Inorganic Polymer Micropillar‐Based Solution Shearing of Large‐Area Organic Semiconductor Thin Films with Pillar‐Size‐Dependent Crystal Size

It is demonstrated that the crystal size of small‐molecule organic semiconductors can be controlled during solution shearing by tuning the shape and dimensions of the micropillars on the blade. Increasing the size and spacing of the rectangular pillars increases the crystal size, resulting in higher thin‐film mobility. This phenomenon is attributed as the microstructure changing the degree and density of the meniscus line curvature, thereby controlling the nucleation process. The use of allylhybridpolycarbosilane (AHPCS), an inorganic polymer, is also demonstrated as the microstructured blade for solution shearing, which has high resistance to organic solvents, can easily be microstructured via molding, and is flexible and durable. Finally, it is shown that solution shearing can be performed on a curved surface using a curved blade. These demonstrations bring solution shearing closer to industrial applications and expand its applicability to various printed flexible electronics.     

Laser‐Ignited Relay‐Domino‐Like Reactions in Graphene Oxide/CL‐20 Films for High‐Temperature Pulse Preparation of Bi‐Layered Photothermal Membranes

Light‐ignited combustions have been proposed for a variety of industrial and scientific applications. They suffer, however, from ultrahigh light ignition thresholds and poor self‐propagating combustion of typical high‐energy density materials, e.g., 2,4,6,8,10,12‐(hexanitrohexaaza)cyclododecane (CL‐20). Here, reported is that both light ignition and combustion performance of CL‐20 are greatly enhanced by embedding ε‐CL‐20 particles in a graphene oxide (GO) matrix. The GO matrix yields a drastic temperature rise that is sufficient to trigger the combustion of GO/CL‐20 under low laser irradiation (35.6 mJ) with only 6 wt% of GO. The domino‐like reduction‐combustion of the GO matrix can serve as a relay and deliver the decomposition‐combustion of CL‐20 to its neighbor sites, forming a relay‐domino‐like reaction. In particular, a synergistic reaction between GO and CL‐20 occurrs, facilitating more energy release of the GO/CL‐20 composite. The novel relay‐domino‐like reaction coupled with the synergistic reaction of CL‐20 and GO results in a deflagration of the material, which generates a high‐temperature pulse (HTP) that can be guided to produce advanced functional materials. As a proof of concept, a bi‐layered photothermal membrane is prepared by HTP treatment in an extremely simple and fast way, which can serve as a model architecture for efficient interfacial water evaporation.     

Synthetic Multifunctional Graphene Composites with Reshaping and Self‐Healing Features via a Facile Biomineralization‐Inspired Process

Since graphene is a type of 2D carbon material with excellent mechanical, electrical, thermal, and optical properties, the efficient preparation of graphene macroscopic assemblies is significant in the potentially large‐scale application of graphene sheets. Conventional preparation methods of graphene macroscopic assemblies need strict conditions, and, once formed, the assemblies cannot be edited, reshaped, or recycled. Herein, inspired by the biomineralization process, a feasible approach of shapeable, multimanipulatable, and recyclable gel‐like composite consisting of graphene oxide/poly(acrylic acid)/amorphous calcium carbonate (GO‐PAA‐ACC) is designed. This GO‐PAA‐ACC material can be facilely synthesized at room temperature with a cross‐linking network structure formed during the preparation process. Remarkably, it is stretchable, malleable, self‐healable, and easy to process in the wet state, but tough and rigid in the dried state. In addition, these two states can be readily switched by adjusting the water content, which shows recyclability and can be used for 3D printing to form varied architectures. Furthermore, GO‐PAA‐ACC can be functionalized or processed to meet a variety of specific application requirements (e.g., energy‐storage, actuators). The preparation method of GO‐PAA‐ACC composite in this work also provides a novel strategy for the versatile macroscopic assembly of other materials, which is low‐cost, efficient, and convenient for broad application.     

Composite Microgels Created by Complexation between Polyvinyl Alcohol and Graphene Oxide in Compressed Double‐Emulsion Drops

Microgels, microparticles made of hydrogels, show fast diffusion kinetics and high reconfigurability while maintaining the advantages of hydrogels, being useful for various applications. Here, presented is a new microfluidic strategy for producing polymer‐graphene oxide (GO) composite microgels without chemical cues or a temperature swing for gelation. As a main component of microgels, polymers that are able to form hydrogen bonds, such as polyvinyl alcohol (PVA), are used. In the mixture of PVA and GO, GO is tethered by PVA through hydrogen bonding. When the mixture is rapidly concentrated in the core of double‐emulsion drops by osmotic‐pressure‐driven water pumping, PVA‐tethered GO sheets form a nematic phase with a planar alignment. In addition, the GO sheets are linked by additional hydrogen bonds, leading to a sol–gel transition. Therefore, the PVA–GO composite remains undissolved when it is directly exposed to water by oil‐shell rupture. These composite microgels can be also produced using poly(ethylene oxide) or poly(acrylic acid), instead of PVA. In addition, the microgels can be functionalized by incorporating other polymers in the presence of the hydrogel‐forming polymers. It is shown that the multicomponent microgels made from a mixture of polyacrylamide, PVA, and GO show an excellent adsorption capacity for impurities.     

Elevated‐Temperature 3D Printing of Hybrid Solid‐State Electrolyte for Li‐Ion Batteries

While 3D printing of rechargeable batteries has received immense interest in advancing the next generation of 3D energy storage devices, challenges with the 3D printing of electrolytes still remain. Additional processing steps such as solvent evaporation were required for earlier studies of electrolyte fabrication, which hindered the simultaneous production of electrode and electrolyte in an all‐3D‐printed battery. Here, a novel method is demonstrated to fabricate hybrid solid‐state electrolytes using an elevated‐temperature direct ink writing technique without any additional processing steps. The hybrid solid‐state electrolyte consists of solid poly(vinylidene fluoride‐hexafluoropropylene) matrices and a Li⁺‐conducting ionic‐liquid electrolyte. The ink is modified by adding nanosized ceramic fillers to achieve the desired rheological properties. The ionic conductivity of the inks is 0.78 × 10 ^?3 S cm^?1. Interestingly, a continuous, thin, and dense layer is discovered to form between the porous electrolyte layer and the electrode, which effectively reduces the interfacial resistance of the solid‐state battery. Compared to the traditional methods of solid‐state battery assembly, the directly printed electrolyte helps to achieve higher capacities and a better rate performance. The direct fabrication of electrolyte from printable inks at an elevated temperature will shed new light on the design of all‐3D‐printed batteries for next‐generation electronic devices.     

Fabrication of Millimeter‐Long Carbon Tubular Nanostructures Using the Self‐Rolling Process Inherent in Elastic Protein Layers

Millimeter‐long conducting fibers can be fabricated from carbon nanomaterials via a simple method involving the release of a prestrained protein layer. This study shows how a self‐rolling process initiated by polymerization of a micropatterned layer of fibronectin (FN) results in the production of carbon nanomaterial‐based microtubular fibers. The process begins with deposition of carbon nanotube (CNT) or graphene oxide (GO) particles on the FN layer. Before polymerization, particles are discrete and nonconducting, but after polymerization the carbon materials become entangled to form an interconnected conducting network clad by FN. Selective removal of FN using high‐temperature combustion yields freestanding CNT or reduced GO microtubular fibers. The properties of these fibers are characterized using atomic force microscopy and Raman spectroscopy. The data suggest that this method may provide a ready route to rapid design and fabrication of aligned biohybrid nanomaterials potentially useful for future electronic applications.     

3D Printed High‐Performance Lithium Metal Microbatteries Enabled by Nanocellulose

Batteries constructed via 3D printing techniques have inherent advantages including opportunities for miniaturization, autonomous shaping, and controllable structural prototyping. However, 3D‐printed lithium metal batteries (LMBs) have not yet been reported due to the difficulties of printing lithium (Li) metal. Here, for the first time, high‐performance LMBs are fabricated through a 3D printing technique using cellulose nanofiber (CNF), which is one of the most earth‐abundant biopolymers. The unique shear thinning properties of CNF gel enables the printing of a LiFePO₄ electrode and stable scaffold for Li. The printability of the CNF gel is also investigated theoretically. Moreover, the porous structure of the CNF scaffold also helps to improve ion accessibility and decreases the local current density of Li anode. Thus, dendrite formation due to uneven Li plating/stripping is suppressed. A multiscale computational approach integrating first‐principle density function theory and a phase‐field model is performed and reveals that the porous structures have more uniform Li deposition. Consequently, a full cell built with a 3D‐printed Li anode and a LiFePO₄ cathode exhibits a high capacity of 80 mA h g^?1 at a charge/discharge rate of 10 C with capacity retention of 85% even after 3000 cycles.     

Micrometer‐Thick Graphene Oxide–Layered Double Hydroxide Nacre‐Inspired Coatings and Their Properties

Robust, functional, and flame retardant coatings are attractive in various fields such as building construction, food packaging, electronics encapsulation, and so on. Here, strong, colorful, and fire‐retardant micrometer‐thick hybrid coatings are reported, which can be constructed via an enhanced layer‐by‐layer assembly of graphene oxide (GO) nanosheets and layered double hydroxide (LDH) nanoplatelets. The fabricated GO–LDH hybrid coatings show uniform nacre‐like layered structures that endow them good mechanic properties with Young's modulus of ≈18 GPa and hardness of ≈0.68 GPa. In addition, the GO–LDH hybrid coatings exhibit nacre‐like iridescence and attractive flame retardancy as well due to their well‐defined 2D microstructures. This kind of nacre‐inspired GO–LDH hybrid thick coatings will be applied in various fields in future due to their high strength and multifunctionalities.     

“All‐in‐One” Gel System for Whole Procedure of Stem‐Cell Amplification and Tissue Engineering

Microsphere (MS)‐based systems provides great advantages for cell expansion and transplantation due to their high surface‐to‐volume ratio and biomimetic environment. However, a MS‐based system that includes cell attachment, proliferation, passage, harvest, cryopreservation, and tissue engineering together has not been realized yet. An “all‐in‐one” gel MS‐based system is established for human adipose‐derived mesenchymal stem cells (hADSCs), realizing real 3D culture with enhanced expansion efficiency and simplified serial cell culture operations, and construction of macrotissues with uniform cell distribution and specific function. A 3D digital light‐processing technology is developed to fabricate gel MSs in an effective way. The printed MSs present a suitable environment with rough surface architecture and the mechanical properties of soft tissues, leading to high cell viability, attachment, proliferation, activity, and differentiation potential. Further, convenient standard operation procedures, including cell passage, detachment, and cryopreservation, are established for cell culture on the gel MSs. Finally, hADSCs‐loaded gel MSs form macrotissues through a “bottom‐up” approach, which demonstrates the potential applications for tissue engineering. These findings exhibit the feasibility and beauty of “all‐in‐one” stem cell culture and tissue engineering system.     

A High‐Rate and Stable Quasi‐Solid‐State Zinc‐Ion Battery with Novel 2D Layered Zinc Orthovanadate Array

Zinc‐ion batteries are under current research focus because of their uniqueness in low cost and high safety. However, it is still desirable to improve the rate performance by improving the Zn²⁺ (de)intercalation kinetics and long‐cycle stability by eliminating the dendrite formation problem. Herein, the first paradigm of a high‐rate and ultrastable flexible quasi‐solid‐state zinc‐ion battery is constructed from a novel 2D ultrathin layered zinc orthovanadate array cathode, a Zn array anode supported by a conductive porous graphene foam, and a gel electrolyte. The nanoarray structure for both electrodes assures the high rate capability and alleviates the dendrite growth. The flexible Zn‐ion battery has a depth of discharge of ≈100% for the cathode and 66% for the anode, and delivers an impressive high‐rate of 50 C (discharge in 60 s), long‐term durability of 2000 cycles at 20 C, and unprecedented energy density ≈115 Wh kg^?1, together with a peak power density ≈5.1 kW kg^?1 (calculation includes masses of cathode, anode, and current collectors). First principles calculations and quantitative kinetics analysis show that the high‐rate and stable properties are correlated with the 2D fast ion‐migration pathways and the introduced intercalation pseudocapacitance.     

Super Moisture‐Absorbent Gels for All‐Weather Atmospheric Water Harvesting

Atmospheric water harvesting (AWH)—producing fresh water via collecting moisture from air—enables sustainable water delivery without geographical and hydrologic limitations. However, the fundamental design principle to prepare materials that can convert the water vapor in the air to collectible liquid water is still mostly unknown. Here, a super moisture‐absorbent gel, which is composed of hygroscopic polypyrrole chloride penetrating in hydrophilicity‐switchable polymeric network of poly N‐isopropylacrylamide, is shown. Based on such design, a high‐efficiency water production by AWH has been achieved in a broad range of relative humidity. The synergistic effect enabled by the molecular level integration of hygroscopic and hydrophilicity‐switchable polymers in a network architecture presents controllable interaction between the gel and water molecules, simultaneously realizing efficient vapor capturing, in situ water liquefaction, high‐density water storage and fast water releasing under different weather conditions. Being an effective method to regulate migration of water molecules, such design represents a novel strategy to improve the AWH, and it is also fundamental to other water management systems for environmental cooling, surficial moisturizing and beyond.     

Spray formed and rolled aluminium‐magnesium‐scandium alloys with high scandium content

Aluminium‐magnesium‐scandium alloys offer good weldability, high corrosion resistance, high thermal stability and the potential for high strength by precipitation hardening. A problem of aluminium‐scandium alloys is the low solubility of about 0.3 mass‐% scandium when using conventional casting methods. The solution of scandium can be raised by higher cooling rates during solidification. This was realised by spray forming of Al‐4.5Mg‐0.7Sc alloys as flat deposits. Further cooling rates after solidification should also be high to prevent coarse precipitation of secondary Al₃Sc. Therefore a cooling device was designed for the spray formed flat deposits. The flat deposits were rolled at elevated temperatures to close the porosity from spray forming. Microstructures, aging behaviour and tensile properties of the rolled sheets were investigated. Strength enhancements of about 100 MPa compared to conventional Al‐Mg‐Sc alloys were achieved.     

Out‐of‐Plane 3D‐Printed Microfibers Improve the Shear Properties of Hydrogel Composites

One challenge in biofabrication is to fabricate a matrix that is soft enough to elicit optimal cell behavior while possessing the strength required to withstand the mechanical load that the matrix is subjected to once implanted in the body. Here, melt electrowriting (MEW) is used to direct‐write poly(ε‐caprolactone) fibers “out‐of‐plane” by design. These out‐of‐plane fibers are specifically intended to stabilize an existing structure and subsequently improve the shear modulus of hydrogel–fiber composites. The stabilizing fibers (diameter = 13.3 ± 0.3 µm) are sinusoidally direct‐written over an existing MEW wall‐like structure (330 µm height). The printed constructs are embedded in different hydrogels (5, 10, and 15 wt% polyacrylamide; 65% poly(2‐hydroxyethyl methacrylate) (pHEMA)) and a frequency sweep test (0.05–500 rad s^?1, 0.01% strain, n = 5) is performed to measure the complex shear modulus. For the rheological measurements, stabilizing fibers are deposited with a radial‐architecture prior to embedding to correspond to the direction of the stabilizing fibers with the loading of the rheometer. Stabilizing fibers increase the complex shear modulus irrespective of the percentage of gel or crosslinking density. The capacity of MEW to produce well‐defined out‐of‐plane fibers and the ability to increase the shear properties of fiber‐reinforced hydrogel composites are highlighted.     

Inkjet‐Printed Lithium–Sulfur Microcathodes for All‐Printed,Integrated Nanomanufacturing

Improved thin‐film microbatteries are needed to provide appropriate energy‐storage options to power the multitude of devices that will bring the proposed “Internet of Things” network to fruition (e.g., active radio‐frequency identification tags and microcontrollers for wearable and implantable devices). Although impressive efforts have been made to improve the energy density of 3D microbatteries, they have all used low energy‐density lithium‐ion chemistries, which present a fundamental barrier to miniaturization. In addition, they require complicated microfabrication processes that hinder cost‐competitiveness. Here, inkjet‐printed lithium–sulfur (Li–S) cathodes for integrated nanomanufacturing are reported. Single‐wall carbon nanotubes infused with electronically conductive straight‐chain sulfur (S@SWNT) are adopted as an integrated current‐collector/active‐material composite, and inkjet printing as a top‐down approach to achieve thin‐film shape control over printed electrode dimensions is used. The novel Li–S cathodes may be directly printed on traditional microelectronic semicoductor substrates (e.g., SiO₂) or on flexible aluminum foil. Profilometry indicates that these microelectrodes are less than 10 µm thick, while cyclic voltammetry analyses show that the S@SWNT possesses pseudocapacitive characteristics and corroborates a previous study suggesting the S@SWNT discharge via a purely solid‐state mechanism. The printed electrodes produce ≈800 mAh g^?1 S initially and ≈700 mAh g^?1 after 100 charge/discharge cycles at C/2 rate.     

Architecting Graphene Oxide Rolled‐Up Micromotors: A Simple Paper‐Based Manufacturing Technology

A graphene oxide rolled‐up tube production process is reported using wax‐printed membranes for the fabrication of on‐demand engineered micromotors at different levels of oxidation, thickness, and lateral dimensions. The resultant graphene oxide rolled‐up tubes can show magnetic and catalytic movement within the addition of magnetic nanoparticles or sputtered platinum in the surface of graphene‐oxide‐modified wax‐printed membranes prior to the scrolling process. As a proof of concept, the as‐prepared catalytic graphene oxide rolled‐up micromotors are successfully exploited for oil removal from water. This micromotor production technology relies on an easy, operator‐friendly, fast, and cost‐efficient wax‐printed paper‐based method and may offer a myriad of hybrid devices and applications.     

Inkjet‐Printed High‐Efficiency Multilayer QLEDs Based on a Novel Crosslinkable Small‐Molecule Hole Transport Material

Quantum dots light‐emitting diodes (QLEDs) have attracted much interest owing to their compatibility with low‐cost inkjet printing technology and potential for use in large‐area full‐color pixelated display. However, it is challenging to fabricate high efficiency inkjet‐printed QLEDs because of the coffee ring effects and inferior resistance to solvents from the underlying polymer film during the inkjet printing process. In this study, a novel crosslinkable hole transport material, 4,4′‐bis(3‐vinyl‐9H‐carbazol‐9‐yl)‐1,1′‐biphenyl (CBP‐V) which is small‐molecule based, is synthesized and investigated for inkjet printing of QLEDs. The resulting CBP‐V film after thermal curing exhibits excellent solvent resistance properties without any initiators. An added advantage is that the crosslinked CBP‐V film has a sufficiently low highest occupied molecular orbital energy level (≈?6.2 eV), high film compactness, and high hole mobility, which can thus promote the hole injection into quantum dots (QDs) and improve the charge carrier balance within the QD emitting layers. A red QLED is successfully fabricated by inkjet printing a CBP‐V and QDs bilayer. Maximum external quantum efficiency of 11.6% is achieved, which is 92% of a reference spin‐coated QLED (12.6%). This is the first report of such high‐efficiency inkjet‐printed multilayer QLEDs and demonstrates a unique and effective approach to inkjet printing fabrication of high‐performance QLEDs.     

Autonomous Ultrafast Self‐Healing Hydrogels by pH‐Responsive Functional Nanofiber Gelators as Cell Matrices

The synthesis of hybrid hydrogels by pH‐controlled structural transition with exceptional rheological properties as cellular matrix is reported. “Depsi” peptide sequences are grafted onto a polypeptide backbone that undergo a pH‐induced intramolecular O–N–acyl migration at physiological conditions affording peptide nanofibers (PNFs) as supramolecular gelators. The polypeptide–PNF hydrogels are mechanically remarkably robust. They reveal exciting thixotropic behavior with immediate in situ recovery after exposure to various high strains over long periods and self‐repair of defects by instantaneous reassembly. High cytocompatibility, convenient functionalization by coassembly, and controlled enzymatic degradation but stability in 2D and 3D cell culture as demonstrated by the encapsulation of primary human umbilical vein endothelial cells and neuronal cells open many attractive opportunities for 3D tissue engineering and other biomedical applications.     

Electro‐Assisted Bioprinting of Low‐Concentration GelMA Microdroplets

Low‐concentration gelatin methacryloyl (GelMA) has excellent biocompatibility to cell‐laden structures. However, it is still a big challenge to stably fabricate organoids (even microdroplets) using this material due to its extremely low viscosity. Here, a promising electro‐assisted bioprinting method is developed, which can print low‐concentration pure GelMA microdroplets with low cost, low cell damage, and high efficiency. With the help of electrostatic attraction, uniform GelMA microdroplets measuring about 100 μm are rapidly printed. Due to the application of lower external forces to separate the droplets, cell damage during printing is negligible, which often happens in piezoelectric or thermal inkjet bioprinting. Different printing states and effects of printing parameters (voltages, gas pressure, nozzle size, etc.) on microdroplet diameter are also investigated. The fundamental properties of low‐concentration GelMA microspheres are subsequently studied. The results show that the printed microspheres with 5% w/v GelMA can provide a suitable microenvironment for laden bone marrow stem cells. Finally, it is demonstrated that the printed microdroplets can be used in building microspheroidal organoids, in drug controlled release, and in 3D bioprinting as biobricks. This method shows great potential use in cell therapy, drug delivery, and organoid building.     

Self‐Organized Graphene Nanosheets with Corrugated,Ordered Tip Structures for High‐Performance Flexible Field Emission

Patterned reduced graphene oxide (rGO) films with vertically aligned tip structures are fabricated by a straightforward self‐assembly method. The size, uniformity of the patterns, and alignment of the tips are successfully controlled according to the concentration of a GO/octadecylamine (ODA)‐dispersed solution. The surface energy difference between the GO/ODA solution and a self‐assembled water droplet is a critical parameter for determining the pattern structure. Numerous rGO nanosheets are formed so as to be vertically aligned with respect to the substrate during film fabrication at GO concentrations below 2.0 g/L. These samples provide high field‐emission characteristics. The patterned rGO arrays are highly flexible with preservation of the field emission properties, even at large bending angles. This is attributed to the high crystallinity, emitter density, and good chemical stability of the rGO arrays, as well as the strong interactions between the rGO arrays and the substrate.     

Polyethylene Glycol and Polyethylenimine Dual‐Functionalized Nano‐Graphene Oxide for Photothermally Enhanced Gene Delivery

Graphene oxide (GO) has been extensively explored in nanomedicine for its excellent physiochemical, electrical, and optical properties. Here, polyethylene glycol (PEG) and polyethylenimine (PEI) are covalently conjugated to GO via amide bonds, obtaining a physiologically stable dual‐polymer‐functionalized nano‐GO conjugate (NGO‐PEG‐PEI) with ultra‐small size. Compared with free PEI and the GO‐PEI conjugate without PEGylation, NGO‐PEG‐PEI shows superior gene transfection efficiency without serum interference, as well as reduced cytotoxicity. Utilizing the NIR optical absorbance of NGO, the cellular uptake of NGO‐PEG‐PEI is shown to be enhanced under a low power NIR laser irradiation, owing to the mild photothermal heating that increases the cell membrane permeability without significantly damaging cells. As the results, remarkably enhanced plasmid DNA transfection efficiencies induced by the NIR laser are achieved using NGO‐PEG‐PEI as the light‐responsive gene carrier. More importantly, it is shown that our NGO‐PEG‐PEI is able to deliver small interfering RNA (siRNA) into cells under the control of NIR light, resulting in obvious down‐regulation of the target gene, Polo‐like kinase 1 (Plk1), in the presence of laser irradiation. This study is the first to use photothermally enhanced intracellular trafficking of nanocarriers for light‐controllable gene delivery. This work also encourages further explorations of functionalized nano‐GO as a photocontrollable nanovector for combined photothermal and gene therapies.