High energy density and superior charge/discharge efficiency polymer dielectrics enabled by rationally designed dipolar polarization

Although many dielectric polymers exhibit high energy storage density(Ue)with enhanced dipolar polarization at room temperature,the substantially increased electric conduction loss at high applied electric fields and high temperatures remains a great challenge.Here,we report a strategy that high contents of medium-polar ester group and end-group(St)modification are introduced into a biode-gradable polymer polylactic acid(PLA)to synergistically reduce the loss and enhance Ue and charge-discharge efficiency(h).The resultant St-modified PLA polymer(PLA-St)exhibits an Ue of 6.5 J/cm^(3)with an ultra-high h(95.4%),far outperforming the best reported dielectric polymers.It is worth noting that the modified molecular structures can generate deep trap centers and restrict the local dipole motions in the polymer,which are responsible for the reduction of conduction loss and improvements in high-temperature capacitive performance.In addition,the PLA-St polymer shows intrinsically excellent self-healing ability and cyclic stability surviving over 500000 charge-discharge cycles.This work offers an efficient route to next-generation eco-friendly dielectric polymers with high energy density,low loss,and long-term stability.

Fabrication and Characterization of Semi-Crystalline and Amorphous Dielectric Polymer Films for Energy Storage

Dielectric polymer films are energy storage materials that are used in pulse power operations, power electronics and sustainable energy applications. This paper reviews energy storage devices with focus on dielectric film capacitors. Two prominent examples of polymer dielectrics Polyetherimide (PEI) and Poly (tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride) (THV) have been discussed. Polyetherimide (PEI) is an amorphous polymer recognized for its high-temperature capability, low dielectric loss and high dielectric strength. THV is a semi-crystalline polymer with high dielectric constant, high-temperature capability and charge-discharge efficiency. The primary focus of this paper is to introduce the reader to the fabrication procedures and characterization techniques used in research labs for processing of dielectric polymers. The fabrication and characterization process of both polymers has been discussed in detail to shed the light on experimental process in this area of research.

Dielectric polymer grafted electrodes enhanced aqueous supercapacitors

Supercapacitors(SCs)have become increasingly important in electrical energy storage and delivery owing to their high power densities and long lifetimes.Aqueous SCs are promising for large-scale engineering applications because of their low cost and safety.However,the low operating voltage and low energy density of aqueous SCs severely limit their practical applications.In this study,a nanoscale dielectric layer is grafted onto a graphene electrode to achieve both a high operating voltage and enhanced capacitance.Compared with an SC without dielectric grafting,a dielectric-enhanced SC(DESC)shows a higher capacitance by 2200%.The mechanism of the capacitance enhancement can be attributed to three factors:the dielectric polarization,the ions desolvation by the dielectric,and the enhanced quantum capacitance from charge transfer and ion adsorption in the polymer molecules.In addition,a 2.5 V pouch DESC with a 1 M KCl electrolyte is confirmed to cycle up to 50,000 times with a capacitance retention of 87.5%.The DESC presents the optimal electrochemical properties after it is grafted with a 5 nm dielectric layer.This study provides new insights into the design of high-voltage and high-energy-density aqueous SCs.

Dielectric nanocomposites with superb high-temperature capacitive performance based on high intrinsic dielectric constant polymer

Advancements in power electronics necessitate dielectric polymer films capable of operating at high temperatures and possessing high energy density.Although significant strides have been achieved by integrating inorganic fillers into high-temperature polymer matrices,the inherently low dielectric constants of these matrices have tempered the magnitude of success.In this work,we report an innovative nanocomposite based on sulfonylated polyimide(SPI),distinguished by the incorporation of sulfonyl groups within the SPI backbone and the inclusion of wide bandgap hafnium dioxide(HfO_(2))nanofillers.The nanocomposite has demonstrated notable enhancements in thermal stability,dielectric properties,and capacitive performance at elevated temperatures.Detailed simulations at both molecular and mesoscopic levels have elucidated the mechanisms behind these improvements,which could be attributed to confined segmental motion,an optimized electronic band structure,and a diminished incidence of dielectric breakdown ascribed to the presence of sulfonyl groups.Remarkably,the SPI-HfO_(2)nanocomposite demonstrates a high charge-discharge efficiency of 95.7%at an elevated temperature of 150℃and an applied electric field of 200 MV/m.Furthermore,it achieves a maximum discharged energy density of 2.71 J/cm^(3),signalling its substantial potential for energy storage applications under extreme conditions.

A Facile Photo-cross-linking Method for Polymer Gate Dielectrics and Their Applications in Fully Solution Processed Low Voltage Organic Field-effect Transistors on Plastic Substrate

A simple and effective photochemical method was developed for cross-linking of polymer gate dielectrics. Laborious synthetic processes for functionalizing polymer dielectrics with photo-cross-linkable groups were avoided. The photo-cross-linker, BBP-4, was added into host polymers by simple solution blending process, which was capable of abstracting hydrogen atoms from polymers containing active C--H groups upon exposure to ultraviolet （UV） radiation. The cross-linking can be completed with a relatively long wavelength UV light （365 nm）. The approach has been applied to methacrylate and styrenic polymers such as commercial poly（methylmethacrylate） （PMMA）, poly（iso-butylmethacrylate） （PiBMA） and poly（4-methylstyrene） （PMS）. The cross-linked networks enhanced dielectric properties and solvent resistance of the thin films. The bottom-gate organic field-effect transistors （OFETs） through all solution processes on plastic substrate were fabricated. The OFET devices showed low voltage operation and steep subthreshold swing at relatively small gate dielectric capacitance.

Manipulating dielectric property of polymer coatings toward highretention-rate lithium metal full batteries under harsh critical conditions

Lithium(Li)metal batteries(LMBs)can potentially deliver much higher energy density but remain plagued by uncontrollable Li plating with dendrite growth,unstable interfaces,and highly abundant excess Li(>50 mAh·cm^(-2)).Herein,different from the artificial layer or three-dimensional(3D)matrix host constructions,various dielectric polymers are initially well-comprehensively investigated from experimental characterizations to theoretical simulation to evaluate their functions in modulating Li ion distribution.As a proof of concept,a 3D interwoven high dielectric functional polymer(HDFP)nanofiber network with polar C-F dipole moments electrospun on copper(Cu)foil is designed,realizing uniform and controllable Li deposition capacity up to 5.0 mAh·cm^(-2),thereby enabling stable Li plating/stripping cycling over 1400 h at 1.0 mA·cm^(-2).More importantly,under the highcathode loading(~3.1 mAh·cm^(-2))and only 0.6×excess Li(N/P ratio of 1.6),the full cells retain capacity retention of 97.4%after 200 cycles at 3.36 mA·cm^(-2)and achieve high energy density(297.7 Wh·kg^(-1)at cell-level)under lean electrolyte conditions(15μL),much better than ever-reported literatures.Our work provides a new direction for designing high dielectric polymer coating toward high-retention-rate practical Li full batteries.

Pendant Group Effect of Polymeric Dielectrics on the Performance of Organic Thin Film Transistors

Polymer dielectric is superior to its inorganic counterparts due to not only the low cost and intrinsic flexibility,but also the readily tunable dielectric constant,surface charge trap density,charge ejection and releasing ability and dipole moment,and all these properties play decisive roles in regulating the characteristic and performances of organic thin film transistors(OTFT).However,systematical studies on the relationship between structure and properties of polymeric dielectrics are rare.To this end,a series of polymeric dielectrics with well-defined linkages(ester or amide bonds)and predesigned pendant groups(alkyl-and aromatic-groups)are synthesized in high yields.Detailed studies show that the polyamide dielectrics exhibit higher dielectric constant,surface charge trapping density,and better charge storage capability than corresponding polyester dielectrics.Further,increasing theπelectron delocalization of the pendant groups generally benefits the charge storage property and transistor memory behavior.Theoretical calculation reveals that the hydrogen bonding between the linkage groups and the energy alignment between polymeric dielectric and semiconductor are responsible for the observed performance differences of OTFT with different polymeric dielectrics.These results may shine light on the design of polymeric dielectrics for OTFTs with different applications.

Fluorinated p-n Type Copolyfluorene as Polymer Electret for Stable Nonvolatile Organic Transistor Memory Device

Abstract In this study, a kind of fluorinated copolyfluorene, named poly[（4-（octyloxy）-9,9-diphenylfluorene-2,7-diyl）-alt- （2,3,5,6-tetrafluoro-1,4-phenylene）] （PODPF-TFP）, is synthesized by facile palladium-based direct aromatization. Compared to the non-fluorinated counterpart, poly[（4-（octyloxy）-9,9-diphenylfluorene-2,7-diyl）-alt-（p-phenylene）] （PODPF-P）, deeper HOMO/LUMO energy level combined with steric hindrance effect endow PODPF-TFP with excellent spectra and morphology stability. Finally, organic field-effect transistor （OFET） memory devices are fabricated with PODPF-P/PODPF- TFP as the dielectric layers, and they both exhibit flash type storage characteristic. Owing to the electronegativity of fluorine atom, the device based on PODPF-TFP exhibits larger memory window and more stable Ion/Ioff ratio during a retention time of 10^4 s as well as a better aging stability. The present study suggests that fluorinated p-n copolyfluorene electrets could enhance the capabilities of charge trapping and storage, which are promising for OFET memory devices.

Dielectric phenomena and electrical energy storage of poly(vinylidene fluoride) based high-k polymers

Polymeric dielectrics have wide range of applications in the field of electrical energy storage because of their light weight and easy processing. However, the state-of-the-art polymer dielectrics, such as biaxially orientated polypropylene, could not meet the demand of minimization of electronic devices because of its low energy density. Recently, poly（vinylidene fluoride） （PVDF） based ferroelectric polymers have attracted considerable interests for energy storage applications because of their high permittivity and high breakdown strength. Unfortunately, the high dielectric loss and/or high remnant polarization of PVDF-based polymers seriously limits their practical applications for electrical energy storage. Since the discovery of relaxor ferroelectric behavior was firstly reported in irradiated poly（vinylidene fluoride- trifluoroethylene） （P（VDF-TrFE）） copolyrner, many strategies have been developed to enhanced the electrical energy storage capability, including copolymerization, grafting, blending and fabricating of multilayer How these methods affect the polymorphs, crystallinity, crystal size of PVDF-based polymers and the connection between these microstructures and their corresponding energy storage properties are discussed in detail.

Electron transport in solution-grown TIPS-pentacene single crystals:Effects of gate dielectrics and polar impurities

The n-channel behavior has been occasionally reported in the organic field-effect transistors （OFETs） that usually exhibit p-channel transport only. Reconfirmation and further examination of these unusual device performances should deepen the understanding on the electron transport in organic semiconductors. 6,13-bis（triisopropyl-silylethynyl） pentacene （TIPS-pentacene）, a widely examined p-channel material as Au is used for source-drain electrodes, has recently been reported to exhibit electron transport when grown from non-polar solvent on divinyltetramethyldisiloxanebis （benzocy- clobutene） （BCB） dielectric, spurring the study on this unusual electron transport. This paper describes FET characteristics of solution-grown TlPS-pentacene single crystals on five polymer gate dielectrics including polystyrene （PS）, poly（methyl methacrylate） （PMMA）, poly（4-vinyl phenol） （PVP）, poly（vinyl alcohol） （PVA） and poly（vinylidene fluoride-trifluoroethylene-chlorofluoroethylene） （P（VDF-TrFE-CFE））. In addition to the p-channel behavior, electron transport occurs in the crystals on PMMA, PS, thick PVA （40 nm） and a bilayer dielectric of PMMA on P（VDF-TrFE-CFE）, while does not on PVP and thin PVA （2 nm）. The two distinct FET characteristics are consistent with the previous reported trap effect of hydroxyl groups （in PVP and PVA） and reduced injection barrier by Na~ ions （as impurity in PVA）. The highest electron mobility of 0.48 cm2 V-1 s-1 has been achieved in the crystals on PMMA. Furthermore, the electron transport is greatly attenuated after the crystals are exposed to the vapor of a variety of polar solvents and the attenuated electron transport partially recovers if the crystals are heated, indicating the adverse effect of polar impurities on electron transport. By reconfirming the n-channel behavior in the OFETs based on TIPS-pentacene, this work has implications for the design of n-channel and ambipolar OFETs.

Percolation of carbon nanomaterials for high-k polymer nanocomposites

High-k polymer composite materials are next-generation dielectrics that show amazing applications in diverse electrical and electronic devices. Establishing near-percolated network of conducting filler in an insulating polymer matrix is a promising approach to develop flexible high-k dielectrics. However, challenges still exist today on fine controlling the network morphology to achieve extremely high k values and low losses simultaneously. The relationship between the network morphology and the dielectric properties of polymer composites is raising a number of fundamental questions. Herein, recent progress towards high-k polymer composites based on carbon nanomaterials is reviewed. Particular attention is paid on the influence of the network morphology on the dielectric properties. Some perspectives that warrant further investigation in the future are also addressed.

Impact of oxygen-containing carbonyl and ether groups on dielectric properties of poly(oxa)norbornene cyclic olefins

Flexible dielectric polymers that can withstand high electric field and simultaneously have high dielectric constant are desired for high-density energy storage.Here,we systematically investigated the impact of oxygen-containing ether and carbonyl groups in the backbone structure on dielectric properties of a series of cyclic olefin.In comparison to the influence of the-CF3 pendant groups that had more impact on the dielectric constant rather than the band gap,the change of the backbone structure affected both the dielectric constant and band gaps.The one polymer with ether and carbonyl groups in the backbone has the largest band gap and highest discharge efficiency,while it has the lowest dielectric constant.The polymer without any ether groups in the backbone has the smallest band gap and lowest discharge efficiency,but it has the highest dielectric constant.Polymers that have no dipolar relaxation exhibit an inversely correlated dielectric constant and band gap.Enhancing the dipolar relaxation through rational molecular structure design can be a novel way to break through the exclusive constraint of dielectric constant and band gap for high-density energy storage.

Stable dielectric response of low-loss aromatic polythiourea thin films on Pt/SiO_(2) substrate

We have investigated dielectric properties of aromatic polythiourea(ArPTU,a polar polymer containing high dipolar moments with very low defect levels)thin films that were developed on Pt/SiO_(2) substrate.The detected response is compared to the response of commercially available polymers,such as high density polyethylene(HDPE)and polypropylene(PP),which are at present used in foil capacitors.Stable values of the dielectric constantε'≈5(being twice higher than in HDPE and PP)over broad temperature and frequency ranges and dielectric losses as low as in commercial systems suggest ArPTU as a promising candidate for future use in a variety of applications.

Changes of the Molecular Mobility of Poly(ε-caprolactone) upon Drawing,Studied by Dielectric Relaxation Spectroscopy

Dielectric relaxation spectroscopy（DRS） of poly（ε-caprolactone） with different draw ratios showed that the mobility of polymer chains in the amorphous part decreases as the draw ratio increases. The activation energy of the α process, which corresponds to the dynamic glass transition, increases upon drawing. The enlarged gap between the activation energies of the α process and the β process results in a change of continuity at the crossover between the high temperature a process and the α and β processes. At low drawing ratios the a process connects with the β process, while at the highest drawing ratio in our measurements, the a process is continuous with the αprocess. This is consistent with X-ray diffraction results that indicate that upon drawing the polymer chains in the amorphous part align and densify upon drawing. As the draw ratio increases, the α relaxation broadens and decreases its intensity, indicating an increasing heterogeneity. We observed slope changes in the α traces, when the temperature decreases below that at which τα≈ 1 s. This may indicate the glass transition from the ‘rubbery＇ state to the non-equilibrium glassy state.

Structural,Dielectric,and Magnetic Studies on Electrospun Magnesium Ferrite-Polyvinylidene Fluoride Core–Shell Composite Fibers

The sub-micron（of the order of 150 nm） thick core–shell composite fibers of magnesium ferrite-polyvinylidene fluoride are prepared by electrospinning.The loading of magnesium ferrite is varied from 1 to 10 wt%.The study results by X-ray diffraction,scanning electron microscope,and infra-red spectroscopy indicate the formation of core–shell structure and an enhancement in the amount of b-phase compared to a-phase in the polyvinylidene fluoride.The particle size of the magnesium ferrite in the fiber is evaluated to be 30 nm.The low frequency dielectric studies indicate that the addition of the magnesium ferrite increases the polarization resulting in the increase in the dielectric constant but decreases the dielectric loss.The magnetization measurements indicate an increased value of coercivity compared to bulk due to the nano-size of the magnesium ferrite.The microwave absorption at the ferromagnetic resonance increases with the increase in the concentration of magnesium ferrite.The resonance field is found to vary with the loading of MFO.