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.

High-Entropy Design for 2D Halide Perovskite.

Hybrid halide perovskites are good candidates for a range of functional materials such as optical electronic and photovoltaic devices due to their tunable band gaps, long carrier diffusion lengths, and solution processability. However, the instability in moisture/air, the toxicity of lead, and rigorous reaction setup or complex postprocessing have long been the bottlenecks for practical application. Herein, we present a simultaneous configurational entropy design at A-sites, B-sites, and X-sites in the typical (CHA)2PbBr4 two-dimensional (2D) hybrid perovskite. Our results demonstrate that the high-entropy effect favors the stabilization of the hybrid perovskite phase and facilitates a simple crystallization process without precise control of the cooling rate to prepare regular crystals. Moreover, high-entropy 2D perovskite crystals exhibit tunable energy band gaps, broadband emission, and a long carrier lifetime. Meanwhile, the high-entropy composition almost maintains the initial crystal structure in deionized water for 18 h while the original (CHA)2PbBr4 crystal mostly decomposes, suggesting obviously improved humidity stability. This work offers a facile approach to synthesize humidity-stable hybrid perovskites under mild conditions, accelerating relevant preparation of optoelectronics and light-emitting devices and facilitating the ultimate commercialization of halide perovskite.

Fully Printed Multilayer Ceramic Capacitors Based on High-k Perovskite Nanosheets.

Printing technology enables the integration of chemically exfoliated perovskite nanosheets into high-performance microcapacitors. Theoretically, the capacitance value can be further enhanced by designing and constructing multilayer structures without increasing the device size. Yet, issues such as interlayer penetration in multilayer heterojunctions constructed using inkjet printing technology further limit the realization of this potential. Herein, a series of multilayer configurations, including Ag/(Ca2NaNb4O13/Ag)n and graphene/(Ca2NaNb4O13/graphene)n (n = 1-3), are successfully inkjet-printed onto diverse rigid and flexible substrates through optimized ink formulations, inkjet printing parameters, thermal treatment conditions, and rational multilayer structural design using high-k perovskite nanosheets, graphene nanosheets and silver. The dielectric performance is optimized by fine-tuning the number of dielectric layers and modifying the electrode/dielectric interface. As a result, the graphene/(Ca2NaNb4O13/graphene)3 multilayer ceramic capacitors exhibit a remarkable capacitance density of 346 ± 12 nF cm-2 and a high dielectric constant of 193 ± 18. Additionally, these devices demonstrate moderate insulation properties, flexibility, thermal stability, and chemical sensitivity. This work shed light on the potential of multilayer structural design in additive manufacturing of high-performance 2D material-based ceramic capacitors.

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.

Direct Ink Writing of Low-Concentration MXene/Aramid Nanofiber Inks for Tunable Electromagnetic Shielding and Infrared Anticounterfeiting Applications.

MXene inks offer a promising avenue for the scalable production and customization of printing electronics. However, simultaneously achieving a low solid content and printability of MXene inks, as well as mechanical flexibility and environmental stability of printed objects, remains a challenge. In this study, we overcame these challenges by employing high-viscosity aramid nanofibers (ANFs) to optimize the rheology of low-concentration MXene inks. The abundant entangled networks and hydrogen bonds formed between MXene and ANF significantly increase the viscosity and yield stress up to 103 Pa·s and 200 Pa, respectively. This optimization allows the use of MXene/ANF (MA) inks at low concentrations in direct ink writing and other high-viscosity processing techniques. The printable MXene/ANF inks with a high conductivity of 883.5 S/cm were used to print shields with customized structures, achieving a tunable electromagnetic interference shielding effectiveness (EMI SE) in the 0.2-48.2 dB range. Furthermore, the MA inks exhibited adjustable infrared (IR) emissivity by changing the ANF ratio combined with printing design, demonstrating the application for infrared anticounterfeiting. Notably, the printed MXene/ANF objects possess outstanding mechanical flexibility and environmental stability, which are attributed to the reinforcement and protection of ANF. Therefore, these findings have significant practical implications as versatile MXene/ANF inks can be used for customizable, scalable, and cost-effective production of flexible printed electronics.

Balancing Polarization and Breakdown for High Capacitive Energy Storage by Microstructure Design.

The compromise of contradictive parameters, polarization, and breakdown strength, is necessary to achieve a high energy storage performance. The two can be tuned, regardless of material types, by controlling microstructures: amorphous states possess higher breakdown strength, while crystalline states have larger polarization. However, how to achieve a balance of amorphous and crystalline phases requires systematic and quantitative investigations. Herein, the trade-off between polarization and breakdown field is comprehensively evaluated with the evolution of microstructure, i.e., grain size and crystallinity, by phase-field simulations. The results indicate small grain size (≈10-35 nm) with moderate crystallinity (≈60-80%) is more beneficial to maintain relatively high polarization and breakdown field simultaneously, consequently contributing to a high overall energy storage performance. Experimentally, therefore an ultrahigh energy density of 131 J cm-3 is achieved with a high efficiency of 81.6% in the microcrystal-amorphous dual-phase Bi3NdTi4O12 films. This work provides a guidance to substantially enhance dielectric energy storage by a simple and effective microstructure design.

Halide Perovskite Inducing Anomalous Nonvolatile Polarization in Poly(vinylidene fluoride)-based Flexible Nanocomposites.

Ferroelectric materials have important applications in transduction, data storage, and nonlinear optics. Inorganic ferroelectrics such as lead zirconate titanate possess large polarization, though they are rigid and brittle. Ferroelectric polymers are light weight and flexible, yet their polarization is low, bottlenecked at 10 µC cm-2. Here we show poly(vinylidene fluoride) nanocomposite with only 0.94% of self-nucleated CH3NH3PbBr3 nanocrystals exhibits anomalously large polarization (~19.6 µC cm-2) while retaining superior stretchability and photoluminance, resulting in unprecedented electromechanical figures of merit among ferroelectrics. Comprehensive analysis suggests the enhancement is accomplished via delicate defect engineering, with field-induced Frenkel pairs in halide perovskite stabilized by the poled ferroelectric polymer through interfacial coupling. The strategy is general, working in poly(vinylidene fluoride-co-hexafluoropropylene) as well, and the nanocomposite is stable. The study thus presents a solution for overcoming the electromechanical dilemma of ferroelectrics while enabling additional optic-activity, ideal for multifunctional flexible electronics applications.

Achieving High-Performance Lithium-Sulfur Batteries by Modulating Li+ Desolvation Barrier with Liquid Crystal Polymers.

Lithium-sulfur (Li-S) batteries offer high theoretical capacity but are hindered by poor rate capability and cycling stability due to sluggish Li2S precipitation kinetics. Here a sulfonate-group-rich liquid crystal polymer (poly-2,2'-disulfonyl-4,4'-benzidine terephthalamide, PBDT) is designed and fabricated to accelerate Li2S precipitation by promoting the desolvation of Li+ from electrolyte. PBDT-modified separators are employed to assemble Li-S batteries, which deliver a remarkable rate capacity (761 mAh g-1 at 4 C) and cycling stability (500 cycles with an average decay rate of 0.088% per cycle at 0.5 C). A PBDT-based pouch cell even delivers an exceptional capacity of ≈1400 mAh g-1 and an areal capacity of ≈11 mAh cm-2 under lean-electrolyte and high-sulfur-loading condition, demonstrating promise for practical applications. Results of Raman spectra, molecular dynamic (MD) and density functional theory (DFT) calculations reveal that the abundant anionic sulfonate groups of PBDT aid in Li+ desolvation by attenuating Li+-solvent interactions and lowering the desolvation energy barrier. Plus, the polysulfide adsorption/catalysis is also excluded via electrostatic repulsion. This work elucidates the critical impact of Li+ desolvation on Li-S batteries and provides a new design direction for advanced Li-S batteries.

A correlated ferromagnetic polar metal by design.

Polar metals have recently garnered increasing interest because of their promising functionalities. Here we report the experimental realization of an intrinsic coexisting ferromagnetism, polar distortion and metallicity in quasi-two-dimensional Ca3Co3O8. This material crystallizes with alternating stacking of oxygen tetrahedral CoO4 monolayers and octahedral CoO6 bilayers. The ferromagnetic metallic state is confined within the quasi-two-dimensional CoO6 layers, and the broken inversion symmetry arises simultaneously from the Co displacements. The breaking of both spatial-inversion and time-reversal symmetries, along with their strong coupling, gives rise to an intrinsic magnetochiral anisotropy with exotic magnetic field-free non-reciprocal electrical resistivity. An extraordinarily robust topological Hall effect persists over a broad temperature-magnetic field phase space, arising from dipole-induced Rashba spin-orbit coupling. Our work not only provides a rich platform to explore the coupling between polarity and magnetism in a metallic system, with extensive potential applications, but also defines a novel design strategy to access exotic correlated electronic states.

Ultrahigh energy storage in high-entropy ceramic capacitors with polymorphic relaxor phase.

Ultrahigh-power-density multilayer ceramic capacitors (MLCCs) are critical components in electrical and electronic systems. However, the realization of a high energy density combined with a high efficiency is a major challenge for practical applications. We propose a high-entropy design in barium titanate (BaTiO3)-based lead-free MLCCs with polymorphic relaxor phase. This strategy effectively minimizes hysteresis loss by lowering the domain-switching barriers and enhances the breakdown strength by the high atomic disorder with lattice distortion and grain refining. Benefiting from the synergistic effects, we achieved a high energy density of 20.8 joules per cubic centimeter with an ultrahigh efficiency of 97.5% in the MLCCs. This approach should be universally applicable to designing high-performance dielectrics for energy storage and other related functionalities.

Boosting Thermoelectric Performance via Weakening Carrier-Phonon Coupling in BiCuSeO-Graphene Composites.

BiCuSeO is a promising oxygen-containing thermoelectric material due to its intrinsically low lattice thermal conductivity and excellent service stability. However, the low electrical conductivity limits its thermoelectric performance. Aliovalent element doping can significantly improve their carrier concentration, but it may also impact carrier mobility and thermal transport properties. Considering the influence of graphene on carrier-phonon decoupling, Bi0.88 Pb0.06 Ca0.06 CuSeO (BPCCSO)-graphene composites are designed. For further practical application, a rapid preparation method is employed, taking less than 1 h, which combines self-propagating high-temperature synthesis with spark plasma sintering. The incorporation of graphene simultaneously optimizes the electrical properties and thermal conductivity, yielding a high ratio of weighted mobility to lattice thermal conductivity (144 at 300 K and 95 at 923 K). Ultimately, BPCCSO-graphene composites achieve exceptional thermoelectric performance with a ZT value of 1.6 at 923 K, bringing a ≈40% improvement over BPCCSO without graphene. This work further promotes the practical application of BiCuSeO-based materials and this facile and effective strategy can also be extended to other thermoelectric systems.

Giant electric field-induced second harmonic generation in polar skyrmions.

Electric field-induced second harmonic generation allows electrically controlling nonlinear light-matter interactions crucial for emerging integrated photonics applications. Despite its wide presence in materials, the figures-of-merit of electric field-induced second harmonic generation are yet to be elevated to enable novel device functionalities. Here, we show that the polar skyrmions, a topological phase spontaneously formed in PbTiO3/SrTiO3 ferroelectric superlattices, exhibit a high comprehensive electric field-induced second harmonic generation performance. The second-order nonlinear susceptibility and modulation depth, measured under non-resonant 800 nm excitation, reach ~54.2 pm V-1 and ~664% V-1, respectively, and high response bandwidth (higher than 10 MHz), wide operating temperature range (up to ~400 K) and good fatigue resistance (>1010 cycles) are also demonstrated. Through combined in-situ experiments and phase-field simulations, we establish the microscopic links between the exotic polarization configuration and field-induced transition paths of the skyrmions and their electric field-induced second harmonic generation response. Our study not only presents a highly competitive thin-film material ready for constructing on-chip devices, but opens up new avenues of utilizing topological polar structures in the fields of photonics and optoelectronics.

Polymer nanocomposite dielectrics for capacitive energy storage.

Owing to their excellent discharged energy density over a broad temperature range, polymer nanocomposites offer immense potential as dielectric materials in advanced electrical and electronic systems, such as intelligent electric vehicles, smart grids and renewable energy generation. In recent years, various nanoscale approaches have been developed to induce appreciable enhancement in discharged energy density. In this Review, we discuss the state-of-the-art polymer nanocomposites with improved energy density from three key aspects: dipole activity, breakdown resistance and heat tolerance. We also describe the physical properties of polymer nanocomposite interfaces, showing how the electrical, mechanical and thermal characteristics impact energy storage performances and how they are interrelated. Further, we discuss multi-level nanotechnologies including monomer design, crosslinking, polymer blending, nanofiller incorporation and multilayer fabrication. We conclude by presenting the current challenges and future opportunities in this field.

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.

Programmable Ferroelectricity in Hf0.5Zr0.5O2 Enabled by Oxygen Defect Engineering.

Ferroelectricity, especially the Si-compatible type recently observed in hafnia-based materials, is technologically useful for modern memory and logic applications, but it is challenging to differentiate intrinsic ferroelectric polarization from the polar phase and oxygen vacancy. Here, we report electrically controllable ferroelectricity in a Hf0.5Zr0.5O2-based heterostructure with Sr-doped LaMnO3, a mixed ionic-electronic conductor, as an electrode. Electrically reversible extraction and insertion of an oxygen vacancy into Hf0.5Zr0.5O2 are macroscopically characterized and atomically imaged in situ. Utilizing this reversible process, we achieved multilevel polarization states modulated by the electric field. Our study demonstrates the usefulness of the mixed conductor to repair, create, manipulate, and utilize advanced ferroelectric functionality. Furthermore, the programmed ferroelectric heterostructures with Si-compatible doped hafnia are desirable for the development of future ferroelectric electronics.

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.

Electric-Field Control of Perpendicularly Magnetized Ferrimagnetic Order and Giant Magnetoresistance in Multiferroic Heterostructures.

Electrical control of magnetism is highly desirable for energy-efficient spintronic applications. Realizing electric-field-driven perpendicular magnetization switching has been a long-standing goal, which, however, remains a major challenge. Here, electric-field control of perpendicularly magnetized ferrimagnetic order via strain-mediated magnetoelectric coupling is reported. We show that the gate voltages isothermally toggle the dominant magnetic sublattice of the compensated ferrimagnet FeTb at room temperature, showing high reversibility and good endurance under ambient conditions. By implementing this strategy in FeTb/Pt/Co spin valves with giant magnetoresistance (GMR), we demonstrate that the distinct high and low resistance states can be selectively controlled by the gate voltages with assisting magnetic fields. Our results provide a promising route to use ferrimagnets for developing electric-field-controlled, low-power memory and logic devices.

Single-Ion Conductive Polymer-Based Composite Electrolytes for High-Performance Solid-State Lithium Metal Batteries.

Flexible composite polymer electrolytes (CPEs) with inorganic electrolyte fillers dispersed in polymer electrolytes integrate the merits of the polymer and inorganic electrolytes and have attracted much attention in recent years. In order to increase the electrochemical performance, especially the low lithium (Li)-ion transference number in traditional dual-ion Li salt-containing CPEs, single-ion conductive CPEs are synthesized with a single-ion polymer conductor (SIPC) as the matrix and Li6.4 La3 Zr1.4 Ta0.6 O12 (LLZTO) particles as the active fillers. The single-ion conductive CPEs show a high Li-ion transference number (up to 0.96), high room-temperature (RT) ionic conductivity (>1.0 × 10-4 S cm-1 ), wide electrochemical stability window (>5.0 V, vs Li/Li+ ), and excellent long-term cycling stability with Li metal at RT (3200 h). Based on the SIPC-LLZTO CPE, the solid-state lithium metal batteries with LiFePO4 - and LiCoO2 -based cathodes deliver average discharge capacities of 159 mAh g-1 for 600 cycles and 119 mAh g-1 for 200 cycles at RT, respectively. This study sheds light on the design of high-performance CPEs for next-generation solid-state lithium metal batteries.

High-Entropy Lithium Argyrodite Solid Electrolytes Enabling Stable All-Solid-State Batteries.

Superionic solid electrolytes (SEs) are essential for bulk-type solid-state battery (SSB) applications. Multicomponent SEs are recently attracting attention for their favorable charge-transport properties, however a thorough understanding of how configurational entropy (ΔSconf ) affects ionic conductivity is lacking. Here, we successfully synthesized a series of halogen-rich lithium argyrodites with the general formula Li5.5 PS4.5 Clx Br1.5-x (0≤x≤1.5). Using neutron powder diffraction and 31 P magic-angle spinning nuclear magnetic resonance spectroscopy, the S2- /Cl- /Br- occupancy on the anion sublattice was quantitatively analyzed. We show that disorder positively affects Li-ion dynamics, leading to a room-temperature ionic conductivity of 22.7 mS cm-1 (9.6 mS cm-1 in cold-pressed state) for Li5.5 PS4.5 Cl0.8 Br0.7 (ΔSconf =1.98R). To the best of our knowledge, this is the first experimental evidence that configurational entropy of the anion sublattice correlates with ion mobility. Our results indicate the possibility of improving ionic conductivity in ceramic ion conductors by tailoring the degree of compositional complexity. Moreover, the Li5.5 PS4.5 Cl0.8 Br0.7 SE allowed for stable cycling of single-crystal LiNi0.9 Co0.06 Mn0.04 O2 (s-NCM90) composite cathodes in SSB cells, emphasizing that dual-substituted lithium argyrodites hold great promise in enabling high-performance electrochemical energy storage.