Multifunctional Conductive Hydrogel Composites with Nickel Nanowires and Liquid Metal Conductive Highways.

The dramatic growth of smart wearable electronics has generated a demand for conductive hydrogels due to their tunability, stimulus responsiveness, and multimodal sensing capabilities. However, the substantial trade-off between mechanical and electrical properties hinders their multifunctionality. Here, we report a double-network hydrogel composite that features a conductive "highway" constructed using magnetic-field-aligned nickel nanowires and liquid metal. The liquid metal fills the gaps between the aligned nickel nanowires. Such interconnected structures can form efficient conductive paths at low filler content, resulting in high conductivity (1.11 × 104 S/m) and mechanical compliance (Young's modulus, 89 kPa; toughness, 721 kJ/m3). When used as a wearable sensor, the hydrogel displays a high sensitivity and fast response for wireless motion detection and human-machine interaction. Furthermore, by exploiting its outstanding conductivity and electrical heating capacity, the hydrogel integrates electromagnetic shielding and thermal management functionalities. Owing to these all-around properties, our design offers a broader platform for expanding hydrogel applications.

Electrospun carbon-based nanomaterials for next-generation potassium batteries.

Rechargeable potassium (K) batteries that are of low cost, with high energy densities and long cycle lives have attracted tremendous interest in affordable and large-scale energy storage. However, the large size of the K-ion leads to sluggish reaction kinetics and causes a large volume variation during the ion insertion/extraction processes, thus hindering the utilization of active electrode materials, triggering a serious structural collapse, and deteriorating the cycling performance. Therefore, the exploration of suitable materials/hosts that can reversibly and sustainably accommodate K-ions and host K metals are urgently needed. Electrospun carbon-based materials have been extensively studied as electrode/host materials for rechargeable K batteries owing to their designable structures, tunable composition, hierarchical pores, high conductivity, large surface areas, and good flexibility. Here, we present the recent developments in electrospun CNF-based nanomaterials for various K batteries (e.g., K-ion batteries, K metal batteries, K-chalcogen batteries), including their fabrication methods, structural modulation, and electrochemical performance. This Feature Article is expected to offer guidelines for the rational design of novel electrospun electrodes for the next-generation K batteries.

Solvent-Exchange-Assisted Wet Annealing: A New Strategy for Superstrong, Tough, Stretchable, and Anti-Fatigue Hydrogels.

Hydrogels are widely used in tissue engineering, soft robots, wearable electronics, etc. However, it remains a great challenge to develop hydrogels possessing simultaneously high strength, large stretchability, great fracture energy, and good fatigue threshold to suit different applications. Herein, a novel solvent-exchange-assisted wet-annealing strategy is proposed to prepare high performance poly(vinyl alcohol) hydrogels by extensively tuning the macromolecular chain movement and optimizing the polymer network. The reinforcing and toughening mechanisms are found to be "macromolecule crystallization and entanglement". These hydrogels have large tensile strengths up to 11.19 ± 0.27 MPa and extremely high fracture strains of 1879 ± 10%. In addition, the fracture energy and fatigue threshold can reach as high as 25.39 ± 6.64 kJ m-2 and ≈1233 J m-2 , respectively. These superb mechanical properties compare favorably to those of other tough hydrogels, organogels, and even natural tendons and synthetic rubbers. This work provides a new and effective method to fabricate superstrong, tough, stretchable, and anti-fatigue hydrogels with potential applications in artificial tendons and ligaments.

Flexible, Highly Thermally Conductive and Electrically Insulating Phase Change Materials for Advanced Thermal Management of 5G Base Stations and Thermoelectric Generators.

Thermal management has become a crucial problem for high-power-density equipment and devices. Phase change materials (PCMs) have great prospects in thermal management applications because of their large capacity of heat storage and isothermal behavior during phase transition. However, low intrinsic thermal conductivity, ease of leakage, and lack of flexibility severely limit their applications. Solving one of these problems often comes at the expense of other performance of the PCMs. In this work, we report core-sheath structured phase change nanocomposites (PCNs) with an aligned and interconnected boron nitride nanosheet network by combining coaxial electrospinning, electrostatic spraying, and hot-pressing. The advanced PCN films exhibit an ultrahigh thermal conductivity of 28.3 W m-1 K-1 at a low BNNS loading (i.e., 32 wt%), which thereby endows the PCNs with high enthalpy (> 101 J g-1), outstanding ductility (> 40%) and improved fire retardancy. Therefore, our core-sheath strategies successfully balance the trade-off between thermal conductivity, flexibility, and phase change enthalpy of PCMs. Further, the PCNs provide powerful cooling solutions on 5G base station chips and thermoelectric generators, displaying promising thermal management applications on high-power-density equipment and thermoelectric conversion devices.

Formation of Head/Tail-to-Body Charged Domain Walls by Mechanical Stress.

Domain walls (DWs) in ferroelectric materials are interfaces that separate domains with different polarizations. Charged domain walls (CDWs) and neutral domain walls are commonly classified depending on the charge state at the DWs. CDWs are particularly attractive as they are configurable elements, which can enhance field susceptibility and enable functionalities such as conductance control. However, it is difficult to achieve CDWs in practice. Here, we demonstrate that applying mechanical stress is a robust and reproducible approach to generate CDWs. By mechanical compression, CDWs with a head/tail-to-body configuration were introduced in ultrathin BaTiO3, which was revealed by in-situ transmission electron microscopy. Finite element analysis shows strong strain fluctuation in ultrathin BaTiO3 under compressive mechanical stress. Molecular dynamics simulations suggest that the strain fluctuation is a critical factor in forming CDWs. This study provides insight into ferroelectric DWs and opens a pathway to creating CDWs in ferroelectric materials.

Hierarchically porous composite fabrics with ultrahigh metal-organic framework loading for zero-energy-consumption heat dissipation.

The long-term safe operation of high-power equipment and integrated electronic devices requires efficient thermal management, which in turn increases the energy consumption further. Hence, the sustainable development of our society needs advanced thermal management with low, even zero, energy consumption. Harvesting water from the atmosphere, followed by moisture desorption to dissipate heat, is an efficient and feasible approach for zero-energy-consumption thermal management. However, current methods are limited by the low absorbance of water, low water vapor transmission rate (WVTR) and low stability, thus resulting in low thermal management capability. In this study, we report an innovative electrospinning method to process hierarchically porous metal-organic framework (MOF) composite fabrics with high-efficiency and zero-energy-consumption thermal management. The composite fabrics are highly loaded with MOF (75 wt%) and their WVTR value can be up to 3138 g m-2 d-1. The composite fabrics also exhibit stable microstructure and performance. Under a conventional environment (30 ℃, 60% relative humidity), the composite fabrics adsorb water vapor for regeneration within 1.5 h to a saturated value Wsat of 0.614 g g-1, and a corresponding equivalent enthalpy of 1705.6 J g-1. In the thermal management tests, the composite fabrics show a strong cooling capability and significantly improve the performance of thermoelectric devices, portable storage devices and wireless chargers. These results suggest that hierarchically porous MOF composite fabrics are highly promising for thermal management of intermittent-operation electronic devices.

Advances on Thermally Conductive Epoxy-Based Composites as Electronic Packaging Underfill Materials-A Review.

The integrated circuits industry has been continuously producing microelectronic components with ever higher integration level, packaging density, and power density, which demand more stringent requirements for heat dissipation. Electronic packaging materials are used to pack these microelectronic components together, help to dissipate heat, redistribute stresses, and protect the whole system from the environment. They serve an important role in ensuring the performance and reliability of the electronic devices. Among various packaging materials, epoxy-based underfills are often employed in flip-chip packaging. However, widely used capillary underfill materials suffer from their low thermal conductivity, unable to meet the growing heat dissipation required of next-generation IC chips with much higher power density. Many strategies have been proposed to improve the thermal conductivity of epoxy, but its application as underfill materials with complex performance requirements is still difficult. In fact, optimizing the combined thermal-electrical-mechanical-processing properties of underfill materials for flip-chip packaging remains a great challenge. Herein, state-of-the-art advances that have been made to satisfy the key requirements of capillary underfill materials are reviewed. Based on these studies, the perspectives for designing high-performance underfill materials with novel microstructures in electronic packaging for high-power density electronic devices are provided.

Manipulating ferroelectric behaviors via electron-beam induced crystalline defects.

Ferroelectric nanoplates are attractive for applications in nanoelectronic devices. Defect engineering has been an effective way to control and manipulate ferroelectric properties in nanoscale devices. Defects can act as pinning centers for ferroelectric domain wall motion, altering the switching properties and domain dynamics of ferroelectrics. However, there is a lack of detailed investigation on the interactions between defects and domain walls in ferroelectric nanoplates due to the limitation of previous characterization techniques, which impedes the development of defect engineering in ferroelectric nanodevices. In this study, we applied in situ biasing transmission electron microscopy to explore how dislocation loops, which were judiciously introduced into barium titanate nanoplates via electron beam irradiation, affect the motion of ferroelectric domain walls. The results show that the motion was dramatically suppressed by these localized defects, because of the local strain fields induced by the defects. The pinning effect can be further enhanced by multiple domain walls embedded with defect arrays. These results indicate the possibility of manipulating domain switching in ferroelectric nanoplates via the electron beam.

Spider Web-Inspired Graphene Skeleton-Based High Thermal Conductivity Phase Change Nanocomposites for Battery Thermal Management.

Phase change materials (PCMs) can be used for efficient thermal energy harvesting, which has great potential for cost-effective thermal management and energy storage. However, the low intrinsic thermal conductivity of polymeric PCMs is a bottleneck for fast and efficient heat harvesting. Simultaneously, it is also a challenge to achieve a high thermal conductivity for phase change nanocomposites at low filler loading. Although constructing a three-dimensional (3D) thermally conductive network within PCMs can address these problems, the anisotropy of the 3D framework usually leads to poor thermal conductivity in the direction perpendicular to the alignment of fillers. Inspired by the interlaced structure of spider webs in nature, this study reports a new strategy for fabricating highly thermally conductive phase change composites (sw-GS/PW) with a 3D spider web (sw)-like structured graphene skeleton (GS) by hydrothermal reaction, radial freeze-casting and vacuum impregnation in paraffin wax (PW). The results show that the sw-GS hardly affected the phase transformation behavior of PW at low loading. Especially, sw-GS/PW exhibits both high cross-plane and in-plane thermal conductivity enhancements of ~ 1260% and ~ 840%, respectively, at an ultra-low filler loading of 2.25 vol.%. The thermal infrared results also demonstrate that sw-GS/PW possessed promising applications in battery thermal management.

Ultrafast Flame-Induced Pyrolysis of Poly(dimethylsiloxane) Foam Materials toward Exceptional Superhydrophobic Surfaces and Reliable Mechanical Robustness.

Superhydrophobic surfaces are imperative in flexible polymer foams for diverse applications; however, traditional surface coatings on soft skeletons are often fragile and can hardly endure severe deformation, making them unstable and highly susceptible to cyclic loadings. Therefore, it remains a great challenge to balance their mutual exclusiveness of mechanical robustness and surface water repellency on flexible substrates. Herein, we describe how robust superhydrophobic surfaces on soft poly(dimethylsiloxane) (PDMS) foams can be achieved using an extremely simple, ultrafast, and environmentally friendly flame scanning strategy. The ultrafast flame treatment (1-3 s) of PDMS foams produces microwavy and nanosilica rough structures bonded on the soft skeletons, forming robust superhydrophobic surfaces (i.e., water contact angles (WCAs) > 155° and water sliding angles (WSAs) < 5°). The rough surface can be effectively tailored by simply altering the flame scanning speed (2.5-15.0 cm/s) to adjust the thermal pyrolysis of the PDMS molecules. The optimized surfaces display reliable mechanical robustness and excellent water repellency even after 100 cycles of compression of 60% strain, stretching of 100% strain, and bending of 90° and hostile environmental conditions (including acid/salt/alkali conditions, high/low temperatures, UV aging, and harsh cyclic abrasion). Moreover, such flame-induced superhydrophobic surfaces are easily peeled off from ice and can be healable even after severe abrasion cycles. Clearly, the flame scanning strategy provides a facile and versatile approach for fabricating mechanically robust and surface superhydrophobic PDMS foam materials for applications in complex conditions.

Direct observation of nanoscale dynamics of ferroelectric degradation.

Failure of polarization reversal, i.e., ferroelectric degradation, induced by cyclic electric loadings in ferroelectric materials, has been a long-standing challenge that negatively impacts the application of ferroelectrics in devices where reliability is critical. It is generally believed that space charges or injected charges dominate the ferroelectric degradation. However, the physics behind the phenomenon remains unclear. Here, using in-situ biasing transmission electron microscopy, we discover change of charge distribution in thin ferroelectrics during cyclic electric loadings. Charge accumulation at domain walls is the main reason of the formation of c domains, which are less responsive to the applied electric field. The rapid growth of the frozen c domains leads to the ferroelectric degradation. This finding gives insights into the nature of ferroelectric degradation in nanodevices, and reveals the role of the injected charges in polarization reversal.

Li metal deposition and stripping in a solid-state battery via Coble creep.

Solid-state lithium metal batteries require accommodation of electrochemically generated mechanical stress inside the lithium: this stress can be1,2 up to 1 gigapascal for an overpotential of 135 millivolts. Maintaining the mechanical and electrochemical stability of the solid structure despite physical contact with moving corrosive lithium metal is a demanding requirement. Using in situ transmission electron microscopy, we investigated the deposition and stripping of metallic lithium or sodium held within a large number of parallel hollow tubules made of a mixed ionic-electronic conductor (MIEC). Here we show that these alkali metals-as single crystals-can grow out of and retract inside the tubules via mainly diffusional Coble creep along the MIEC/metal phase boundary. Unlike solid electrolytes, many MIECs are electrochemically stable in contact with lithium (that is, there is a direct tie-line to metallic lithium on the equilibrium phase diagram), so this Coble creep mechanism can effectively relieve stress, maintain electronic and ionic contacts, eliminate solid-electrolyte interphase debris, and allow the reversible deposition/stripping of lithium across a distance of 10 micrometres for 100 cycles. A centimetre-wide full cell-consisting of approximately 1010 MIEC cylinders/solid electrolyte/LiFePO4-shows a high capacity of about 164 milliampere hours per gram of LiFePO4, and almost no degradation for over 50 cycles, starting with a 1× excess of Li. Modelling shows that the design is insensitive to MIEC material choice with channels about 100 nanometres wide and 10-100 micrometres deep. The behaviour of lithium metal within the MIEC channels suggests that the chemical and mechanical stability issues with the metal-electrolyte interface in solid-state lithium metal batteries can be overcome using this architecture.

Fiber-in-Tube Design of Co9 S8 -Carbon/Co9 S8 : Enabling Efficient Sodium Storage.

The sodium-ion battery is a promising battery technology owing to its low price and high abundance of sodium. However, the sluggish kinetics of sodium ion makes it hard to achieve high-rate performance, therefore impairing the power density. In this work, a fiber-in-tube Co9 S8 -carbon(C)/Co9 S8 is designed with fast sodiation kinetics. The experimental and simulation analysis show that the dominating capacitance mechanism for the high Na-ion storage performance is due to abundant grain boundaries, three exposed layer interfaces, and carbon wiring in the design. As a result, the fiber-in-tube hybrid anode shows a high specific capacity of 616 mAh g-1 after 150 cycles at 0.5 A g-1 . At 1 A g-1 , a capacity of ca. 451 mAh g-1 can be achieved after 500 cycles. More importantly, a high energy density of 779 Wh kg-1 and power density of 7793 W kg-1 can be obtained simultaneously.

Spider-Web-Inspired Stretchable Graphene Woven Fabric for Highly Sensitive, Transparent, Wearable Strain Sensors.

Advanced wearable strain sensors with high sensitivity and stretchability are an essential component of flexible and soft electronic devices. Conventional metal- and semiconductor-based strain sensors are rigid, fragile, and opaque, restricting their applications in wearable electronics. Graphene-based percolative structures possess high flexibility and transparency but lack high sensitivity and stretchability. Inspired by the highly flexible spider web architecture, we propose semitransparent, ultrasensitive, and wearable strain sensors made from an elastomer-filled graphene woven fabric (E-GWF) for monitoring human physiological signals. The highly flexible elastomer microskeleton and the hierarchical structure of a graphene tube offer the strain sensor with both excellent sensing and switching capabilities. Two different types of E-GWF sensors, including freestanding E-GWF and E-GWF/polydimethylsiloxane (PDMS) composites, are developed. When their structure is controlled and optimized, the E-GWF strain sensors simultaneously exhibit extraordinary characteristics, such as a high gauge factor (70 at 10% strain, which ascends to 282 at 20%) in respect to other semitransparent or transparent strain sensors, a broad sensing range up to 30%, and excellent linearity. The E-GWF/PDMS composite sensor shows a unique reversible switching behavior at a high strain level of 30-50%, making it a suitable material for fast and reversible strain switching required in many early warning systems. With a view to real-world applications of these sensors and switches, we demonstrate human motion detection and switch controls of light-emitting-diode lamps and liquid-crystal-display circuits. Their unique structure and capabilities can find a wide range of practical applications, such as health monitoring, medical diagnosis, early warning systems for structural failure, and wearable displays.

Scalable Approach to Construct Self-Assembled Graphene-Based Films with An Ordered Structure for Thermal Management.

Large-area bulk oxidized cellulose nanocrystal (OCNC)/graphene nanocomposites with highly oriented structures were produced through a straightforward, cost-effective large-scale evaporation-induced self-assembly process followed by thermal curing. Well-aligned nano-sized graphene layers were evident and separated by the OCNC planar layers, which facilitate highly interconnected and continuous thermal transport parallel to the alignment. Hence, the laminated graphene-based nanocomposites possess an excellent in-plane thermal conductivity of 25.66 W/m K and a thermal conductivity enhancement (η) of 7235% with only a 4.1 vol % graphene loading. This value is the highest recorded among all laminated composite films with <70 wt % filler content reported to date. Using this design strategy, other large-area aligned composites with other functional nanomaterials, already in large-scale production, can be made for use in a wide range of applications.

Graphene/Boron Nitride-Polyurethane Microlaminates for Exceptional Dielectric Properties and High Energy Densities.

Hexagonal boron nitride (h-BN) has tremendous potential for dielectric energy storage by rationally assembling with graphene. We report the fabrication of microlaminate composites consisting of alternating reduced graphene oxide (rGO) and h-BN nanosheets embedded in a polyurethane (PU) matrix using a novel, two-step bidirectional freeze casting process. Porous, highly-aligned rGO-PU aerogels having ultrahigh dielectric constants with relatively high dielectric losses and low dielectric strengths are fabricated by initial freeze casting. The losses are suppressed, whereas the dielectric strengths are restored by assembling the porous rGO-PU skeleton with electrically insulating BN-PU tunneling barrier layers in the second freeze casting routine. The ligaments bridging the conductive rGO-PU layers are effectively removed by the BN-PU barrier layers, eliminating the current leakage in the transverse direction. The resultant rGO-PU/BN-PU microlaminate composites deliver a remarkable dielectric constant of 1084 with a low dielectric loss of 0.091 at 1 kHz. By virtue of synergy arising from both the rGO-PU layers with a high dielectric constant and the BN-PU barrier layers with a high dielectric strength, the microlaminate composites present a maximum energy density of 22.7 J/cm3, 44 folds of the neat rGO-PU composite acting alone. The promising overall dielectric performance based on a microlaminate structure offers a new insight into the development of next-generation dielectric materials.

Ultralow-Carbon Nanotube-Toughened Epoxy: The Critical Role of a Double-Layer Interface.

Understanding the chemistry and structure of interfaces within epoxy resins is important for studying the mechanical properties of nanofiller-filled nanocomposites as well as for developing high-performance polymer nanocomposites. Despite the intensive efforts to construct nanofiller/matrix interfaces, few studies have demonstrated an enhanced stress-transferring efficiency while avoiding unfavorable deformation due to undesirable interface fractures. Here, we report an optimized method to prepare epoxy-based nanocomposites whose interfaces are chemically modulated by poly(glycidyl methacrylate)-block-poly(hexyl methacrylate) (PGMA-b-PHMA)-functionalized multiwalled carbon nanotubes (bc@fMWNTs) and also offer a fundamental explanation of crack growth behavior and the toughening mechanism of the resulting nanocomposites. The presence of block copolymers on the surface of the MWNT results in a promising double-layered interface, in which (1) the outer-layered PGMA segment provides good dispersion in and strong interface bonding with the epoxy matrix, which enhances load transfer efficiency and debonding stress, and (2) the interlayered rubbery PHMA segment around the MWNT provides the maximum removable space for nanotubes as well as triggering cavitation while promoting local plastic matrix deformation, for example, shear banding to dissipate fracture energy. An outstanding toughening effect is achieved with only a 0.05 wt % carbon nanotube loading with the bc@fMWNT, that is, needing only a 20-times lower loading to obtain improvements in fracture toughness comparable to epoxy-based nanocomposites. The enhancements of their corresponding ultimate mode-I fracture toughnesses and fracture energies are 4 times higher than those of pristine MWNT-filled epoxy. These results demonstrate that a MWNT/epoxy interface could be optimized by changing the component structure of grafted modifiers, thereby facilitating the transfer of both mechanical load and energy dissipation across the nanofiller/matrix interface. This work provides a new route for the rational design and development of polymer nanocomposites with exceptional mechanical performance.

Superior flame retardancy and smoke suppression of epoxy-based composites with phosphorus/nitrogen co-doped graphene.

Phosphorus and/or nitrogen doping is an effective method of improving the physical and chemical properties of reduced graphene oxide (rGO). In this work, phosphorus and nitrogen co-doped rGO (PN-rGO), synthesized using a scalable hydrothermal and microwave process, was used as an additive to improve the flame retardancy of epoxy resin (EP) for the first time. Chemical structure and morphology characterization confirmed that the nitrogen and phosphorus atoms were doped into the graphite lattice adopting pyrrolic-N, pyridinic-N, quaternary-N and pyrophosphate and metaphosphate forms. Doping increased the oxidization resistance of rGO and the thermal-oxidative stability of its composites' char, while also improving the catalytic charring ability of polymer. Both effects resulted in the formation of a stable char protective layer during burning and to a significant improvement in flame retardation and smoke suppression in the final composites. The peak heat release rate (PHRR), total heat release (THR) and total smoke production (TSP) for the EP-based composite (containing 5 wt% PN-rGO) decreased by 30.9%, 29.3% and 51.3%, respectively, compared to neat EP. Our work has produced a promising graphene-based flame retardant additive for the mass production of high-performance composites, also expended the application of heteroatom-doped graphene.

Efficient Flame Detection and Early Warning Sensors on Combustible Materials Using Hierarchical Graphene Oxide/Silicone Coatings.

Design and development of smart sensors for rapid flame detection in postcombustion and early fire warning in precombustion situations are critically needed to improve the fire safety of combustible materials in many applications. Herein, we describe the fabrication of hierarchical coatings created by assembling a multilayered graphene oxide (GO)/silicone structure onto different combustible substrate materials. The resulting coatings exhibit distinct temperature-responsive electrical resistance change as efficient early warning sensors for detecting abnormal high environmental temperature, thus enabling fire prevention below the ignition temperature of combustible materials. After encountering a flame attack, we demonstrate extremely rapid flame detection response in 2-3 s and excellent flame self-extinguishing retardancy for the multilayered GO/silicone structure that can be synergistically transformed to a multiscale graphene/nanosilica protection layer. The hierarchical coatings developed are promising for fire prevention and protection applications in various critical fire risk and related perilous circumstances.

Super-hydrophobic coatings based on non-solvent induced phase separation during electro-spraying.

HYPOTHESIS: The polymer solution concentration determines whether electrospinning or electro-spraying occurs, while the addition of the non-solvent into the polymer solution strongly influences the surface morphology of the obtained products. Both smooth and porous surfaces of the electro-sprayed microspheres can be harvested by choosing different non-solvent and its amount as well as incorporating polymeric additives. EXPERIMENTS: The influences of the solution concentration, weight ratio between the non-solvent and the copolymer, and the polymeric additives on the surface morphology and the wettability of the electro-sprayed products were systematically studied. FINDINGS: Surface pores and/or asperities on the microsphere surface were mainly caused by the non-solvent induced phase separation (NIPS) and subsequent evaporation of the non-solvent during electro-spraying. With increasing polymer solution concentration, the microsphere was gradually changed to the bead-on-string geometry and finally to a nanofiber form, leading to a sustained decrease of the contact angle (CA). It was found that the substrate coatings derived from the microspheres possessing hierarchical surface pores or dense asperities had high surface roughness and super-hydrophobicity with CAs larger than 150° while sliding angles smaller than 10°; but coatings composed of microspheres with smooth surfaces gave relatively low CAs.