Modified crosslinked polyethylene (XLPE) with appreciably enhanced DC electrical insulation properties has been developed by chemical modification of grafting chloroacetic acid allyl ester (CAAE), exploring the trapping mechanism of charge transport inhibition. The bound state traps deriving from grafted molecule are analyzed by first-principles calculations, in combination with the electrical DC conductivity and dielectric breakdown strength experiments to study the underlying mechanism of improving the electrical insulation properties. In contrast to pure XLPE, the XLPE-graft-CAAE represents significantly suppressed space charge accumulation, increased breakdown strength, and reduced conductivity. The substantial deep traps are generated in XLPE-graft-CAAE molecules by polar group of grafted CAAE and accordingly decrease charge mobility and raise charge injection barrier, consequently suppressing space charge accumulation and charge carrier transport. The well agreement of experiments and quantum mechanics calculations suggests a prospective material modification strategy for achieving high-voltage polymer dielectric materials without nanotechnology difficulties as for nanodielectrics.
In order to achieve both high toughness and favorable dielectric properties of polypropylene materials, a styrene–butadiene–styrene block copolymer (SEBS) was employed as a toughening filler, in addition to a copolymerized polypropylene grafted by maleic anhydride (cPP-g-MAH) as a compatibilization modifier, to develop a novel isotactic polypropylene (iPP) composite (cPP-g-MAH/iPP/SEBS composite) with significantly improved direct-current (DC) dielectric performance and tenacity. The underlying physical and chemical mechanisms of modifying electric insulation were studied utilizing micro-structure characterization methods in combination with multiple thermal–mechanic–electric tests. The SEBS phase islands are uniformly distributed in the PP matrix with evidently improved dispersion due to cPP-g-MAH compatibilization. Compared with iPP, the elastic modulus of cPP-g-MAH/iPP/SEBS composites can be reduced by 58% with doubled thermal elongation, which is still superior to that of cross-linked polyethylene (XLPE), implying that the composites are qualified in terms of mechanical properties for use as power cables. The space charge accumulation and electric conduction are considerably suppressed in comparison with pure iPP and the iPP/SEBS composite. In the interest of charge-trapping characteristics modified by chemically grafting MAH, the deep traps introduced into polypropylene by grafting MAH were measured with a thermal stimulation current experiment to be 1.2 and 1.6 eV of energy level in trapping depth, verified through the first-principles electronic structure calculations with an all-electron numerical orbital scheme. It was concluded that the acquired high density of deep traps can effectively restrict the carrier transport and suppress the injection of space charge, resulting in a remarkable improvement of DC dielectric properties for the MAH grafted composites. The present work demonstrates that the cPP-g-MAH/iPP/SEBS composites are eligible to be applied to polypropylene-based high-voltage DC cables due to their excellent DC insulation performance, together with the appropriate mechanical properties.
Space charge characteristics of cross-linked polyethylene (XLPE) at elevated temperatures have been evidently improved by the graft modifications with ultraviolet (UV) initiation technique, which can be efficiently utilized in industrial cable manufactures. Maleic anhydride (MAH) of representative cyclic anhydride has been successfully grafted onto polyethylene molecules through UV irradiation process. Thermal stimulation currents and space charge characteristics at the elevated temperatures are coordinately analyzed to elucidate the trapping behavior of blocking charge injection and impeding carrier transport which is caused by grafting MAH. It is also verified from the first-principles calculations that the bound states as charge carrier traps can be introduced by grafting MAH onto polyethylene molecules. Compared with pure XLPE, the remarkably suppressed space charge accumulations at high temperatures have been achieved in XLPE-g-MAH. The polar groups on the grafted MAH can provide deep traps in XLPE-g-MAH, which will increase charge injection barrier by forming a charged layer of Coulomb-potential screening near electrodes and simultaneously reduce the electrical mobility of charge carriers by trap-carrier scattering, resulting in an appreciable suppression of space charge accumulations inside material. The exact consistence of experimental results with the quantum mechanics calculations demonstrates a promising routine for the modification strategy of grafting polar molecules with UV initiation technique in the development of high-voltage DC cable materials.
Direct current (DC) electrical performances of crosslinked polyethylene (XLPE) have been evidently improved by developing graft modification technique with ultraviolet (UV) photon-initiation. Maleic anhydride (MAH) molecules with characteristic cyclic anhydride were successfully grafted to polyethylene molecules under UV irradiation, which can be efficiently realized in industrial cable production. The complying laws of electrical current varying with electric field and the Weibull statistics of dielectric breakdown strength at altered temperature for cable operation were analyzed to study the underlying mechanism of improving electrical insulation performances. Compared with pure XLPE, the appreciably decreased electrical conductivity and enhanced breakdown strength were achieved in XLPE-graft-MAH. The critical electric fields of the electrical conduction altering from ohm conductance to trap-limited mechanism significantly decrease with the increased testing temperature, which, however, can be remarkably raised by grafting MAH. At elevated temperatures, the dominant carrier transport mechanism of pure XLPE alters from Poole–Frenkel effect to Schottky injection, while and XLPE-graft-MAH materials persist in the electrical conductance dominated by Poole–Frenkel effect. The polar group of grafted MAH renders deep traps for charge carriers in XLPE-graft-MAH, and accordingly elevate the charge injection barrier and reduce charge mobility, resulting in the suppression of DC electrical conductance and the remarkable amelioration of insulation strength. The well agreement of experimental results with the quantum mechanics calculations suggests a prospective strategy of UV initiation for polar-molecule-grafting modification in the development of high-voltage DC cable materials.
The use of high electrochemical active binary nickel−cobalt sulfides/ phosphides/selenides (Ni−Co−X, X = S, P, Se) as electrochemical energy storage materials still has a space for improvement because they become electrochemically unstable during long-term use. Herein, a facile and cost-effective dual-ligand synergistic modulation tactic is described to substantially improve the durability of Ni−Co−X (X = S, P, Se) at the atomic level by partially substituting S, P, and Se ligands into the nickel−cobalt hydroxide precursor, respectively. Remarkably, the dual-ligand electrodes on Ni-foam achieve superior durability and high electrochemical activity when used as positive electrodes in supercapacitors. Impressively, the density functional theory calculations demonstrate that the OH ligand in NiCo 2 (MOH) x (M = S, P, Se) could attract electrons from metal−S/metal−P/metal−Se bonds to the metal−O bond, enhancing the binding energy of metal−S/metal−P/metal−Se bonds and improving the long-term durability of Ni−Co−X (X = S, P, Se) in alkaline electrolytes. Moreover, OH and S/P/Se ligands could effectively alter the electron structure and result in favorable electrochemical activity. Overall, this tactic could offer an exciting avenue to achieve long-term durability and electrochemical activity of supercapacitor electrodes simultaneously.
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