Wood-inspired anisotropic hydrogel electrolyte with large modulus and low tortuosity realizing durable dendrite-free zinc-ion batteries.

While aqueous zinc-ion batteries exhibit great potential, their performance is impeded by zinc dendrites. Existing literature has proposed the use of hydrogel electrolytes to ameliorate this issue. Nevertheless, the mechanical attributes of hydrogel electrolytes, particularly their modulus, are suboptimal, primarily ascribed to the substantial water content. This drawback would severely restrict the dendrite-inhibiting efficacy, especially under large mass loadings of active materials. Inspired by the structural characteristics of wood, this study endeavors to fabricate the anisotropic carboxymethyl cellulose hydrogel electrolyte through directional freezing, salting-out effect, and compression reinforcement, aiming to maximize the modulus along the direction perpendicular to the electrode surface. The heightened modulus concurrently serves to suppress the vertical deposition of the intermediate product at the cathode. Meanwhile, the oriented channels with low tortuosity enabled by the anisotropic structure are beneficial to the ionic transport between the anode and cathode. Comparative analysis with an isotropic hydrogel sample reveals a marked enhancement in both modulus and ionic conductivity in the anisotropic hydrogel. This enhancement contributes to significantly improved zinc stripping/plating reversibility and mitigated electrochemical polarization. Additionally, a durable quasi-solid-state Zn//MnO2 battery with noteworthy volumetric energy density is realized. This study offers unique perspectives for designing hydrogel electrolytes and augmenting battery performance.

Transition Metal ß-Diketonate Adhesion Promoters in Epoxy-Anhydride Resin.

Epoxy to copper adhesion supports the reliability of numerous structures in electronic packaging. Compared to substrate pre-treatment, processing and cost considerations are in favor of adhesion promoters loaded in epoxy formulations. In this work, first row transition metal ß-diketonates present such a compelling case when added in epoxy/anhydride resins: over 30% (before moisture aging) and 50% (after moisture aging) enhancement in lap shear strength are found using Co(II) and Ni(II) hexafluoroacetylacetonate. From extensive X-ray photoelectron spectroscopy (XPS) analyses on the adhesively failed sample surfaces, increased population of oxygen-containing functional groups, especially esters, is linked to the adhesion improvement. Assisted by XPS depth profile on the fractured epoxy side and in situ Fourier-transform infrared spectroscopy (FTIR), the previously discovered latent cure characteristics endowed by the metal chelates interacting with phosphine catalysts are regarded pivotal for pacing the anhydride consumption and allowing interfacial esterification reactions to occur. Further examinations on the XPS binding energy shifts and dielectric properties of the doped epoxy also reveal metal-polymer coordination that contribute to the adhesion and moisture resistance properties. These findings should stimulate future research of functional additives targeting at cure kinetics control and polar group coordination ideas for more robust epoxy-Cu joints.

Numerical homogenization of thermal conductivity of particle-filled thermal interface material by fast Fourier transform method.

Thermal interface material (TIM) is pivotal for the heat dissipation between layers of high-density electronic packaging. The most widely used TIMs are particle-filled composite materials, in which highly conductive particulate fillers are added into the polymer matrix to promote heat conduction. The numerical simulation of heat transfer in the composites is essential for the design of TIMs; however, the widely used finite element method (FEM) requires large memory and presents limited computational time for the composites with dense particles. In this work, a numerical homogenization algorithm based on fast Fourier transform was adopted to estimate the thermal conductivity of composites with randomly dispersed particles in 3D space. The unit cell problem is solved by means of a polarization-based iterative scheme, which can accelerate the convergence procedure regardless of the contrast between various components. The algorithm shows good precision and requires dramatically reduced computation time and cost compared with FEM. Moreover, the effect of the particle volume fraction, interface thermal resistance between particles (R-PP), interface thermal resistance between particle and matrix (R-PM), and particle size have been estimated. It turns out that the effective conductivity of the particulate composites increases sharply at a critical filler volume fraction, after which it is sensitive to the variation of filler loading. We can observe that the effective thermal conductivity of the composites with low filler volume fraction is sensitive to R-PM, whereas the it is governed by R-PP for the composites with high filler content. The algorithm presents excellent efficiency and accuracy, showing potential for the future design of highly thermally conductive TIMs.

Flexible and electrically conductive composites based on 3D hierarchical silver dendrites.

Conductive polymer composites have gained increasing popularity as essential components for next-generation flexible electronics. Chemical tuning of the polymer matrix and shape engineering of conductive fillers are two promising routes for material development to improve the electromechanical characteristics. Here we describe highly conductive and flexible polyurethane (PU)-based composites using 3D hierarchical silver dendrite (SD) micro/nanostructures as conductive fillers. The highly crystalline SDs adopt a 6-fold symmetry with high aspect ratio branches, which can be interlocked to provide better electrical contact under strain and sintered at low temperature to reduce contact resistance. By selecting the appropriate chemistry, SD fillers lubricated with surfactants can be well dispersed into PU resin and the surfactants can be in situ removed during the curing process due to the presence of polyols in the formulation. The unique SD structures and modified polymer-filler interface are key elements in realizing excellent electrical and mechanical properties. Specifically, the SD-PU composites demonstrated an ultralow resistivity of 7.6 × 10-5 Ω cm, a low percolation threshold of 3 vol%, minimal resistance change under mechanical strains, and strong adhesion to substrates. The evolution of temperature-dependent resistivity has been correlated with polymer dynamics and sintering behavior to understand the conduction mechanism.

Hybrid Anodic and Metal-Assisted Chemical Etching Method Enabling Fabrication of Silicon Carbide Nanowires.

Silicon carbide (SiC) is one of the most important third-generation semiconductor materials. However, the chemical robustness of SiC makes it very difficult to process, and only very limited methods are available to fabricate nanostructures on SiC. In this work, a hybrid anodic and metal-assisted chemical etching (MACE) method is proposed to fabricate SiC nanowires based on wet etching approaches at room temperature and under atmospheric pressure. Through investigations of the etching mechanism and optimal etching conditions, it is found that the metal component plays at least two key roles in the process, i.e., acting as a catalyst to produce hole carriers and introducing band bending in SiC to accumulate sufficient holes for etching. Through the combined anodic and MACE process the required electrical bias is greatly lowered (3.5 V for etching SiC and 7.5 V for creating SiC nanowires) while enhancing the etching efficiency. Furthermore, it is demonstrated that by tuning the etching electrical bias and time, various nanostructures can be obtained and the diameters of the obtained pores and nanowires can range from tens to hundreds of nanometers. This facile method may provide a feasible and economical way to fabricate SiC nanowires and nanostructures for broad applications.

Highly Ordered 3D Porous Graphene Sponge for Wearable Piezoresistive Pressure Sensor Applications.

Wearable sensors with excellent flexibility and sensitivity have emerged as a promising field for healthcare, electronic skin, and so forth. Three-dimensional (3D) graphene sponges (GS) have emerged as high-performance piezoresistive sensors; however, problems, such as limited flexibility, high cost, and low sensitivity, remain. Meanwhile, device-level wearable pressure sensors with GS have rarely been demonstrated. In this work, highly ordered 3D porous graphene sponges (OPGSs) were first successfully prepared and controlled through an emulsion method, and then a device-level wearable pressure sensor with high flexibility and sensitivity was assembled with a gold electrode and polydimethylsiloxane into a reliable package. The pH values were carefully controlled to form a stable emulsion and the OPGSs showed a highly ordered 3D structure with ultralow density, high porosity, and conductivity; this resulted in a gauge factor of 0.79-1.46, with 50 % compression strain and excellent long-term reproducibility over 500 cycles of compression-relaxation. Moreover, the well-packaged pressure sensor devices exhibited ultrahigh sensitivity to detect human motions, such as wrist bending, elbow bending, finger bending, and palm flexing. Thus, the developed pressure sensors exhibited great potential in the fields of human-interactive applications, biomechanical systems, electronic skin, and so forth.

Self-Healable Polyelectrolytes with Mechanical Enhancement for Flexible and Durable Supercapacitors.

The practical application of advanced personalized electronics is inseparable from flexible, durable, and even self-healable energy storage devices. However, the mechanical and self-healing performance of supercapacitors is still limited at present. Herein, highly transparent, stretchable, and self-healable poly(2-acrylamido-2-methyl-1-propanesulfonic acid) (PAMPSA)/poly(vinyl alcohol) (PVA)/LiCl polyelectrolytes were facilely prepared by one-step radical polymerization. The cooperation of PAMPSA and PVA significantly increased the mechanical and self-healing capacity of the polyelectrolyte, which exhibited superior stretchability of 938 %, stress of 112.68 kPa, good electrical performance (ionic conductivity up to 20.6 mS cm-1 ), and high healing efficiency of 92.68 % after 24 h. After assembly with polypyrrole-coated single-walled carbon nanotubes, the resulting as-prepared supercapacitor had excellent electrochemical properties with high areal capacitance of 297 mF cm-2 at 0.5 mA cm-2 and good rate capability (218 mF cm-2 at 5 mA cm-2 ). Besides, after cutting in two the supercapacitor recovered 99.2 % of its original specific capacitance after healing for 24 h at room temperature. The results also showed negligible change in the interior contact resistance of the supercapacitor after ten cutting/healing cycles. The present work provides a possible solution for the development of smart and durable energy storage devices with low cost for next-generation intelligent electronics.

Facile and scalable fabrication of self-assembled Cu architecture with superior antioxidative properties and improved sinterability as a conductive ink for flexible electronics.

The inherent susceptibility to oxidation and poor sinterability significantly limit the practical application of Cu-based conductive inks. Most methodologies employed for the inks like organic polymer coatings and inorganic metal deposition are generally ineffective. Herein, we report the design of a novel hierarchical Cu architecture to simultaneously improve the antioxidative and sinterability via a self-passivation mechanism and loose interior structures. The hierarchical Cu architecture was prepared using copper hydroxide, L-ascorbic acid, and polyvinylpyrrolidone in aqueous solution; 40 g Cu were prepared in a scale-up experiment. A possible growth mechanism is proposed, involving the Cu2O-templated and mediated nucleation and growth of Cu nanocrystals, followed by the PVP-directed electrostatic self-assembly of Cu nanocrystals. The synthesized Cu shows high oxidation resistance after stored in ambient environment for 90 d by self-passivation, wherein the dense oxidized external layer prevented further oxidation of Cu, unlike other antioxidative strategies. In addition, the structure became 2D flake after a simple ball-milling for 10 min of 2000r, thus forming a good conductive network at the temperature of 180 °C. Importantly, no obvious decline in the electrical performance after severe surface oxidation. Although the structure cannot offer excellent conductive performance, but it proposes a new solution for the balance of antioxidative capabilities and good sinterability in Cu nanomaterials, thus facilitating greater utilization of Cu-based conductive inks for emerging flexible electronic applications.

High-Quality CH3NH3PbI3 Films Obtained via a Pressure-Assisted Space-Confined Solvent-Engineering Strategy for Ultrasensitive Photodetectors.

High-quality organic-inorganic hybrid perovskite films are crucial for excellent performance of photoelectric devices. Herein, we demonstrate a pressure-assisted space-confined solvent-engineering strategy to grow highly oriented, pinhole-free thin films of CH3NH3PbI3 with large-scale crystalline grains, high smoothness, and crystalline fusion on grain boundaries. These single-crystalline grains vertically span the entire film thickness. Such a film feature dramatically reduces recombination loss and then improves the transport property of charge carriers in the films. Consequently, the photodetector devices, based on the high-quality CH3NH3PbI3 films, exhibit high photocurrent (105 µA under 671 nm laser with a power density of 20.6 mW/cm2 at 10 V), good stability, and, especially, an ultrahigh on/off ratio (Ilight/Idark > 2.2 × 104 under an incident light of 20.6 mW/cm2). These excellent performances indicate that the high-quality films will be potential candidates in other CH3NH3PbI3-based photoelectric devices.

Construction of 3D Skeleton for Polymer Composites Achieving a High Thermal Conductivity.

Owing to the growing heat removal issue in modern electronic devices, electrically insulating polymer composites with high thermal conductivity have drawn much attention during the past decade. However, the conventional method to improve through-plane thermal conductivity of these polymer composites usually yields an undesired value (below 3.0 Wm-1 K-1 ). Here, construction of a 3D phonon skeleton is reported composed of stacked boron nitride (BN) platelets reinforced with reduced graphene oxide (rGO) for epoxy composites by the combination of ice-templated and infiltrating methods. At a low filler loading of 13.16 vol%, the resulting 3D BN-rGO/epoxy composites exhibit an ultrahigh through-plane thermal conductivity of 5.05 Wm-1 K-1 as the best thermal-conduction performance reported so far for BN sheet-based composites. Theoretical models qualitatively demonstrate that this enhancement results from the formation of phonon-matching 3D BN-rGO networks, leading to high rates of phonon transport. The strong potential application for thermal management has been demonstrated by the surface temperature variations of the composites with time during heating and cooling.

Anticorrosive, Ultralight, and Flexible Carbon-Wrapped Metallic Nanowire Hybrid Sponges for Highly Efficient Electromagnetic Interference Shielding.

Metal-based materials with exceptional intrinsic conductivity own excellent electromagnetic interference (EMI) shielding performance. However, high density, corrosion susceptibility, and poor flexibility of the metal severely restrict their further applications in the areas of aircraft/aerospace, portable and wearable smart electronics. Herein, a lightweight, flexible, and anticorrosive silver nanowire wrapped carbon hybrid sponge (Ag@C) is fabricated and employed as ultrahigh efficiency EMI shielding material. The interconnected Ag@C hybrid sponges provide an effective way for electron transport, leading to a remarkable conductivity of 363.1 S m-1 and superb EMI shielding effectiveness of around 70.1 dB in the frequency range of 8.2-18 GHz, while the density is as low as 0.00382 g cm-3 , which are among the best performances for electrically conductive sponges/aerogels/foams by far. More importantly, the Ag@C sponge surprisingly exhibits super-hydrophobicity and strong corrosion resistance. In addition, the hybrid sponges possess excellent mechanical resilience even with a large strain (90% reversible compressibility) and an outstanding cycling stability, which is far better than the bare metallic aerogels, such as silver nanowire aerogels and copper nanowire foams. This strategy provides a facile methodology to fabricate lightweight, flexible, and anticorrosive metal-based sponge for highly efficient EMI shielding applications.

Advancements in Copper Nanowires: Synthesis, Purification, Assemblies, Surface Modification, and Applications.

Copper nanowires (CuNWs) are attracting a myriad of attention due to their preponderant electric conductivity, optoelectronic and mechanical properties, high electrocatalytic efficiency, and large abundance. Recently, great endeavors are undertaken to develop controllable and facile approaches to synthesize CuNWs with high dispersibility, oxidation resistance, and zero defects for future large-scale nano-enabled materials. Herein, this work provides a comprehensive review of current remarkable advancements in CuNWs. The Review starts with a thorough overview of recently developed synthetic strategies and growth mechanisms to achieve single-crystalline CuNWs and fivefold twinned CuNWs by the reduction of Cu(I) and Cu(II) ions, respectively. Following is a discussion of CuNW purification and multidimensional assemblies comprising films, aerogels, and arrays. Next, several effective approaches to protect CuNWs from oxidation are highlighted. The emerging applications of CuNWs in diverse fields are then focused on, with particular emphasis on optoelectronics, energy storage/conversion, catalysis, wearable electronics, and thermal management, followed by a brief comment on the current challenges and future research directions. The central theme of the Review is to provide an intimate correlation among the synthesis, structure, properties, and applications of CuNWs.

Electrospun N-Doped Hierarchical Porous Carbon Nanofiber with Improved Degree of Graphitization for High-Performance Lithium Ion Capacitor.

The lithium-ion capacitor (LIC) has been regarded as a promising device that combines the merits of lithium-ion batteries and supercapacitors, and that meets the requirements for both high energy and high power density. The development of advanced electrode materials is the key requirement. Herein, we report the bottom-up synthesis of activated carbon nanofiber (a-PANF) with a hierarchical porous structure and a high degree of graphitization. Electrospinning has been employed to prepare an interconnected fiber network with macropores, and ferric acetylacetonate has been introduced as both a mesopore-creating agent and a graphitic catalyst to increase the degree of graphitization. Furthermore, chemical activation enlarges the specific surface area by producing abundant micropores. Half-cell evaluation of the as-prepared a-PANF gave a discharge capacity of 80 mA h g-1 at 0.1 A g-1 within 2-4.5 V and no capacity fading after 1000 cycles at 2 A g-1 , which represents a significant improvement compared to conventional activated carbon (AC). Furthermore, an as-assembled LIC with a-PANF cathode and Fe3 O4 anode showed a superior energy density of 124.6 W h kg-1 at a specific power of 93.8 W kg-1 , which remained at 103.7 W h kg-1 at 4687.5 W kg-1 . This indicates promising application potential of a-PANF as an electrode material for efficient energy storage systems.

An Omni-Healable and Highly Sensitive Capacitive Pressure Sensor with Microarray Structure.

Capacitive pressure sensors with high flexibility, sensitivity, and excellent healable properties are desirable for a wide variety of applications, such as e-skin. However, implementing these characteristics onto a device presently remains a great challenge. In this work, a flexible pressure sensor with high sensitivity and strong healable properties has been developed based on healable polyurethane (HPU), silver nanowires and graphene. The HPU-based microstructured capacitive pressure sensor exhibited a high sensitivity of 1.9 kPa-1 (<3 kPa), a fast response time (<100 ms), low detection limit (10 Pa), and long-term durability (1000 cycles). Touch-finger and vocal-cord vibration detection have been demonstrated and exhibit a high sensitivity to both static and dynamic pressure. More notably, the entire pressure sensor including the dielectric layer and electrodes is omni-healable after complete separation. The prototype has experimentally shown tremendous potential for wearable, healable applications, such as healthcare monitoring and human-machine interfaces.

Processing and characterization of silver-filled conductive polysulfide sealants for aerospace applications.

Polysulfide (PS) rubbers have been widely used as high performance sealants to line or seal aircraft fuel tanks. However, safety concerns arise when electrostatic charges are built up due to the motion of flammable fuels. In this report, electrically conductive sealants were designed in order to dissipate these hazardous charges. Silver fillers with various sizes and surface coatings were incorporated into a polysulfide matrix to make conductive sealants. The low electrical conductivity of the sealants led to the assumption that unique filler-resin interactions occurred at their interfaces. To verify this assumption, various characterization methods were employed to investigate the chemical, thermal, morphological, electrical, and mechanical properties of the sealants. In addition, carbon fillers and other room temperature-cured polymer resins were used for comparative study. The systematic analysis revealed that the formation of coordination compounds at silver/PS interfaces could block electron conduction pathways between fillers. Based on the chemical understanding, post cure thermal annealing was utilized to break the coordinated bonds and restore high conductivity (>106 S m-1) of the sealants. Conductivity change as a function of annealing temperature and time was also explored to optimize processing conditions.

A facile and clean process for exfoliating MoS2 nanosheets assisted by a surface active agent in aqueous solution.

A facile, efficient and environmentally friendly process to exfoliate MoS2 is essentially critical to apply the obtained mono- and few-layer nanosheets in various electronic devices and sensors. Here we report a liquid phase exfoliation method for exfoliation of MoS2, which employs a surfactant of sodium dodecyl benzene sulfonate (SDBS) in water. The nonpolar benzene rings in SDBS can firmly bind to the MoS2 layer, facilitating the effective exfoliation of nanosheets in aqueous solution. It is found that the exfoliation efficiency and thickness of MoS2 nanosheets are related to the concentration of SDBS, and the mechanism was investigated. Defect free mono- and few-layer MoS2 nanosheets are obtained by controlling the amount of SDBS in solution, which exhibit stable dispersion in water over months, and it renders them as having great potential for solution-based device fabrication.

Fabricating and Controlling Silicon Zigzag Nanowires by Diffusion-Controlled Metal-Assisted Chemical Etching Method.

Silicon (Si) zigzag nanowires (NWs) have a great potential in many applications because of its high surface/volume ratio. However, fabricating Si zigzag NWs has been challenging. In this work, a diffusion-controlled metal-assisted chemical etching method is developed to fabricate Si zigzag NWs. By tailoring the composition of etchant to change its diffusivity, etching direction, and etching time, various zigzag NWs can be easily fabricated. In addition, it is also found that a critical length of NW (>1 µm) is needed to form zigzag nanowires. Also, the amplitude of zigzag increases as the location approaches the center of the substrate and the length of zigzag nanowire increases. It is also demonstrated that such zigzag NWs can help the silicon substrate for self-cleaning and antireflection. This method may provide a feasible and economical way to fabricate zigzag NWs and novel structures for broad applications.

Ultrafast Molecular Stitching of Graphene Films at the Ethanol/Water Interface for High Volumetric Capacitance.

Compact graphene film electrodes with a high ion-accessible surface area have the promising potential to realize high-density electrochemical energy storage (or high volumetric capacitance), which is vital for the development of flexible, portable, and wearable energy storage devices. Here, a novel, ultrafast strategy for stitching graphene sheets into films, in which p-phenylenediamine (PPD) molecules are uniformly intercalated between the graphene sheets, is simply constructed at the ethanol/water interface. Due to uniformly interlayer spacing (∼1.1 nm), good wettability, and an interconnected ion transport channel, the binder-free PPD-graphene film with a high packing density (1.55 g cm-3) delivers an ultrahigh volumetric capacitance (711 F cm-3 at a current density of 0.5 A g-1), high rate performance, high power and energy densities, and excellent cycling stability in aqueous electrolytes. This interfacial stitching strategy holds new promise for the future design of enhanced electrochemical energy-storage devices.

Controlling Kink Geometry in Nanowires Fabricated by Alternating Metal-Assisted Chemical Etching.

Kinked silicon (Si) nanowires (NWs) have many special properties that make them attractive for a number of applications, such as microfluidics devices, microelectronic devices, and biosensors. However, fabricating NWs with controlled three-dimensional (3D) geometry has been challenging. In this work, a novel method called alternating metal-assisted chemical etching is reported for the fabrication of kinked Si NWs with controlled 3D geometry. By the use of multiple etchants with carefully selected composition, one can control the number of kinks, their locations, and their angles by controlling the number of etchant alternations and the time in each etchant. The resulting number of kinks equals the number times the etchant is alternated, the length of each segment separated by kinks has a linear relationship with the etching time, and the kinking angle is related to the surface tension and viscosity of the etchants. This facile method may provide a feasible and economical way to fabricate novel silicon nanowires, nanostructures, and devices for broad applications.

Binary Synergistic Sensitivity Strengthening of Bioinspired Hierarchical Architectures based on Fragmentized Reduced Graphene Oxide Sponge and Silver Nanoparticles for Strain Sensors and Beyond.

Recently, stretchable electronics have been highly desirable in the Internet of Things and electronic skins. Herein, an innovative and cost-efficient strategy is demonstrated to fabricate highly sensitive, stretchable, and conductive strain-sensing platforms inspired by the geometries of a spiders slit organ and a lobsters shell. The electrically conductive composites are fabricated via embedding the 3D percolation networks of fragmentized graphene sponges (FGS) in poly(styrene-block-butadiene-block-styrene) (SBS) matrix, followed by an iterative process of silver precursor absorption and reduction. The slit- and scale-like structures and hybrid conductive blocks of FGS and Ag nanoparticles (NPs) provide the obtained FGS-Ag-NP-embedded composites with superior electrical conductivity of 1521 S cm-1 , high break elongation of 680%, a wide sensing range of up to 120% strain, high sensitivity of ≈107 at a strain of 120%, fast response time of ≈20 ms, as well as excellent reliability and stability of 2000 cycles. This huge stretchability and sensitivity is attributed to the combination of high stretchability of SBS and the binary synergistic effects of designed FGS architectures and Ag NPs. Moreover, the FGS/SBS/Ag composites can be employed as wearable sensors to detect the modes of finger motions successfully, and patterned conductive interconnects for flexible arrays of light-emitting diodes.