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How to better understand the influence of electromagnetic parameters on the absorbing properties of electromagnetic wave absorbers (EMAs) is an essential prerequisite for further synthesis and development of high-performance EMAs. In this work, an improved wave cancellation theory is used as a guiding principle to prepare N-doped carbon-coated cobalt nanoparticles (Co@NC) using ZIF-8@ZIF-67 as the precursor, thus enabling controllable electromagnetic parameters by regulating the conduction loss and dipole polarization ability. The Co@NC generated by pyrolysis at 700 °C under H2 atmosphere presents an optimized absorption performance. Benefiting from developed wave cancellation theory, the thickness of the film can be accurately adjusted so that the difference between the amplitude of the reflected and transmitted electromagnetic waves is only 0.001 and the phase difference is 180.05°, thus achieving a minimum reflection loss (RLmin (dB)) of -64.0 dB. Meanwhile, a maximum effective absorption bandwidth of 5.4 GHz is achieved simultaneously attributing to its most suitable electromagnetic parameters. Accordingly, the current research based on wave cancellation theory significantly contributes to understand the relationships between electromagnetic parameters and wave absorption properties, therefore providing a theoretical insight into the further development of high-performance EMAs.
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The construction of ordered hierarchical porous structures in metal-organic frameworks (MOFs) and their derivatives is highly promising to meet the low-density and high-performance demands of microwave absorption materials. However, traditional methods based on sacrificial templates or corrosive agents inevitably suffer from the collapse of the microporous framework and the accumulation of nanoparticles during the carbonization transformation, resulting in the deteriorating impedance match, which greatly limits the incident and attenuation of microwaves. Herein, an induced crystallization and controllable nanoarchitectonics strategy is employed to replace traditional growing-etching methods and successfully synthesize carbonized 3D-ordered macroporous Co@N-doped carbon (3DOM Co@NDC) based on the 3D-ordered template. The obtained 3D-ordered macroporous structure ensures the stable growth of hybrid carbon frameworks and CoC nanoparticles without collapse, preserves abundant interfaces for both the incident and attenuation performance, so as to significantly improve the impedance matching and absorption properties compared to conventional MOFs derivatives. The minimum reflection loss of 3DOM Co@NDC is -57.36 dB at the thickness of 1.9 mm, and the effective bandwidth is 7.36 GHz at 1.6 mm. Moreover, the innovative strategy to prepare 3D-ordered hierarchical macroporous structures opens up a new avenue for advanced MOFs-derived absorbers with excellent performance.
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The combination of 2D magnetic nanosheets and mesoporous carbon with unique interfaces shows considerable prospects for microwave absorption (MA). However, traditional assembly procedures make it impossible to accurately manage the assembly of magnetic nanosheets in carbon matrices. Herein, a reverse strategy for preparing complex magnetic nanosheet cores inside carbon-based yolk-shell structures is developed. This innovative approach focuses on controlling the initial crystallite formation sites in a hydrothermal reaction as well as the inflow and in situ growth behavior of 2D NiCo-layered double hydroxide precursors based on the capillary force induced by hollow mesoporous carbon nanospheres. Accordingly, the as-prepared YS-CNC-2 absorber exhibits remarkable MA performances, with an optimal reflection loss as low as -60.30 dB at 2.5 mm and an effective absorption bandwidth of 5.20 GHz at 2.0 mm. The loss of electromagnetic waves (EMW) depends on natural resonance loss, dipole polarization relaxation, and multiple scattering behavior. On top of that, the functionalized super-hydrophobic MA coating is produced in spraying and curing processes utilizing YS-CNC-2 nanoparticles and fumed silica additives in the polydimethylsiloxane matrix. The excellent thermal insulation, self-cleaning capability, and durability in diverse solutions of the coating promise potential applications for military equipment in moist situations.
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Constructing the adjustable surface conductive networks is an innovation that can achieve a balance between enhanced attenuation and impedance mismatch according to the microwave absorption mechanism. However, the traditional design strategies remain significant challenges in terms of rational selection and controlled growth of conductive components. Herein, a hierarchical construction strategy and quantitative construction technique are employed to introduce conductive metal-organic frameworks (MOFs) derivatives in the classic yolk-shell structure composed of electromagnetic components and the cavity for remarkable optimized performance. Specifically, the surface conductive networks obtained by carbonized ZIF-67 quantitative construction, together with the Fe3 O4 magnetic core and dielectric carbon layer linked by the cavity, achieve the cooperative enhancement of impedance matching optimization and synergistic attenuation in the Fe3 O4 @C@Co/N-Doped C (FCCNC) absorber. This interesting design is further verified by experimental results and simulation calculations. The products FCCNC-2 yield a distinguished minimum reflection loss of -66.39 dB and an exceptional effective absorption bandwidth of 6.49 GHz, indicating that moderate conduction excited via hierarchical and quantitative design can maximize the absorption capability. Furthermore, the proposed versatile methodology of surface assembly paves a new avenue to maximize beneficial conduction effect and manipulate microwave attenuation in MOFs derivatives.
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With the rapid development of integrated circuits towards miniaturization and complexity, there is an urgent need for materials with low dielectric constant/loss and high processing temperatures to effectively prevent signal delay and crosstalk. With high porosity, thermal stability, and easy structural modulation, covalent organic frameworks have great potential in the field of low dielectric materials. However, the optimization of dielectric properties by modulating the conjugated/plane curvature structure of covalent organic frameworks (COFs) has rarely been reported. Accordingly, we herein innovatively prepare COF films with adjustable planar curvature, hence possessing ultralow dielectric constant (1.9 at 1â kHz), ultralow dielectric loss at 1â kHz (0.0029 at room temperature, 0.0052 at 200 °C), high thermal decomposition temperature (5 % weight loss temperature, 473 °C) and good hydrophobicity (water contact angle, 105.3°). Also, to the best of our knowledge, we are the first to report that the resulting COF film enables high surface potential (≈320â V) for one week, attributing to its intrinsic high porosity, thus presenting great potential in electret applications. Accordingly, this innovative work provides a readily available and scalable idea to prepare materials with comprehensively excellent dielectric and electret properties as well as high processing temperatures simultaneously for advanced electronic device applications.
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Aiming at the excellent killing effect of N-phenylmaleimide (N-PMI) on microorganisms, this article used structural simulation analysis, fluorescence analysis, confocal laser scanning microscope and SEM to find that the double bond in N-PMI could interact with the sulfur groups in the membrane protein, changing its conformation, rupturing the plasma membrane of the cell, leaking the contents, and ultimately causing the death of the microorganisms. Therefore, once the double bond participated in the polymerization, N-PMI lost its antimicrobial function. N-PMI could achieve azeotropic copolymerization with MMA through reactive extrusion polymerization. N-PMI with a content of 5 % can be evenly inserted into the PMMA chain segment during the copolymerization reaction, thereby increasing the Tg of pure PMMA by up to 15 °C, which provided the PMMA-co-PMI copolymer with resistance to boiling water sterilization advantageous conditions. In addition, N-PMI with a content of 5 % has little effect on the transparency of PMMA after participating in the copolymerization. Moreover, the trace amount of residual N-PMI made the material have excellent antimicrobial function, and the bacteriostatic zone is extremely small, which provided an excellent guarantee for the safety and durability of the material. As a medical biological material, the PMMA-co-PMI copolymer has a good industrialization application prospects.
Assuntos
Anti-Infecciosos , Polimetil Metacrilato , Antibacterianos/farmacologia , Maleimidas , Polímeros/química , Polímeros/farmacologia , Polimetil Metacrilato/química , Polimetil Metacrilato/farmacologiaRESUMO
Perovskite solar cells suffer from poor reproducibility due to the degradation of perovskite precursor solution. Herein, we report an effective precursor stabilization strategy via incorporating 3-hydrazinobenzoic acid (3-HBA) containing carboxyl (-COOH) and hydrazine (-NHNH2 ) functional groups as stabilizer. The oxidation of I- , deprotonation of organic cations and amine-cation reaction are the main causes of the degradation of mixed organic cation perovskite precursor solution. The -NHNH2 can reduce I2 defects back to I- and thus suppress the oxidation of I- , while the H+ generated by -COOH can inhibit the deprotonation of organic cations and subsequent amine-cation reaction. The above degradation reactions are simultaneously inhibited by the synergy of functional groups. The inverted device achieves an efficiency of 23.5 % (certified efficiency of 23.3 %) with an excellent operational stability, retaining 94 % of the initial efficiency after maximum power point tracking for 601â hours.
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High-temperature thermosets are usually prepared from resins containing alkynyl groups, and their properties depend much upon the curing process containing various types of curing reactions. However, how the curing process affects the properties remains unclear due to the complicated curing reactions. We used molecular dynamics simulations to investigate the effect of curing reaction types, including cyclotrimerization, Diels-Alder reaction, and radical reaction, on the structures and properties of imide oligomers terminated with alkynyl groups. The results show that the cycloadditions such as cyclotrimerization and Diels-Alder reaction endow the thermosets with rigid structures and high moduli. Compared with the cycloadditions, the radical reaction enables the formation of flexible cured structures, which can enhance the toughness of thermosets. The differences in thermal and mechanical properties caused by different curing types were elucidated by the relaxation processes of fragments in these cured systems and were explained by the variation of torsion energy in different curing forms. As this work aims to optimize the curing procedure to obtain high-performance resins with desired properties, different curing procedures were finally designed according to the theoretical studies, and the obtained cured polymers show significant differences in the properties from different curing ways. The results can guide the preparation of desired thermosetting resins by tuning the curing procedure.
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Highly efficient removal of toxic Cr(VI) from aqueous media remains a crucial concern for ecosystem protection and public health. Herein, we demonstrated a new approach to solve this issue by constructing alkyl thiol-containing Zr-based metal-organic framework (MOF) adsorbents using simple and inexpensive mercaptosuccinic acid (MSA) and meso-dimercaptosuccinic acid (DMSA) as ligands. These chemically stable MOFs could be prepared in an uncomplicated, green, cost-effective, and scalable way. The interaction mechanism between alkyl thiol groups in MOFs and Cr(VI) was investigated in detail. Thanks to the formation of a Cr(VI)-thiolate complex and the oxidation of thiol groups, these designed MOFs not only exhibited high Cr(VI) adsorption capacities (202.0 and 138.7 mg/g for Zr-MSA and Zr-DMSA, respectively) but also displayed the immobilization ability for concomitant resultant Cr(III). Even in the presence of high concentrations of possibly coexistent interfering ions, the thiol-containing MOFs can still work effectively to decontaminate the Cr(VI) species. In addition, the strategy of introducing thiol groups into MOFs for Cr(VI) reduction and concomitant Cr(III) immobilization is universal for other MOFs, as verified by thiol-containing UiO-66 and MOF-808 prepared by a one-pot method. Therefore, our work not only produces several effective Cr(VI) adsorbents but also sets a general guideline for the construction of Cr(VI) adsorbents by introducing thiol groups into porous materials.
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Top-emitting microcavity polymer light-emitting diodes (TMPLEDs) are of great significance for active matrix PLED displays with high color purity. However, the complex device structures of highly efficient microcavity organic light-emitting diodes fabricated by the full vapor deposition technology are not suitable for solution-processed PLEDs. Solution-processed TMPLEDs with simple device structures are promising candidates for large-area, mass production display techniques. In this work, three strategies were used to apply microcavity into PLEDs: (1) double Ag electrodes performed as the mirrors of cavity, instead of a multi-layer Bragg reflector, which simplified the device structure and fabrication process; (2) three solution-processed functional layers were specially designed for avoiding the inter-infiltration between the different solutions and to improve the interface contacts; (3) high order microcavities were utilized according to the optical simulation results, in which thick EMLs benefited from thickness control and reproductivity. As a result, the full-color emission including pure red, green, blue was realized, and quasi-white light was also achieved from a single polymer emitting material. The achievement of color purity always requires the sacrifice of part of the current efficiency due to the spectra narrowing, while the higher current efficiency of green TMPLED (10.08 cd A-1) compared to that of non-cavity PLED (~8.60 cd A-1) cast a light on future improvements.
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A new monocarboxylic acid etching (MAE) strategy was developed for transforming chemically stable Zr-based metal-organic frameworks (MOFs) of UiO-66 to their hierarchical porous counterpart. The key design element was based on the incomplete replacement of bridging ligands in MOFs by monocarboxylic acids (MAs), leading to the departure of partial ligands and metal clusters to create mesopores in MOFs. A series of MAs with different acidity and carbon chain length were tested, and propionic acid (PA) was screened to be the suitable choice. The textural features including pore size distribution, specific surface area, and pore volume of the obtained products can be controlled by adjusting the MA concentration and reaction temperature. The obtained hierarchical porous MOFs inherited excellent stability from their parent materials. Additionally, the MAE strategy was universal to construct hierarchical porous Zr-based MOFs, and it was expanded to etch UiO-66 derivatives. The excellent adsorption behavior of the resultant hierarchical porous Zr-based MOFs over two enzymes with different size was also successfully exemplified, demonstrating their application potentials with bulky molecules involved.
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Zr-based mesoporous metal-organic frameworks (mesoMOFs) with uniform mesochannels and crystallized microporous framework were constructed in a water-based system using amphoteric surfactants as templates. Aqueous-phase synthesis guaranteed the formation of rod-shaped surfactant micelles. Meanwhile, the carboxylate groups of amphoteric surfactants provided the anchoring to bridge Zr-oxo clusters and surfactant assemblies. As a result, the directed crystallization of MOFs proceeded around cylindrical micelles and the hierarchical micro- and mesostructure was produced. The dimensions of mesopores were easily tailored by changing the alkyl chain length of the applied surfactants. The included surfactant was effectively extracted thanks to the exceptional stability of the obtained Zr-based mesoMOFs. The almost complete occupation of the mesopore by cytochromeâ c exemplifies the accessibility of the mesochannels, suggesting the potential applications of the obtained mesoMOFs with bulky molecules.
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Given the serious harm of CrVI to human health, development of efficient techniques for its degradation and subsequent inâ situ adsorptive removal is highly desirable. Herein, UiO-66 type metal-organic frameworks (MOFs) integrated with various hydroxyl groups (UiO-66, UiO-66-OH, and UiO-66-(OH)2 ) were successfully explored for the efficient decontamination of CrVI from aqueous solution. The abundant hydroxyl groups in organic ligands not only served as reductive sites for the degradation of CrVI to less toxic CrIII but also acted as inherent anchorages for the efficient capture of CrIII . Thanks to their inherent hydroxyl groups and high porosity, UiO-66-(OH)2 presented almost complete removal of Cr species in simulated industrial wastewater. The total Cr content could be reduced from 5â ppm to 48â ppb under optimized adsorption conditions, which is much lower than the limits of total Cr in drinking water established by the US Environmental Protection Agency (EPA). These outstanding CrVI decontamination features, combined with the exceptional chemical stability as well as high porosity prefigured the great potentials of the current adsorbents for the remediation of real-world CrVI -containing industrial wastewater.
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The all-organic high-temperature polymer dielectrics with promising scale-up potential have witnessed much progress in the energy storage area, etc. However, the electron suppression trap mechanisms behind many all-organic dielectrics are still unclear, especially for high temperature resistant poly(p-phenylene benzobisoxazole) (PBO) polymers. To resolve this tough issue, we herein innovatively prepared PBO-based all-organic thin films containing sulfone-based polyimide (P(DSDA-ODA)) functioning as an electron trap phase using a facile and scalable co-curing method. The great linear dielectric properties of the prepared P(DSDA-ODA)/PBO films hold high dielectric thermal stability over the temperature range from 25 °C to 200 °C. The 60 wt% P(DSDA-ODA) systems yield the lowest leakage current (3.8 × 10-8 A cm-2). The tight structure and reduced leakage current enable an enhanced breakdown strength of 60 wt% P(DSDA-ODA)/PBO (470 kV mm-1), which is 1.7 times that of pure PBO. Meanwhile, it can reach 4.16 J cm-3 of energy density, which is 257% higher than that for pure PBO thin films while concurrently maintaining a long stable charge-discharge cycle (at least 5000 times) and high charge-discharge efficiency at 85.10%. Moreover, P(DSDA-ODA)/PBO still exhibits excellent energy storage performance at high temperature compared to PBO. This innovative strategy is further verified by replacing P(DSDA-ODA) with P(6FDA-ODA), and therefore lays a solid foundation for more investigation on scalable all-organic dielectrics.
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Mixing fillers featured with wide band gaps in polymers can effectively meet the requirement of higher energy storage densities. However, the fundamental relationship between the crystal structures of fillers and the dielectric properties of the corresponding nanocomposites is still unclear. Accordingly, we introduced ultralow contents of the synthesized cubic Hafnium dioxide (c-HfO2) or monoclinic Hafnium dioxide (m-HfO2) as deep traps into poly(ether imide) (PEI) to explore their effects on dielectric properties and the charge-blocking mechanism. m-HfO2/PEI showed better charge trapping due to the higher electron affinity and deeper trap energy. At room temperature, the 0.4 vol % m-HfO2/PEI maintains an ultralow dielectric loss of 0.008 while obtaining a dielectric constant twice that of pure PEI at 1 kHz, simultaneously outperforming in terms of leakage current density, breakdown strength (452 kV mm-1), discharge energy density (Ud, 5.03 J cm-3), charge-discharge efficiency (η, 92%), and dielectric thermal stability. At 125 °C, it exhibits a considerable Ud of 2.48 J cm-3 and a high η of 85% at 300 kV mm-1, surpassing the properties of pure PEI. This promising work opens up a new path for studying HfO2-derived dielectrics with unique crystal structures.
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The bidirectional migration of halides and silver causes irreversible chemical corrosion to the electrodes and perovskite layer, affecting long-term operation stability of perovskite solar cells. Here we propose a silver coordination-induced n-doping of [6,6]-phenyl-C61-butyric acid methyl ester strategy to safeguard Ag electrode against corrosion and impede the migration of iodine within the PSCs. Meanwhile, the coordination between DCBP and silver induces n-doping in the PCBM layer, accelerating electron extraction from the perovskite layer. The resultant PSCs demonstrate an efficiency of 26.03% (certified 25.51%) with a minimal non-radiative voltage loss of 126 mV. The PCE of resulting devices retain 95% of their initial value after 2500 h of continuous maximum power point tracking under one-sun irradiation, and > 90% of their initial value even after 1500 h of accelerated aging at 85 °C and 85% relative humidity.
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In two-dimensional/three-dimensional (2D/3D) perovskite heterostructure, randomly distributed multiple quantum wells (QW) 2D perovskites are frequently generated, which are detrimental to carrier transport and structural stability. Here, the high quality 2D/3D perovskite heterostructure is constructed by fabricating functional-group-induced single QW Dion-Jacobson (DJ) 2D perovskites. The utilization of âOCH3 in the precursor solution facilitates the formation of colloidal particles with uniform size, resulting in the production of a pure 2D DJ perovskite with an n value of 3. This strategy facilitates the improvement of 3D structural stability and expedites carrier transport. The resultant devices accomplish a power conversion efficiency of 25.26% (certified 25.04%) and 23.56% at a larger area (1 cm2 ) with negligible hysteresis. The devices maintain >96% and >89% of their initial efficiency after continuous maximum power point tracking under simulated AM1.5 illumination for 1300 h and under damp-heat conditions (85 °C and 85% RH) for 1010 h, respectively.
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In this study, poly(p-phenylene benzobisoxazole) (PBO)/graphene composites were prepared using PBO and poly(4,6-dihydroxymetaphenylenediamine terephthalamide) (PHA)-modified graphene oxide (GO-PHA). PHA is the precursor of PBO. GO-PHA was obtained via chemical coupling reaction of amino-terminated PHA and acyl-chloride-functionalized GO. Partially reduced graphene nanosheets and benzoxazole rings were formed after heating. GO-PHA could be stably dispersed in methane sulfonic acid (MSA), which facilitated its uniform distribution in the PBO matrix. The PBO/graphene nanocomposites were obtained by the dissolution of GO-PHA and PBO in MSA. The thermogravimetric analysis results showed that the PBO/graphene composites had good thermal stability below 400 ° C. The dielectric constant of the composites increased as the amount of GO-PHA increased, and the percolation threshold was f(c) = 0.037. The nanocomposite had a dielectric constant of 15.8, which was approximately five times larger than that of pure PBO polymer.
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In this study, the mechanism of radical polymerization was further explored by pre-dissolving different polymers and studying the kinetics of the bulk polymerization of methyl methacrylate (MMA) under shear-free conditions. Based on the analysis of the conversion and absolute molecular weight, it was found that, contrary to the shearing effect, the inert polymer with viscosity was the key factor to preventing the mutual termination of radical active species and reducing the termination rate constant k t. Therefore, pre-dissolving the polymer could increase the polymerization rate and molecular weight of the system simultaneously, making the polymerization system enter the automatic acceleration zone faster and greatly reducing the generation of small molecular weight polymers, leading to a narrower molecular weight distribution. When the system entered the auto-acceleration zone, k t decreased rapidly and greatly and entered the second steady-state polymerization stage. Then, with the increase in the polymerization conversion, the molecular weight gradually increased, while the polymerization rate gradually decreased. In shear-free bulk polymerization systems, k t can be minimized and radical lifetimes maximized, but the polymerization system is at best a long-lived polymerization rather than a living polymerization. On this basis, by using MMA to pre-dissolve ultrahigh molecular weight PMMA and core-shell particles (CSR), the mechanical properties and heat resistance of the PMMA with pre-dissolved polymer obtained by reactive extrusion polymerization were better than for pure PMMA obtained under the same conditions. Compared with pure PMMA, the flexural strength and impact strength of PMMA with pre-dissolved CSR were up to 166.2% and 230.5%. With the same quality of CSR, the same two mechanical properties of the samples obtained by the blending method were just improved by 29.0% and 20.4%. This was closely related to the distribution of CSR in the pre-dissolved PMMA-CSR matrix with a distribution of spherical single particles 200-300 nm in diameter, which enabled PMMA-CSR to exhibit a high degree of transparency. This one-step process for realizing PMMA polymerization and high performance shows extremely high industrial application prospects.
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The development of pulse power systems and electric power transmission systems urgently require the innovation of dielectric materials possessing high-temperature durability, high energy storage density, and efficient charge-discharge performance. This study introduces a core-double-shell-structured iron(II,III) oxide@barium titanate@silicon dioxide/polyetherimide (Fe3O4@BaTiO3@SiO2/PEI) nanocomposite, where the highly conductive Fe3O4 core provides the foundation for the formation of microcapacitor structures within the material. The inclusion of the ferroelectric ceramic BaTiO3 shell enhances the composite's polarization and interfacial polarization strength while impeding free charge transfer. The outer insulating SiO2 shell contributes excellent interface compatibility and charge isolation effects. With a filler content of 9 wt%, the Fe3O4@BaTiO3@SiO2/PEI nanocomposite achieves a dielectric constant of 10.6, a dielectric loss of 0.017, a high energy density of 5.82 J cm-3, and a charge-discharge efficiency (η) of 72%. The innovative aspect of this research is the design of nanoparticles with a core-double-shell structure and their PEI-based nanocomposites, effectively enhancing the dielectric and energy storage performance. This study provides new insights and experimental evidence for the design and development of high-performance dielectric materials, offering significant implications for the fields of electronic devices and energy storage.