Tailoring Heterostructure Growth on Liquid Metal Nanodroplets through Interface Engineering.

Liquid metal (LM) nanodroplets possess intriguing surface properties, thus offering promising potential in chemical synthesis, catalysis, and biomedicine. However, the reaction kinetics and product growth at the surface of LM nanodroplets are significantly influenced by the interface involved, which has not been thoroughly explored and understood. Here, we propose an interface engineering strategy, taking a spontaneous galvanic reaction between Ga0 and AuCl4- ions as a representative example, to successfully modulate the growth of heterostructures on the surface of Ga-based LM nanodroplets by establishing a dielectric interface with a controllable thickness between LM and reactive surroundings. Combining high-resolution electron energy-loss spectroscopy (EELS) analysis and theoretical simulation, it was found that the induced charge distribution at the interface dominates the spatiotemporal distribution of the reaction sites. Employing tungsten oxide (WOx) with varying thicknesses as the demonstrated dielectric interface of LM, Ga@WOx@Au with distinct core-shell-satellite or dimer-like heterostructures has been achieved and exhibited different photoresponsive capabilities for photodetection. Understanding the kinetics of product growth and the regulatory strategy of the dielectric interface provides an experimental approach to controlling the structure and properties of products in LM nanodroplet-involved chemical processes.

High-entropy enhanced capacitive energy storage.

Electrostatic dielectric capacitors are essential components in advanced electronic and electrical power systems due to their ultrafast charging/discharging speed and high power density. A major challenge, however, is how to improve their energy densities to effectuate the next-generation applications that demand miniaturization and integration. Here, we report a high-entropy stabilized Bi2Ti2O7-based dielectric film that exhibits an energy density as high as 182 J cm-3 with an efficiency of 78% at an electric field of 6.35 MV cm-1. Our results reveal that regulating the atomic configurational entropy introduces favourable and stable microstructural features, including lattice distorted nano-crystalline grains and a disordered amorphous-like phase, which enhances the breakdown strength and reduces the polarization switching hysteresis, thus synergistically contributing to the energy storage performance. This high-entropy approach is expected to be widely applicable for the development of high-performance dielectrics.

Grain-orientation-engineered multilayer ceramic capacitors for energy storage applications.

Dielectric ceramics are highly desired for electronic systems owing to their fast discharge speed and excellent fatigue resistance. However, the low energy density resulting from the low breakdown electric field leads to inferior volumetric efficiency, which is the main challenge for practical applications of dielectric ceramics. Here, we propose a strategy to increase the breakdown electric field and thus enhance the energy storage density of polycrystalline ceramics by controlling grain orientation. We fabricated high-quality <111>-textured Na0.5Bi0.5TiO3-Sr0.7Bi0.2TiO3 (NBT-SBT) ceramics, in which the strain induced by the electric field is substantially lowered, leading to a reduced failure probability and improved Weibull breakdown strength, on the order of 103 MV m-1, an ~65% enhancement compared to their randomly oriented counterparts. The recoverable energy density of <111>-textured NBT-SBT multilayer ceramics is up to 21.5 J cm-3, outperforming state-of-the-art dielectric ceramics. The present research offers a route for designing dielectric ceramics with enhanced breakdown strength, which is expected to benefit a wide range of applications of dielectric ceramics for which high breakdown strength is required, such as high-voltage capacitors and electrocaloric solid-state cooling devices.

Interface-Strengthened Polymer Nanocomposites with Reduced Dielectric Relaxation Exhibit High Energy Density at Elevated Temperatures Utilizing a Facile Dual Crosslinked Network.

High-temperature ceramic/polymer nanocomposites with large energy density as the reinforcement exhibit great potential for energy storage applications in modern electronic and electrical power systems. Yet, a general drawback is that the increased dielectric constant is usually achieved at the cost of decreased breakdown strength, thus leading to moderate improvement of energy density and even displaying a marked deterioration under high temperatures and high electric fields. Herein, a new strategy is reported to simultaneously improve breakdown strength and discharged energy density by a step-by-step, controllable dual crosslinking process, which constructs a strengthened interface as well as reduces molecular chains relaxation under elevated temperatures. Great breakdown strength and discharged energy density is achieved in the dual crosslinked network BT-BCB@DPAES nanocomposites at elevated temperatures when compared to noninterfacial-strengthened, BT/DPAES composites, i.e., an enhanced breakdown strength and a discharged energy density of 442 MV m-1 and 3.1 J cm-3 , increasing by 66% and 162%, and a stable cyclic performance over 10 000 cycles is demonstrated at 150 °C. Moreover, the enhancement through the synergy of two crosslinked networks is rationalized via a comprehensive phase-field model for the composites. This work offers a strategy to enhance the electric storage performances of composites at high temperatures.

Bioinspired Dielectric Nanocomposites with High Charge-Discharge Efficiency Enabled by Superspreading-Induced Alignment of Nanosheets.

High-performance dielectric nanocomposites are promising candidates for thin-film dielectric capacitors for high-power pulse devices. However, the existing nanocomposites suffer from low charge-discharge efficiency (η), which results in severe generation and accumulation of Joule heat and subsequently the failure of the devices. In this work, we report nacre-inspired dielectric nanocomposites with outstanding η, which are enabled by superspreading shear flow-induced highly aligned two-dimensional (2D) nanofillers. Taking boron nitride nanosheets (BNNS) as an example, the highly aligned BNNS in the poly(vinylidene fluoride) (PVDF)-based nanocomposites contributes to a highly efficient Coulomb blockade effect for the injected charge carriers. Therefore, the bioinspired nanocomposites with highly aligned BNNS show significantly reduced dielectric loss (tan δ) (63.3%) and improved η (144.8%), compared to the ones with partially aligned nanosheets fabricated by solution casting. Furthermore, the optimized loading content of BNNS is as low as 3.6 wt %. The resulting nanocomposites exhibit reduced tan δ (0.018) and enhanced Eb (687 kV/mm), η (71%), and Ue (16.74 J/cm3). Our work demonstrates that the realization of high alignment of 2D nanofillers enabled by the superspreading shear flow is a promising way for the development of high-performance dielectric nanocomposites.

Magnetic-assisted alignment of nanofibers in a polymer nanocomposite for high-temperature capacitive energy storage applications.

Flexible polymer-based dielectrics with high energy storage characteristics over a wide temperature range are crucial for advanced electrical and electronic systems. However, the intrinsic low dielectric constant and drastically degraded breakdown strength hinder the development of polymer-based dielectrics at elevated temperatures. Here, we propose a magnetic-assisted approach for fabricating a polyethyleneimine (PEI)-based nanocomposite with precisely aligned nanofibers within the polymer matrix, and with Al2O3 deposition layers applied on the surface. The resulting polymer nanocomposite exhibits simultaneously increased dielectric constant and enhanced breakdown strength at high temperatures compared to pristine PEI. The enhanced dielectric constant is contributed by the depolarization effect of out-of-plane orientated nanofibers in composite films, while the surficial Al2O3 layers, with a wide bandgap, effectively prevent charge injection and transport at the electrode/dielectric interface. The optimally aligned composite films exhibit a significantly enhanced discharged energy density of 6.5 J cm-3 at 150 °C, with approximately 41% and 132% enhancement compared to random films and pristine PEI films, respectively. Additionally, a metalized multilayer polymer-based capacitor utilizing this composite film produces a high capacitance of 88 nF, while demonstrating excellent cyclability and flexibility at 150 °C. This work offers an effective strategy for developing polymer-based composite dielectrics with superior capacitive performance at elevated temperatures and demonstrates the potential of fabricating high-quality flexible capacitors.

Polymorphic Localized Heterostructure Design for High-Performance Amorphous/Nanocrystalline Composite Film.

Analogous to linear dielectric, amorphous perovskite dielectrics characterized of high breakdown strength and low remanent polarization possess in-depth application in the sea, land, and air fields. Amorphous engineering is a common approach to balance the inverse relationship between polarization and breakdown strength in dielectric ceramic capacitor, however, the low polarization is the major barrier limiting the improvement of energy storage density. To address this concern, the polymorphic localized heterostructure confirmed by high-resolution transmission electron microscope (HR-TEM) and HADDF images is constructed in BaTiO3-Bi(Ni0.5Zr0.5)O3 amorphous/nanocrystalline composite film with SiO2 addition (BT-BNZ-xS, x = 3, 5, 7, 10 mol%). The stability of nanocrystalline region achieved by Si-rich transition region and the enhancive ultra-short-range ordering in the amorphous region synergistically result in large breakdown strength and nonhysteretic polarized response. This polymorphic localized heterostructure optimizes the thermal stability in a wide temperature range and contributes ultrahigh energy storage density of 149.9 J cm-3 with markedly enhanced efficiency of 79.0%. This study provides a universal strategy to design the polarization behavior in other amorphous perovskite-based dielectrics.

Programming Polarity Heterogeneity of Energy Storage Dielectrics by Bidirectional Intelligent Design.

Dielectric capacitors, characterized by ultra-high power densities, are considered as fundamental energy storage components in electronic and electrical systems. However, synergistically improving energy densities and efficiencies remains a daunting challenge. Understanding the role of polarity heterogeneity at the nanoscale in determining polarization response is crucial to the domain engineering of high-performance dielectrics. Here, a bidirectional design with phase-field simulation and machine learning is performed to forward reveal the structure-property relationship and reversely optimize polarity heterogeneity to improve energy storage performance. Taking BiFeO3-based dielectrics as typical systems, this work establishes the mapping diagrams of energy density and efficiency dependence on the volume fraction, size and configuration of polar regions. Assisted by CatBoost and Wolf Pack algorithms, this work analyzes the contributions of geometric factors and intrinsic features and find that nanopillar-like polar regions show great potential in achieving both high polarization intensity and fast dipole switching. Finally, a maximal energy density of 188 J cm-3 with efficiency above 95% at 8 MV cm-1 is obtained in BiFeO3-Al2O3 systems. This work provides a general method to study the influence of local polar heterogeneity on polarization behaviors and proposes effective strategies to enhance energy storage performance by tuning polarity heterogeneity.

Generative learning facilitated discovery of high-entropy ceramic dielectrics for capacitive energy storage.

Dielectric capacitors offer great potential for advanced electronics due to their high power densities, but their energy density still needs to be further improved. High-entropy strategy has emerged as an effective method for improving energy storage performance, however, discovering new high-entropy systems within a high-dimensional composition space is a daunting challenge for traditional trial-and-error experiments. Here, based on phase-field simulations and limited experimental data, we propose a generative learning approach to accelerate the discovery of high-entropy dielectrics in a practically infinite exploration space of over 1011 combinations. By encoding-decoding latent space regularities to facilitate data sampling and forward inference, we employ inverse design to screen out the most promising combinations via a ranking strategy. Through only 5 sets of targeted experiments, we successfully obtain a Bi(Mg0.5Ti0.5)O3-based high-entropy dielectric film with a significantly improved energy density of 156 J cm-3 at an electric field of 5104 kV cm-1, surpassing the pristine film by more than eight-fold. This work introduces an effective and innovative avenue for designing high-entropy dielectrics with drastically reduced experimental cycles, which could be also extended to expedite the design of other multicomponent material systems with desired properties.

Electrically and mechanically driven rotation of polar spirals in a relaxor ferroelectric polymer.

Topology created by quasi-continuous spatial variations of a local polarization direction represents an exotic state of matter, but field-driven manipulation has been hitherto limited to creation and destruction. Here we report that relatively small electric or mechanical fields can drive the non-volatile rotation of polar spirals in discretized microregions of the relaxor ferroelectric polymer poly(vinylidene fluoride-ran-trifluoroethylene). These polar spirals arise from the asymmetric Coulomb interaction between vertically aligned helical polymer chains, and can be rotated in-plane through various angles with robust retention. Given also that our manipulation of topological order can be detected via infrared absorption, our work suggests a new direction for the application of complex materials.

Improved Breakdown Strength and Restrained Leakage Current of Sandwich Structure Ferroelectric Polymers Utilizing Ultra-Thin Al2O3 Nanosheets.

Flexible capacity applications demand a large energy storage density and high breakdown electric field strength of flexible films. Here, P(VDF-HFP) with ultra-thin Al2O3 nanosheet composite films were designed and fabricated through an electrospinning process followed by hot-pressing into a sandwich structure. The results show that the insulating ultra-thin Al2O3 nanosheets and the sandwich structure can enhance the composites' breakdown strength (by 24.8%) and energy density (by 30.6%) compared to the P(VDF-HFP) polymer matrix. An energy storage density of 23.5 J/cm3 at the ultrahigh breakdown strength of 740 kV/mm can be therefore realized. The insulating test and phase-field simulation results reveal that ultra-thin nanosheets insulating buffer layers can reduce the leakage current in composites; thus, it affects the electric field spatial distribution to enhance breakdown strength. Our research provides a feasible method to increase the breakdown strength of ferroelectric polymers, which is comparable to those of non-ferroelectric polymers.

Compressible Polymer Composites with Enhanced Dielectric Temperature Stability.

High-dielectric-constant polymer composites have broad application prospects in flexible electronics and electrostatic energy storage capacitors. Substantial enhancement in dielectric constants (εr ) of polymer composites so far can only be obtained at a high loading of nanofillers, resulting in high dielectric loss and high elastic modulus of polymer composites. Addressing the polarization shielding and the consequent polarization discontinuity at polymer/filler interfaces has been a long-standing challenge to achieve flexible polymer composite with high εr . Herein, a polymer composite with interconnected BaTiO3 (BT) ceramic scaffold is proposed and demonstrated, which exhibits a high εr of ≈210 at a low BT volume fraction of ≈18 vol%, approaching the upper limit predicted by the parallel model. By incorporating relaxor Ba(Zrx Ti1-x )O3 phase in BT scaffold, dielectric temperature stability is further achieved with Δεr below ±10% within a broad temperature range (25-140 °C). Moreover, the dielectric performances remain stable under a compressive strain of up to 80%. This work provides a facile approach to construct large-scale polymer composites with robust dielectric performance against changes in thermal and mechanical conditions, which are promising for high-temperature applications in flexible electronics.

Texture Engineering Modulating Electromechanical Breakdown in Multilayer Ceramic Capacitors.

Understanding the electromechanical breakdown mechanisms of polycrystalline ceramics is critical to texture engineering for high-energy-density dielectric ceramics. Here, an electromechanical breakdown model is developed to fundamentally understand the electrostrictive effect on the breakdown behavior of textured ceramics. Taking the Na0.5 Bi0.5 TiO3 -Sr0.7 Bi0.2 TiO3 ceramic as an example, it is found that the breakdown process significantly depends on the local electric/strain energy distributions in polycrystalline ceramics, and reasonable texture design could greatly alleviate electromechanical breakdown. Then, high-throughput simulations are performed to establish the mapping relationship between the breakdown strength and different intrinsic/extrinsic variables. Finally, machine learning is conducted on the database from the high-throughput simulations to obtain the mathematical expression for semi-quantitatively predicting the breakdown strength, based on which some basic principles of texture design are proposed. The present work provides a computational understanding of the electromechanical breakdown behavior in textured ceramics and is expected to stimulate more theoretical and experimental efforts in designing textured ceramics with reliable electromechanical performances.

Polarity Modulation Induced High Electrostrain Performance with Near-Zero Hysteresis in a (Sr0.7Bi0.2□0.1)TiO3-Based System.

High-precision piezo actuators necessitate dielectrics with high electrostrain performance with low hysteresis. Polarity-modulated (Sr0.7Bi0.2□0.1)TiO3-based ceramics exhibit extraordinarily discrete multiphase coexistence regions: (i) the relaxor phase coexistence (RPC) region with local weakly polar tetragonal (T) and pseudocubic (Pc) short-range polar nanodomains and (ii) the ferroelectric phase coexistence (FPC) region with T long-range domains and Pc nanodomains. The RPC composition features a specially high and pure electrostrain performance with near-zero hysteresis (S ∼ 0.185%, Q33 ∼ 0.038 m4·C-2), which is double those of conventional Pb(Mg1/3Nb2/3)O3-based ceramics. Particular interest is paid to the RPC and FPC with multiscale characterization to unravel local structure-performance relationships. Guided by piezoelectric force microscopy, scanning transmission electron microscopy, and phase-field simulations, the RPC composition with multiphase low-angle weakly polar nanodomains shows local structural heterogeneity and contributes to a flat local free energy profile and thus to nanodomain switching and superior electrostrain performance, in contrast to the FPC composition with a macroscopic domain that shows stark hysteresis. This work provides a paradigm to design high-precision actuator materials with large electrostrain and ultralow hysteresis, extending our knowledge of multiphase coexistence species in ferroelectrics.

Unraveling bilayer interfacial features and their effects in polar polymer nanocomposites.

Polymer nanocomposites with nanoparticles dispersed in polymer matrices have attracted extensive attention due to their significantly improved overall performance, in which the nanoparticle-polymer interface plays a key role. Understanding the structures and properties of the interfacial region, however, remains a major challenge for polymer nanocomposites. Here, we directly observe the presence of two interfacial polymer layers around a nanoparticle in polar polymers, i.e., an inner bound polar layer (~10 nm thick) with aligned dipoles and an outer polar layer (over 100 nm thick) with randomly orientated dipoles. Our results reveal that the impacts of the local nanoparticle surface potential and interparticle distance on molecular dipoles induce interfacial polymer layers with different polar molecular conformations from the bulk polymer. The bilayer interfacial features lead to an exceptional enhancement in polarity-related properties of polymer nanocomposites at ultralow nanoparticle loadings. By maximizing the contribution of inner bound polar layer via a nanolamination design, we achieve an ultrahigh dielectric energy storage density of 86 J/cm3, far superior to state-of-the-art polymers and nanocomposites.

Stretchable polymer composites with ultrahigh piezoelectric performance.

Flexible piezoelectric materials capable of withstanding large deformation play key roles in flexible electronics. Ferroelectric ceramics with a high piezoelectric coefficient are inherently brittle, whereas polar polymers exhibit a low piezoelectric coefficient. Here we report a highly stretchable/compressible piezoelectric composite composed of ferroelectric ceramic skeleton, elastomer matrix and relaxor ferroelectric-based hybrid at the ceramic/matrix interface as dielectric transition layers, exhibiting a giant piezoelectric coefficient of 250 picometers per volt, high electromechanical coupling factor keff of 65%, ultralow acoustic impedance of 3MRyl and high cyclic stability under 50% compression strain. The superior flexibility and piezoelectric properties are attributed to the electric polarization and mechanical load transfer paths formed by the ceramic skeleton, and dielectric mismatch mitigation between ceramic fillers and elastomer matrix by the dielectric transition layer. The synergistic fusion of ultrahigh piezoelectric properties and superior flexibility in these polymer composites is expected to drive emerging applications in flexible smart electronics.

High Conduction Band Inorganic Layers for Distinct Enhancement of Electrical Energy Storage in Polymer Nanocomposites.

Dielectric polymer nanocomposites are considered as one of the most promising candidates for high-power-density electrical energy storage applications. Inorganic nanofillers with high insulation property are frequently introduced into fluoropolymer to improve its breakdown strength and energy storage capability. Normally, inorganic nanofillers are thought to introducing traps into polymer matrix to suppress leakage current. However, how these nanofillers effect the leakage current is still unclear. Meanwhile, high dopant (> 5 vol%) is prerequisite for distinctly improved energy storage performance, which severely deteriorates the processing and mechanical property of polymer nanocomposites, hence brings high technical complication and cost. Herein, boron nitride nanosheet (BNNS) layers are utilized for substantially improving the electrical energy storage capability of polyvinylidene fluoride (PVDF) nanocomposite. Results reveal that the high conduction band minimum of BNNS produces energy barrier at the interface of adjacent layers, preventing the electron in PVDF from passing through inorganic layers, leading to suppressed leakage current and superior breakdown strength. Accompanied by improved Young's modulus (from 1.2 GPa of PVDF to 1.6 GPa of nanocomposite), significantly boosted discharged energy density (14.3 J cm-3) and charge-discharge efficiency (75%) are realized in multilayered nanocomposites, which are 340 and 300% of PVDF (4.2 J cm-3, 25%). More importantly, thus remarkably boosted energy storage performance is accomplished by marginal BNNS. This work offers a new paradigm for developing dielectric nanocomposites with advanced energy storage performance.

Concurrent Enhancement of Breakdown Strength and Dielectric Constant in Poly(vinylidene Fluoride) Film with High Energy Storage Density by Ultraviolet Irradiation.

Polyvinylidene fluoride (PVDF) film with high energy storage density has exhibited great potential for applications in modern electronics, particle accelerators, and pulsed lasers. Typically, dielectric/ferroelectric properties of PVDF film have been tailored for energy storage through stretching, annealing, and defect modification. Here, PVDF films were prepared by the solution casting method followed by an ultraviolet (UV) irradiation process, with special emphasis on how such treatment influences their dielectric and energy storage properties. Upon UV irradiation, the dielectric constant and breakdown strength of the PVDF film were enhanced simultaneously. A high energy density of 18.6 J/cm3, along with a charge-discharge efficiency of 81% at 600 MV/m, was achieved in PVDF after exposure to UV for 15 min. This work may provide a simple and yet effective route to enhance energy storage density of PVDF-based polymers.

Chemical adsorption on 2D dielectric nanosheets for matrix free nanocomposites with ultrahigh electrical energy storage.

Relaxor ferroelectric polymers display great potential in capacitor dielectric applications because of their excellent flexibility, light weight, and high dielectric constant. However, their electrical energy storage capacity is limited by their high conduction losses and low dielectric strength, which primarily originates from the impact-ionization-induced electronmultiplication, low mechanical modulus, and low thermal conductivity of the dielectric polymers. Here a matrix free strategy is developed to effectively suppress electron multiplication effects and to enhance mechanical modulus and thermal conductivity of a dielectric polymer, which involves the chemical adsorption of an electron barrier layer on boron nitride nanosheet surfaces by chemically adsorbing an amino-containing polymer. A dramatic decrease of leakage current (from 2.4 × 10-6 to 1.1 × 10-7 A cm-2 at 100 MV m-1) and a substantial increase of breakdown strength (from 340 to 742 MV m-1) were achieved in the nanocompostes, which result in a remarkable increase of discharge energy density (from 5.2 to 31.8 J cm-3). Moreover, the dielectric strength of the nanocomposites suffering an electrical breakdown could be restored to 88% of the original value. This study demonstrates a rational design for fabricating dielectric polymer nanocomposites with greatly enhanced electric energy storage capacity.

Polymer dielectric films exhibiting superior high-temperature capacitive performance by utilizing an inorganic insulation interlayer.

With the rapid development of next-generation electrical power equipment and microelectronics, there is an urgent demand for dielectric capacitor films which can work efficiently under extreme conditions. However, sharply increased electrical conduction and drastically degrading electric breakdown strength are inevitable at elevated temperatures. Herein, a facile but effective method is proposed to improve high temperature capacitive performance. We report that utilizing an inorganic insulation interlayer can significantly increase the discharge energy density with a high efficiency above 90% at 150 °C, i.e., a discharged energy density of 4.13 J cm-3 and an efficiency of >90% measured at 150 °C, which is superior to the state-of-the-art dielectric polymers. Combining the experimental results and computational simulations reveals that the remarkable improvement in energy storage performance at high temperature is attributed to the blocking effects that reduce the leakage current and maintain the breakdown strength. The proposed facile method provides great inspiration for developing polymer dielectric films with high capacitive performance under extreme environments.