated, and their dielectric, conductive, and electrical breakdown properties were investigated. Finally, the effect of interfacial bonding between the V₂C and ZnS phases was investigated by density functional theory calculations, and the contribution of V₂C/ZnS interfacial bonding to the higher dielectric constant of the ternary composites than that of the binary composites was explained. The ternary composites exhibited balanced electrical properties suitable for energy storage applications. The ternary composite with 10 wt% hybrid filler loading exhibited a high dielectric constant of ~52, a low dielectric loss of ~0.11 at 100 Hz, and a high electrical breakdown strength of ~202 MV m⁻¹. This study paves the way for the facile fabrication of high-performance composite dielectrics for application in advanced capacitors.     

Enabling high dielectric response and low electrical leakage in polymer/mesoporous-silica@CdTe-quantum-dots nanocomposites by excitonic dipoles and pore-canal restriction

High dielectric response and low leakage conduction are desired in polymer/ceramic composite dielectrics for capacitive energy storage. Rational structural design of hybrid ceramic filler can lead to a balance between high dielectric constant and insulation in composites. In this study, high dielectric constant and breakdown strength were achieved in fluoropolymer/mesoporous silica@CdTe nanocomposite films. Mesoporous silica nanoparticles (MSNs) were employed owing to their high insulation and complex electron-leakage channel. CdTe quantum dots combined with pore-canal inwalls of MSNs were employed because of their internal exciton polarization and MSNs/CdTe interface polarization. Compared with polymer/MSNs composites, polymer/MSNs@CdTe composites exhibited remarkably improved dielectric constant, slightly increased dielectric loss, and slightly reduced breakdown strength. High dielectric constant of ternary composites was ascribed to exciton orientation inside CdTe and interfacial dipole orientation between MSNs and CdTe. High breakdown strength was attributed to high insulation in MSNs and long-range electron transfer inside MSNs@CdTe. An optimal ternary composite with 12 wt% MSNs@CdTe showed a high dielectric constant of ~56, low dielectric loss of ~0.19 at 100 Hz, and high breakdown strength of ~308 MV m^-1. The results of this study can provide insights for enabling large-scale fabrication of modern composite dielectrics based on mesoporous particles@semi-conductive quantum dots fillers.     

Enhanced dielectric constant and breakdown strength in dielectric composites using TiO2@HfO2 nanowires with gradient dielectric constant

To investigate the influence of modification of ceramic fillers on the dielectric properties of polymer-based composites, TiO₂ and core-shell structured TiO₂@HfO₂ nanowires were synthesized, and investigated in this study. TiO₂ nanowires/polyvinylidene fluoride (PVDF) and TiO₂@HfO₂ nanowires/PVDF nanocomposites were prepared using the solution casting method. The experimental results showed that the TiO₂@HfO₂ nanowires/PVDF composites had improved dielectric properties compared with that of the TiO₂ nanowires/PVDF composites. Owing to the enhanced interfacial polarisation by the multilevel interface, the composites with 10 wt % TiO₂@HfO₂ nanowires achieved the highest permittivity of 12.56 at 1 kHz, which was enhanced by ～72% compared to the PVDF matrix. The electric field was evenly distributed by building the fillers with a gradient dielectric constant. The characteristic breakdown strength of the composite with 5 wt % TiO₂@HfO₂ reached 377.76 kV/mm, compared with that of 334.37 kV/mm for the composite with 5 wt % TiO₂ nanowires. This study initiated a novel strategy for preparing dielectrics with high dielectric constant and improved breakdown strength.     

Novel dielectric behaviors in PVDF‐based semiconductor composites

Composites of polyvinylidene fluoride (PVDF) filled with different conductive fillers as carbon black (CB), nickel (Ni), zinc (Zn), and tungsten (W), respectively, were prepared at same processing condition. The temperature dependence of dielectric behaviors of composites was studied at wide filler concentration and wide frequency ranges. Results show that there are giant dielectric constants as the concentration of filler is near the percolation threshold. The dielectric constants of all studied composites decrease slowly with increasing of frequency and rise gradually with increasing filler contents in the composites. Two relaxation peak regions of dielectric constant are observed from ?30 to 40°C and from 100 to 150°C, which can be attributed to the contribution of polar effect of PVDF. The CB filled PVDF (CB/PVDF) composites present a lower percolation threshold than other metallic‐filler filled PVDF composites. The maximal dielectric constant was found in the Ni filled PVDF (Ni/PVDF) composite. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Improved dielectric and mechanical properties of Ti3C2Tx MXene/silicone rubber composites achieved by adding a few boron nitride nanoplates

MXenes have attracted great attentions in the fabrication of dielectric polymer composites because of their excellent electrical conductivity. However, the high dielectric loss tangent would suppress the application of such polymer-based composites. Incorporating insulating fillers might be a solution. Herein, Ti₃C₂T_x MXene/silicone rubber (SR) composites incorporated with boron nitride (BN) nanoplates were prepared. The homogeneous distribution of fillers was obtained in the composites, which was also thermally stable up to 400 °C. Dielectric constant of 7.06 (2.54 times of pure SR) and dielectric loss tangent of 0.00131 were achieved when the filling contents of MXene and BN in SR composite were 1.2 wt% and 5 wt%, respectively. The improved dielectric constant can be ascribed to the enhanced interfacial polarization and the formation of conductive network, while the low dielectric loss tangent can be due to the insulating interlayers of BN which could inhibit the transfer of free electrons from conductive fillers to the insulating polymer matrices. BN/MXene/SR composites displayed improved mechanical properties (tensile stress of 671 kPa and elongation at break of 353%) and good flexibility (elastic modulus of 540 kPa) due to the low filling content of fillers. This work is promising for preparing dielectric polymer composites in applications of electronic devices.     

Poly(arylene ether nitrile) ternary dielectric composites modulated via polydopamine-assisted BaTiO3 decorating MoS2 sheets

Flexible, high-k and thermostability polymer-based dielectric composites are the core components in electrostatic capacitors and embedded devices. Herein, the dielectric polymer matrix composites are developed by embedding polydopamine (PDA)-encapsulated hydroxylated barium titanate (BTH) and molybdenum disulfide (MoS₂) into poly(arylene ether nitrile) (PEN) matrix. The MoS₂/PDA@BTH-1 particles served as fillers are prepared by polydopamine deposition technology assisted with hydrogen bonding interactions. The introduction of PDA intermediate layer contributes to the construction of multiple interfaces and nanocapacitor networks, enhancing interfacial polarization. Based on this, the resulted dielectric composite with 15 wt% MoS₂/PDA@BTH-1 loading exhibits the dielectric constant of 17.3 at 1 kHz, higher than that of 4.2 of PEN, while can maintain relatively low dielectric loss simultaneously. The possible mechanisms and synergistic enhancement effect of MoS₂/PDA@BTH-1 particles on the dielectric properties of composites are also proposed. The results of permittivity-temperature stability show that the dielectric constant of PEN-based dielectric composites is stable when reaches 158 °C, indicating that the film can be used in capacitor at temperatures up to 150 °C, higher than that of most polymer capacitors. All in all, a feasible pathway is provided to design PEN-based dielectric composites with high-k to adopt the high-temperature environment in electrostatic capacitors and embedded devices.     

Flexible BaTiO3/SiC@PbTiO3/epoxy composite films with enhanced dielectric performance at high frequency

Flexible polymer composites with high dielectric constants and low dielectric losses at high frequencies are highly desired in microwave and RF applications. However, a high dielectric constant is often obtained at the expense of flexibility because a high loading of filler is needed. In this work, we synthesize a core-shell structured 1D filler by coating high-dielectric-constant PbTiO₃ onto the surface of low-thermal-expansion-coefficient SiC nanofibers, which are then incorporated into the epoxy matrix together with BaTiO₃ nanoparticles to form the multi-phase BaTiO₃/SiC@PbTiO₃/epoxy composite film. A high dielectric constant (35 at 100 Hz and 20 at 5 GHz) and a low dielectric loss (0.023 at 100 Hz and 0.13 at 5 GHz) are achieved as the filling content of SiC@PbTiO₃ and BaTiO₃ is 5.24 wt% and 80 wt%, respectively. Prediction models of the effective dielectric constant of polymer-based composites reveal that a continuous polarization network is constructed in the composites owing to the physical contact between BaTiO₃ and PbTiO₃. The construction of the multi-phase filler provides a feasible way to effectively adjust and improve the dielectric properties of polymer-based composite films.     

Multifunctional fiberglass-reinforced PMMA-BaTiO3 structural/dielectric composites

Fiberglass-reinforced polymer composites were investigated for potential use as structural dielectrics in multifunctional capacitors that require simultaneous excellent mechanical properties and good energy storage characteristics. Composites were fabricated employing poly(methyl methacrylate), PMMA, as the structural matrix. While barium titanate (BaTiO₃) nanopowder was added to the composites for its high room temperature dielectric constant, fiberglass was employed to confer high stiffness. A conductive polymer blend of poly (3,4-ethylenedioxythiophene) and polystyrene sulfonate (PEDOT:PSS) was used to coat the BaTiO₃ nanoparticles with the purpose of further elevating the dielectric constant of the resultant PMMA-composites. FTIR spectroscopy, TGA and SEM measurements were conducted to prove the successful coating of BaTiO₃ nanoparticles with the PEDOT:PSS blend. TEM measurements revealed a good dispersion of coated nanoparticles throughout the PMMA matrix. The fiberglass-reinforced-PMMA composites containing neat and coated BaTiO₃ were found to exhibit excellent stiffness. In addition, the use of PEDOT:PSS in conjunction with BaTiO₃ was observed to improve the dielectric constant of the composites. Finally, the dielectric constant of the structural composites was found to vary only slightly with temperature.     

High dielectric permittivity and low loss in PVDF filled by core-shell Zn@ZnO particles

In this study, metal-semiconductor Zn@ZnO core-shell particles were prepared by the heat treatment of raw Zn powder under air atmosphere, and the prepared Zn@ZnO particles were incorporated into poly(vinylidene fluoride) (PVDF) to obtain high dielectric permittivity polymer. The results indicate that the Zn@ZnO particles remarkably increased the dielectric constant of the PVDF composites compared with the raw Zn/PVDF due to the duplex interfacial polarizations induced by ZnO-Zn interface and ZnO-PVDF interface. Moreover, the dielectric permittivity of the Zn@ZnO/PVDF composites can be further optimized by adjusting the thickness of ZnO shell. The dielectric loss and conductivity were still remained at low acceptable level owing to the presence of ZnO shell between Zn core and PVDF matrix which serves as an interlayer between the Zn cores preventing them from contacting with each other. The developed Zn@ZnO/PVDF polymer composites with high dielectric constant and low loss are potential for embedded capacitor applications.     

Structural,dielectric and mechanical behaviors of (La,Nb) Co-doped TiO2/Silicone rubber composites

Ceramic/polymer composites have great potential to achieve the concomitant enhancement of both dielectric constant and breakdown field while maintaining other superior properties of the polymer matrix, ideal for elastomer sensors, actuators, capacitive energy storage, and many other applications. However, material incompatibility between the ceramic filler and the polymer matrix often leads to void formation, particle aggregation and phase separation, with significantly degraded performance. Herein, through surface modification, co-doped TiO₂ particles were uniformly dispersed and bridged onto the silicone rubber matrix via a silane coupling agent for fabricating composites via mechanical mixing and hot-pressing. The synthesized composites exhibit enhanced dielectric constant, increased from 2.78 to 5.06 when 50 wt% co-doped TiO₂ particles are incorporated. Their dielectric loss is less than 0.001 in a broad frequency range. Theoretical modelling and experimental results reveal that the morphology and dispersion state of co-doped TiO₂ particles were crucial to the dielectric properties of the silicone rubber-based composites. Besides, the composites are thermally stable up to 400 °C. Significantly increased tensile strength (612 kPa) and elongation at break (330%) were obtained for the composite incorporated with 30 wt% co-doped TiO₂ particles, accompanied by a moderate increased elastic module (540 kPa). Such composites have the potential for different applications.     

Measurement of AC conductivity and dielectric properties of flexible conductive styrene–butadiene rubber‐carbon black composites

Flexible conductive polymer composites were prepared using styrene–butadiene rubber (SBR) as a matrix and conductive carbon black as filler. The filler loading was varied from 10 to 60 phr. The effect of frequency, filler loading, temperature, and applied pressure on the AC conductivity, permittivity, and loss factor of the composites was studied. The AC conductivity of low and high loaded composites was found to be frequency dependent and independent respectively. The permittivity and the loss factor were continuously decreasing with increasing frequency. The increase in filler loading increased the AC conductivity, dielectric constant, and loss factor of the composites. Increase in temperature imposed increase in conductivity and permittivity of the composites. With increasing applied pressure the properties showed exponential increase. The effect of time under a constant compressive stress was studied and dielectric relaxation times were evaluated. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 986–995, 2007     

Exceptional dielectric properties of chlorine-doped graphene oxide/poly (vinylidene fluoride) nanocomposites

Herein, we report a facile method to significantly enhance the dielectric performance of reduced graphene oxide-based polymer composites. Addition of thionyl chloride into graphene oxide (GO) dispersion induces synergistic modifications of the structure, chemistry, charge carrier density and electrical conductivity of GO, as well as the interfacial interaction and phase of the surrounding matrix in the poly (vinylidene fluoride) (PVDF) composite. The composites reinforced with a very low reduced chlorinated GO (Cl-rGO) content of 0.2 vol% deliver an exceptional dielectric constant of 364 with a moderate dielectric loss of 0.077 at 1 kHz. These values are well contrasted with the corresponding properties of the neat PVDF polymer with a constant of 28 and a loss of 0.0029. Synergistic effects arising from chlorination are identified, including the much enhanced electrical conductivity of Cl-GO sheets by more than 3 orders of magnitude through introducing charge-transfer complexes, the improved interfacial interactions between the fillers and the PVDF matrix through hydrogen bonds, and the transformation of PVDF to β-phase with an inherently high dielectric constant due to dipolar interaction. The comparison with the literature data confirms superior dielectric performance of the present Cl-rGO/PVDF composites.     

Flexible and low cost lead free composites with high dielectric constant

Highly flexible lead free composite film having random distribution of ceramic filler was synthesized using Barium Titanate (BT) as a filler and inexpensive Thermoplastic Polyurethane (TPU) as a matrix. The results show that the 30 vol% BT-TPU composite has a dielectric constant of ~31 which is comparable to the expensive and difficult to produce PVDF based composites. With a breakdown field of 150 kV/mm, an energy density value of ~3 J/cm³ was estimated. These lead-free TPU based composites provide an alternative to PVDF based composites for energy storage applications.     

Dielectric property and electromagnetic interference shielding effectiveness of ethylene vinyl acetate‐based conductive composites: Effect of different type of carbon fillers

Carbon black, short carbon fiber (SCF), and multiwall carbon nano‐tube (MWNT)‐filled conductive composites were prepared from ethylene vinyl acetate copolymer. The dielectric property and electromagnetic interference (EMI) shielding of carbon black, MWNT, and SCF‐filled composites were studied with different filler loadings. The dielectric constant and loss of filled polymer composites is due to the formation of interfacial polarization in the polymer matrix. It was found that the dielectric constant, dielectric loss, and EMI shielding of filled composites depends on amount and type of filler loading. The results of different experiments have been discussed in the light of break down and formation of continuous conductive network in polymer matrix. The results indicate that these composites can be used as effective EMI shielding materials. POLYM. COMPOS., 2011. © 2011 Society of Plastics Engineers.     

Core-shell structured BaTiO3@SiO2@PDA for high dielectric property nanocomposites with ultrahigh energy density

Flexible nanocomposite dielectrics with high dielectric constant and discharge energy density have broad application prospects in the field of energy storage. However, dielectrics with high dielectric constant tend to have a high dielectric loss. Herein, we prepared a dielectric composite material with ultra-high discharge energy density by modifying the interface between nanoparticles and poly(vinylidene fluoride-co-hexafluoropropylene) (P[VDF-HFP]). After coating a shell of insulating amorphous SiO₂ (~7 nm) outside the barium titanate (BT), the electric field concentration and current density inside BT particles can be significantly reduced. In addition, coating the SiO₂ shell with a polydopamine (PDA) shell (~7 nm) not only enhances the interface interaction between the nanoparticles and the polymer matrix, but also can form lots of microcapacitors in the composite. As a result, an ultra-high discharge energy density of 13.78 J/cm³ at the expense of relatively inconspicuous efficiency (~59.8%) in the BT@SiO₂@PDA/P (VDF-HFP) with 2.5 wt% loading has been achieved under 460 kV/mm. This is mainly attributed to the increases of dielectric constant from 12.1 to 14.2 and the relatively low dielectric loss (0.086) at 100 Hz. Moreover, compared with the pure P (VDF-HFP) (400 kV/mm), the breakdown voltage of the composite with 2.5 wt% loading is surged to 460 kV/mm, which benefited from the hindrance of nanoparticles on carrier migration at low content. This work has realized a thin-film dielectric with ultra-high discharge energy density through a novel design of the nanoparticle structure, providing a theoretical direction for the development of polymer dielectric capacitors.     

Improved dispersion and interfacial interaction of SiO2@polydopamine fillers in polytetrafluoroethylene composites for reduced thermal expansion and suppressed dielectric deterioration

Copper-clad laminate (CCL) comprised of copper foil and polytetrafluoroethylene (PTFE) faces severe thermal expansion mismatch due to the discrepancy in coefficient of thermal expansion (CTE) between the two components. Incorporating inorganic fillers with low CTE into PTFE has been proved to be a promising way to achieve the goal. However, it is a challenge to achieve homogeneous distribution and good interfacial interaction of fillers in PTFE composites owing to the characteristics of PTFE emulsion. In this work, core@shell structured SiO₂@polydopamine fillers (SiO₂@PDA) were synthesized and incorporated into PTFE matrix to form SiO₂@PDA/PTFE composites. Due to the presence of PDA shell, SiO₂@PDA exhibited improved dispersion and interfacial interaction, contributing to the reduced CTE and suppressed dielectric deterioration of SiO₂@PDA/PTFE composites. With 40 vol% of filler, the CTE of SiO₂@PDA/PTFE composite was efficiently reduced (50%), coupled with a limited sacrifice of only 2% and 40% of increments for dielectric constant (D_k, 2.3) and dielectric loss (D_f, 2.4 × 10⁻³), respectively (@40 GHz), as compared with that of the corresponding SiO₂/PTFE composite. The fillers and composites were comprehensively characterized to verify the mechanism of CTE and dielectric properties of the composites.     

Novel polymer composites of RuO2@nBaTiO3/PVDF with a high dielectric constant

The dielectric properties of a novel polymer dielectric material were investigated. The conductive phase of RuO₂ was synthesized for deposition on the surface of a nanosized BaTiO₃ (nBT). The RuO₂@nBT hybrid particles were incorporated into a poly (vinylidene fluoride) (PVDF) as a three-phase composite (RuO₂@nBT/PVDF). The obtained dielectric constant (ε′) was significantly high (3837.16) for the composite with a volume fraction of $f_{Ru{O}_2@nBT}$ = 0.50. The large interfacial polarization between the RuO₂?nBT and RuO₂?PVDF interfaces considerably increased the value of ε′. Therefore, interfacial polarization is a critical factor in improving the dielectric properties. The dielectric behavior of the RuO₂@nBT/PVDF composites can be described using the effective medium percolation theory model, which indicates the significant contributions of the conductive RuO₂ phase and high-permittivity nBT phase.     

Preparation of high‐k composites with low dielectric loss based on the double‐layer coaxial structure of inorganic/polymer

This study presents a novel and simple modification of cladding multiwalled carbon nanotubes (MWCNTs) using organic polymer and inorganic nanoparticles to synthesize a product, which has a double‐cladding coaxial structure and can be applied as filler in the dielectric field. The first layer of MWCNTs was coated with polyaniline (PANI) through the oxidation–reduction reaction mechanism using Ce(NH₄)₂(NO₃)₆ as oxidizing agent and metal precursor of cerium oxide. Cerium ions on the second cladding layer of MWCNTs were directly deposited from the solution to the surface of the PANI layer forming the double‐cladding hybrid (CeO₂/PANI@MWCNTs). The external inorganic layer provides an insulating shell, which can prevent the contact between the conductive particles and hinder the migration of electrons between the MWCNTs. The intermediate layer of PANI provides the bonding between CeO₂ and the conductive core of MWCNTs, which also shows lower conductivity than carbon nanotubes. The CeO₂/PANI@MWCNTs were compounded with epoxy (EP) resin and formed a dielectric material with the advantage of reducing dielectric loss while ensuring high dielectric constant. The dielectric constant of the coated MWCNTs/EP composites was 194.90 at 10³ Hz with the content of fillers reaching 30 wt %, which is 28 times that of the pure EP. Accordingly, the dielectric loss of 30 wt % coated MWCNTs/EP composites was only 0.09 at 10³ Hz, which is only 2.25 times that of the pure EP. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46299.     

Novel composites of copper nanowire/PVDF with superior dielectric properties

Novel copper nanowires (CuNWs)/poly(vinylidene fluoride) (PVDF) nanocomposites with high dielectric permittivity (ε′) and low dielectric loss (ε″) were prepared by a precipitation technique followed by melt compression. Their dielectric properties over the broadband frequency range, i.e. 10¹–10⁶ Hz, were compared with multi-walled carbon nanotubes (MWCNT)/PVDF nanocomposites prepared by the same technique. It was observed that the CuNWs/PVDF nanocomposites had higher dielectric permittivity, lower dielectric loss and thus significantly lower dissipation factor (tan δ) than the MWCNT/PVDF nanocomposites at room temperature. This behavior was ascribed to a higher conductivity of the fresh core of the CuNWs relative to the MWCNT, which provided the composites with a higher amount of mobile charge carriers participating in the interfacial polarization. Moreover, the presence of oxide layers on the CuNWs surfaces diminished the conductive network formation leading to a low dielectric loss.     

Eco-friendly poly(vinyl alcohol)/delaminated V2C MXene high-k nanocomposites with low dielectric loss enabled by moderate polarization and charge density at the interface

High-dielectric-constant (high-k) polymer/conductor composites with low dielectric loss are desirable for energy storage. However, high leakage currents from interfacial regions with high charge density are difficult to handle. In this work, high permittivity and low dielectric loss were achieved in poly(vinyl alcohol) (PVA)/V₂C MXene nanocomposite films fabricated by solution casting by taking advantage of the interfacial compatibility and moderate interfacial charge density of the nanocomposites. Water-soluble PVA was utilized as the polymer matrix. Delaminated V₂C MXene nanosheets with appropriate conductivity were prepared and used as the filler. The mild interface polarization of the nanocomposites was responsible for achieving favourable permittivity values. The small gap between the work functions of PVA and V₂C contributed to moderate interfacial charge density values and thus low dielectric loss values. A proportional correlation between the interfacial charge density and the conductivity of composites was also verified. The depth of charge injection from the MXene to PVA was found to be half of the interlamellar spacing of the delaminated MXene. The dependence of the electrical properties of the nanocomposites on the frequency and MXene content was also studied. The composite with 4 wt% MXene exhibited a permittivity of ~24 (16 times that of PVA) and a dielectric loss of ~0.14 (1.5 times that of PVA) at 1 kHz, as well as breakdown strength of ~31 MV m⁻¹ (63% of PVA). This work might enable environmentally friendly fabrication of promising composite dielectrics.