Recent Progress and Future Prospects on All-Organic Polymer Dielectrics for Energy Storage Capacitors.

With the development of advanced electronic devices and electric power systems, polymer-based dielectric film capacitors with high energy storage capability have become particularly important. Compared with polymer nanocomposites with widespread attention, all-organic polymers are fundamental and have been proven to be more effective choices in the process of scalable, continuous, and large-scale industrial production, leading to many dielectric and energy storage applications. In the past decade, efforts have intensified in this field with great progress in newly discovered dielectric polymers, fundamental production technologies, and extension toward emerging computational strategies. This review summarizes the recent progress in the field of energy storage based on conventional as well as heat-resistant all-organic polymer materials with the focus on strategies to enhance the dielectric properties and energy storage performances. The key parameters of all-organic polymers, such as dielectric constant, dielectric loss, breakdown strength, energy density, and charge-discharge efficiency, have been thoroughly studied. In addition, the applications of computer-aided calculation including density functional theory, machine learning, and materials genome in rational design and performance prediction of polymer dielectrics are reviewed in detail. Based on a comprehensive understanding of recent developments, guidelines and prospects for the future development of all-organic polymer materials with dielectric and energy storage applications are proposed.

Polymer Dielectrics with Outstanding Dielectric Characteristics via Passivation with Oxygen Atoms through C-F Vacancy Carbonylation.

The development of advanced electrical equipment necessitates polymer dielectrics with a higher electric strength. Unfortunately, this bottleneck problem has yet to be solved because current material modification methods do not allow direct control of deep traps. Here, we propose a method for directly passivating deep traps. Measurements of nanoscale microregion charge characteristics and trap parameters reveal a significant reduction in the number of deep traps. The resulting polymer dielectric has an impressively high electrical strength, less surface charge accumulation, and a significantly increased flashover voltage and breakdown strength. In addition, the energy storage density is increased without sacrificing the charge-discharge efficiency. This reveals a new approach to increasing the energy storage density by reducing the trap energy levels at the electrode-dielectric interface. We further calculated and analyzed the microscopic physical mechanism of deep trap passivation based on density functional theory and characterized the contributions of orbital composition and orbital hybridization.

High-Temperature Polymer Dielectrics Designed Using an Invertible Molecular Graph Generative Model.

Generating new molecules with the desired physical or chemical properties is the key challenge of computational material design. Deep learning techniques are being actively applied in the field of data-driven material informatics and provide a promising way to accelerate the discovery of innovative materials. In this work, we utilize an invertible graph generative model to generate hypothetical promising high-temperature polymer dielectrics. A molecular graph generative model based on the invertible normalizing flow is trained on a data set containing 250k polymer molecular graphs (mostly generated by an RNN-based generative model) to learn the invertible transformations between latent distributions and molecular graph structures. When generating molecular graphs, a sample vector is drawn from the latent space, and then an adjacency tensor and node attribute matrix are generated through two invertible flows in two steps and assembled into a molecular graph. The model has the merits of exact likelihood training and an efficient one-shot generation process. The learned latent space is used to generate polymers with a high glass-transition temperature (Tg) and a wide band gap (Eg) for the application of high-temperature energy storage film capacitors. This work contributes to the efficient design of high-temperature polymer dielectrics by using deep generative models.

Alternating [1.1.1]Propellane-(Meth)Acrylate Copolymers: A New Class of Dielectrics with High Energy Density for Film Capacitors.

Polymer dielectrics with high energy density are of urgent demand in electric and electronic devices, but the tradeoff between dielectric constant and breakdown strength is still unsolved. Herein, the synthesis and molar mass control of three alternating [1.1.1]propellane-(meth)acrylate copolymers, denoted as P-MA, P-MMA, and P-EA, respectively, are reported. These copolymers exhibit high thermal stability and are semi-crystalline with varied glass transition temperatures and melting temperatures. The rigid bicyclo[1.1.1]pentane units in the polymer backbone promote the orientational polarization of the polar ester groups, thus enhancing the dielectric constants of these polymers, which are 4.50 for P-EA, 4.55 for P-MA, and 5.11 for P-MMA at 10 Hz and room temperature, respectively. Moreover, the high breakdown strength is ensured by the non-conjugated nature of bicyclo[1.1.1]pentane unit. As a result, these copolymers show extraordinary energy storage performance; P-MA exhibits a discharge energy density of 9.73 J cm-3 at 750 MV m-1 and ambient temperature. This work provides a new type of promising candidates as polymer dielectrics for film capacitors, and offers an efficient strategy to improve the dielectric and energy storage properties by introducing rigid non-conjugated bicyclo[1.1.1]pentane unit into the polymer backbone.

Vertical Crystal Plane Matching between AgZn3 (002) and Zn (002) Achieving a Dendrite-Free Zinc Anode.

Metallic zinc anodes in zinc-ion batteries suffer from problematic Zn dendrite chemistry. Previous works have shown that preferred-orientation crystal planes can help dendrite-free metal anodes. This work reports a nanothickness (≈570 nm) AgZn3  coating to regulate the Zn growth. First, AgZn3 @Zn anode avoids the problem, in Ag@Zn anode, that the rate of electrochemical Ag-Zn alloying is slower than that of Zn dendrites growth. Batteries life increased from 112 h (pure Zn) and 932 h (Ag@Zn) to 1360 h (AgZn3 @Zn) at 2 mA cm-2  and 1 mAh cm-2 . Then, plasma sputtering can remove nonconductive ZnO and improve Zn-ion affinity, which brings a longer life for AuZn3 @Zn (423 h), CuZn3 @Zn (385 h), and AgZn3 @Zn (1150 h) than pure Zn (93 h) at 1 mAh cm-2 . More importantly, AgZn3 (002) has a high matching with the Zn (002), which can guide ordered Zn epitaxial deposition, thereby achieving dense and dendrite-free Zn growth. This work clearly captures the fascinating structure of the densely stacked Zn layers on the AgZn3  layer. This strategy not only improves the performance of zinc-ion batteries greatly but will also help one understand the matching mechanism of the (002) vertical crystal plane.

All-Organic Dielectrics with High Breakdown Strength and Energy Storage Density for High-Power Capacitors.

Polymer-based film capacitors with high breakdown strength and excellent flexibility are crucial in the field of advanced electronic devices and electric power systems. Although massive works are carried to enhance the energy storage performances, it is still a great challenge to improve the energy density of polymer composites under the premise of large-scale industrial production. Herein, a general strategy is proposed to improve the intrinsic breakdown strength and energy storage performances by blending core-shell structured methyl methacrylate-butadiene-styrene (MBS) rubber particles into a polymer matrix. Good compatibility and uniform dispersion state of MBS particles are observed in the matrix. Polarizing microscopy images show that blended films exhibit clear reduction of crystalline grains with the addition of MBS particles. Accordingly, an increased breakdown strength of 515 MV m-1 and discharged energy density of 12.33 J cm-3 are observed in poly(vinylidene fluoride-co-hexafluoropropylene)-based composite films. Through comprehensive characterizations, it is believed that the superior energy storage performance of composite films is attributed to decreased crystalline grains, improved mechanical properties, and restriction on carrier motion. These results provide a novel design of dielectric polymers for high breakdown strength and discharged energy density applications.

Largely enhanced dielectric constant of PVDF nanocomposites through a core-shell strategy.

Core-shell structured TiO2@carbon nanowire (TiO2@C NW) hybrids with different carbon shell thicknesses were synthesized by a combination of a hydrothermal reaction and the chemical vapor deposition (CVD) method. Pristine TiO2 NWs with a high aspect ratio were obtained by a hydrothermal reaction and the as-synthesized TiO2 NWs were subsequently employed as the template for carbon shell deposition during the CVD procedure. The obtained TiO2@C NW hybrids have a uniform carbon shell and the thickness of the carbon shell could be precisely designed from 4 nm to 40 nm by controlling the deposition time. With the help of solution and melt blending methods, the TiO2@C NW hybrids were subsequently incorporated into the PVDF matrix to fabricate TiO2@C NWs/PVDF nanocomposites, which exhibit a similar percolative dielectric behavior to that reported in other percolative nanocomposites. Moreover, the dielectric properties of the TiO2@C NWs/PVDF nanocomposites could be accurately adjusted by tuning the carbon shell thickness of the TiO2@C NW hybrids. The highest dielectric constant (2171) of the TiO2@C NWs/PVDF nanocomposites is 80 times larger than those of the pristine TiO2-filled ones at the same filler loading, and 241 times higher than that of the pure PVDF matrix. The enhanced dielectric performance could be attributed to the improved interfacial polarizations of TiO2/C and C/PVDF interfaces. This approach provides an interesting alternative to fabricate high-performance dielectric nanocomposites for practical applications in the electronic industry.

Mechanistic Investigation of Visible-Light-Induced Intermolecular [2 + 2] Photocycloaddition Catalyzed with Chiral Thioxanthone.

The recent thioxanthone-sensitizer-catalyzed intermolecular [2 + 2] cycloaddition induced by visible-light irradiation set the stage for the future development of feasible photocycloadditions. Nonetheless, the mechanism of this reaction still remains under debate, especially on the activation mode of the thioxanthone photosensitizer (energy transfer, bielectron exchange, and hydrogen transfer are all possible mechanisms). To settle this issue, systematic density functional theory calculations have been carried out. The results indicate that the energy-transfer pathway is more favorable than the bielectron-exchange and the hydrogen-transfer pathways. Meanwhile, the overall transformations involve the complexation and excitation of photosensitizer, the first C-C bond formation, the dissociation of the sensitizer, the triplet-to-singlet electronic state crossing, and the second C-C bond formation. The first C-C bond formation is the rate- and selectivity-determining step, and synergistic energy and electron transfer from photosensitizer to substrate moieties takes place along this process. On this basis, the effect of olefin substrates (ethyl vinyl ketone vs vinyl acetate) on the stereoselectivity was finally analyzed.

1D/2D Carbon Nanomaterial-Polymer Dielectric Composites with High Permittivity for Power Energy Storage Applications.

With the development of flexible electronic devices and large-scale energy storage technologies, functional polymer-matrix nanocomposites with high permittivity (high-k) are attracting more attention due to their ease of processing, flexibility, and low cost. The percolation effect is often used to explain the high-k characteristic of polymer composites when the conducting functional fillers are dispersed into polymers, which gives the polymer composite excellent flexibility due to the very low loading of fillers. Carbon nanotubes (CNTs) and graphene nanosheets (GNs), as one-dimensional (1D) and two-dimensional (2D) carbon nanomaterials respectively, have great potential for realizing flexible high-k dielectric nanocomposites. They are becoming more attractive for many fields, owing to their unique and excellent advantages. The progress in dielectric fields by using 1D/2D carbon nanomaterials as functional fillers in polymer composites is introduced, and the methods and mechanisms for improving dielectric properties, breakdown strength and energy storage density of their dielectric nanocomposites are examined. Achieving a uniform dispersion state of carbon nanomaterials and preventing the development of conductive networks in their polymer composites are the two main issues that still need to be solved in dielectric fields for power energy storage. Recent findings, current problems, and future perspectives are summarized.

Density functional theory investigation on Pd-catalyzed cross-coupling of azoles with aryl thioethers.

In the present study, a density functional theory (DFT) study has been carried out on the Pd-catalyzed coupling of azoles with aryl thioethers. Our effort is mainly put into identifying the most feasible catalytic cycle, and especially the origin of chemoselectivity for the exclusive aromatic Csp(2)-S bond activation (in the presence of an alkyl Csp(3)-S bond). The coupling mainly consists of three steps: C-S activation, NaO(t)Bu mediated C-H palladation, and reductive elimination. The Csp(2)-S activation is favored over Csp(3)-S activation, and thus di(hetero)aryls are the predicted products. This conclusion well reproduces Wang's recent experimental observations. The rate- and chemoselectivity determining steps of the C-H/Csp(2)-S activation mechanism are C-H palladation and C-S activation steps, respectively. Analyzing the origin of chemoselectivity, we found that the easiness of Pd catalyzed C-S activation is independent of the C-S bond strengths in thioether substrates. By contrast, d-π* backdonation in Csp(2)-S-Pd intermediates is the main driving force for the favorable Csp(2)-S activation (over the Csp(3)-S activation).

Mechanistic study on Rh-catalyzed stereoselective C-C/C-H activation of tert-cyclobutanols.

A mechanistic study was performed on the Rh-catalyzed stereoselective C-C/C-H activation of tert-cyclobutanols. The present study corroborated the previous proposal that the reaction occurs by metalation, ß-C elimination, 1,4-Rh transfer, C=O insertion, and a final catalyst-regeneration step. The rate-determining step was found to be the 1,4-Rh transfer step, whereas the stereoselectivity-determining step did not correspond to any of the aforementioned steps. It was found that both the thermodynamic stability of the product of the ß-C elimination and the kinetic feasibility of the 1,4-Rh transfer and C=O insertion steps made important contributions. In other words, three steps (i.e., ß-C elimination, 1,4-Rh transfer, and C=O insertion) were found to be important in determining the configurations of the two quaternary stereocenters.

Accurate predictions of C-SO2R bond dissociation enthalpies using density functional theory methods.

The dissociation of the C-SO2R bond is frequently involved in organic and bio-organic reactions, and the C-SO2R bond dissociation enthalpies (BDEs) are potentially important for understanding the related mechanisms. The primary goal of the present study is to provide a reliable calculation method to predict the different C-SO2R bond dissociation enthalpies (BDEs). Comparing the accuracies of 13 different density functional theory (DFT) methods (such as B3LYP, TPSS, and M05 etc.), and different basis sets (such as 6-31G(d) and 6-311++G(2df,2p)), we found that M06-2X/6-31G(d) gives the best performance in reproducing the various C-S BDEs (and especially the C-SO2R BDEs). As an example for understanding the mechanisms with the aid of C-SO2R BDEs, some primary mechanistic studies were carried out on the chemoselective coupling (in the presence of a Cu-catalyst) or desulfinative coupling reactions (in the presence of a Pd-catalyst) between sulfinic acid salts and boryl/sulfinic acid salts.

Quantum-chemical predictions of pKa's of thiols in DMSO.

The deprotonation of thiols (on the S-H bond) is widely involved in organic and bio-organic reactions. With the aid of density functional theory (DFT) calculations, the present study focuses on predicting the pKa's of thiols. Efforts were first put in searching for an appropriate computational method. To achieve this goal, the accuracy of 13 different DFT functionals (i.e., B3LYP, BB1K, PBE, M06, M05, M06-2X, M06-L, M05-2X, TPSS, MPW1K, MPWB1K, MPW3LYP, TPSSLYP1W) and 6 different total electron basis sets (6-31G(d), 6-31+G(d), 6-31+G(d,p), 6-311+G(d,p), 6-311++G(d,p), 6-311++G(2df,2p)) (with DMSO solvent and SMD solvation model) were examined. The M06-2X/6-311++G(2df,2p) (M1) method was found to give the best performance in reproducing the reported 16 pKa's of thiols, with a standard deviation (SD) of about 0.5 pKa unit. Meanwhile, the M1 method was found to be excellent in reproducing the gas phase Gibbs free energies of 17 thiols, providing extra evidence for the reliability of the M1 method in treating thiol systems. On this basis, M1 was then used to predict the pKa's of 291 thiols whose experimental pKa values remain unknown. Accordingly, the scope of pKa's of different thiols was constructed.

Simulation of electrical rectification effect in two-dimensional MoSe2/WSe2lateral heterostructures.

Two-dimensional (2D) transition metal dichalcogenides lateral heterostructures exhibit excellent performance in electrics and optics. The electron transport of the heterostructures can be effectively regulated by ingenious design. In this study, we construct a monolayer MoSe2/WSe2lateral heterostructure, covalently connecting monolayer MoSe2and monolayer WSe2. Using the Extended Huckel Theory method, we explored current-voltage characteristics under varied conditions, including altering carrier density, atomic replacement and interface angles. Calculations demonstrate a significant electrical rectification ratio (ERR) ranging from 200 to 800. Additionally, Employing Density Functional Theory with non-equilibrium Green's function method, we investigated electronic properties, attributing the rectification effect to electronic state distribution differences, asymmetric transmission coefficients and band bending of projected local density of states. The expandability of the interfacial energy barrier enhances the rectification effect through adjustments in carrier concentration, atomic replacements and interface size. However, these enhancements introduce challenges such as increased electron-boundary scattering and reduced ambipolarity, resulting in a lower ERR. This study provides valuable theoretical insights for optimizing 2D electronic diode devices, offering avenues for precise control of the rectification effect.

Atomic-Level Matching Metal-Ion Organic Hybrid Interface to Enhance Energy Storage of Polymer-Based Composite Dielectrics.

In this work, a distinctive "metal-ion organic hybrid interface" (MOHI) between polyimide (PI) and calcium niobate (CNO) nanosheets is designed. The metal ions in the MOHI can achieve atomic-level matching not only with the inorganic CNO, but also with the PI chains, forming uniform and strong chemical bonds. These results are demonstrated by experiment and theory calculations. Significantly, the MOHI reduces the free volume and introduces deep traps across the filler-matrix interfacial area, thus suppressing the electric field distortion in PI-based composite dielectrics. Consequently, PI-based dielectric containing the MOHI exhibits excellent energy storage performance. The energy storage densities (Ue) of the composite dielectric reach 9.42 J cm-3 and 4.75 J cm-3 with energy storage efficiency (η) of 90% at 25 °C and 150 °C respectively, which are 2.6 and 11.6 times higher than those of pure PI. This study provides new ideas for polymer-based composite dielectrics in high energy storage.

Suppressing the Loss of Polymer-Based Dielectrics for High Power Energy Storage.

Polymer-based dielectrics have received intensive interest from academic community in the field of high-power energy storage owing to their superior flexibility and fast charge-discharge ability. Recently, how to suppress the loss of polymer-based dielectrics has been increasingly recognized as a critical point to attain a high charge-discharge efficiency in the film capacitors. Some achievements are made in analyzing the source of loss and suppressing loss via Edison's trial and error method. In this review, the significance of suppressing loss in polymer-based dielectrics is firstly emphasized. Then, different sources of loss are discussed carefully and an in-depth analysis of the related measurements is presented. Next, recent research results in suppressing loss are summarized and discussed in detail according to different strategies. Finally, the challenges and opportunities in the loss suppression research for the rational design of high-efficiency polymer-based dielectrics are proposed.

Simultaneous Inhibition of Conduction Loss and Enhancement of Polarization Intensity of Polyetherimide Dielectrics for High-Temperature Capacitive Energy Storage.

Polymer dielectrics with excellent high-temperature capacitive energy storage performance are in urgent demand for modern power electronic devices and high-voltage electrical systems. Nevertheless, the energy storage capability usually degrades dramatically at increased temperatures, owing to the exponentially increased conduction loss. Herein, a trace of commercially available aluminum nitride (AlN) nanoparticles is incorporated into the poly(ether imide) (PEI) matrix to inhibit the conduction loss. The nanostructured AlN component with a large specific surface area can provide abundant sites for the collision of carriers. More importantly, the generated new trap energy levels can immobilize the carriers, accordingly contributing to the reduction in leakage current. From this, the discharged energy density at 150 °C of PEI composites increases by 82.13% from 2.63 J/cm3 for pristine PEI to 4.79 J/cm3 for PEI composites. This work establishes a facile approach to enhancing the high-temperature capacitive performance of polymer dielectrics.

Unifying and Suppressing Conduction Losses of Polymer Dielectrics for Superior High-Temperature Capacitive Energy Storage.

Superior high-temperature capacitive performance of polymer dielectrics is critical for the modern film capacitor demanded in the harsh-environment electronic and electrical systems. Unfortunately, the capacitive performance degrades rapidly at elevated temperatures owing to the exponential growth of conduction loss. The conduction loss is mainly composed of electrode and bulk-limited conduction. Herein, the contribution of surface and bulk factors is unified to conduction loss, and the loss is thoroughly suppressed. The experimental results demonstrate that the polar oxygen-containing groups on the surface of polymer dielectrics can act as the charge trap sites to immobilize the injected charges from electrode, which can in turn establish a built-in field to weaken the external electric field and augment the injection barrier height. Wide bandgap aluminum oxide (Al2 O3 ) nanoparticle fillers can serve as deep traps to constrain the transport of injected or thermally activated charges in the bulk phase. From this, at 200 °C, the discharged energy density with a discharge-charge efficiency of 90% increases by 1058.06% from 0.31 J cm-3 for pristine polyetherimide to 3.59 J cm-3 for irradiated composite film. The principle of simultaneously inhibiting the electrode and bulk-limited conduction losses could be easily extended to other polymer dielectrics for high-temperature capacitive performance.

Enhanced High-Temperature Capacitive Performance of a Bilayer-Structured Composite Film Employing a Charge Blocking Layer.

The great development potential of polymer dielectric capacitors in harsh environments urgently requires enhancing capacitive performance at high temperatures. However, the exponentially increased conduction loss at high temperature and high field results in a drastic drop in energy density and charge-discharge efficiency. Here, a bilayer-structured polyimide (PI) composite film containing a wide-band gap inorganic layer as a charge blocking layer is designed. The inorganic layer improves the charge trapping ability and regulates the charge mobility at the electrode/dielectric interface. The charge injection mechanism in the interface-optimized PI/boron nitride nanosheet (BNNS) composite films is investigated by finite element simulation, and the effect of the BNNS layer on high temperature conduction is further understood. An appropriate thickness of the charge blocking layer establishes an effective energy barrier. Therefore, the composite films exhibit significantly suppressed conduction loss and excellent capacitive performance at a high temperature. A high energy density of 4.37 J cm-3 with efficiency of 92% is obtained at 200 °C and 500 MV m-1, which is superior to reported high-temperature dielectric polymers and their composite films. This work provides a promising approach to improve the energy storage performance of polymer materials at high temperatures.

Dynamic Covalent Adaptable Polyimide Hybrid Dielectric Films with Superior Recyclability.

Polyimides (PIs) used in advanced electrical and electronic devices can be electrically/mechanically damaged, resulting in a significant waste of resources. Closed-loop chemical recycling may prolong the service life of synthetic polymers. However, the design of dynamic covalent bonds for preparing chemically recyclable crosslinked PIs remains a challenging task. Herein, new crosslinked PI films containing a PI oligomer, chain extender, and crosslinker are reported. They exhibit superior recyclability and excellent self-healable ability owing to the synergistic effect of the chain extender and crosslinker. The produced films can be completely depolymerized in an acidic solution at ambient temperature, leading to efficient monomer recovery. The recovered monomers may be used to remanufacture crosslinked PIs without deteriorating their original performance. In particular, the designed films can serve as corona-resistant films with a recovery rate of approximately 100%. Furthermore, carbon fiber reinforced composites (CFRCs) with PI matrices are suitable for harsh environments and can be recycled multiple times at a non-destructive recycling rate up to 100%. The preparation of high-strength dynamic covalent adaptable PI hybrid films from simple PI oligomers, chain extenders, and crosslinkers may provide a solid basis for sustainable development in the electrical and electronic fields.