Scalable Design of Ru-Embedded Carbon Fabric Using Conventional Carbon Fiber Processing for Robust Electrocatalysts.

Metal-carbon composites are extensively utilized as electrochemical catalysts but face critical challenges in mass production and stability. We report a scalable manufacturing process for ruthenium surface-embedded fabric electrocatalysts (Ru-SFECs) via conventional fiber/fabric manufacturing. Ru-SFECs have excellent catalytic activity and stability toward the hydrogen evolution reaction, exhibiting a low overpotential of 11.9 mV at a current density of 10 mA cm-2 in an alkaline solution (1.0 M aq KOH solution) with only a slight overpotential increment (6.5%) after 10,000 cycles, whereas under identical conditions, that of commercial Pt/C increases 6-fold (from 1.3 to 7.8 mV). Using semipilot-scale equipment, a protocol is optimized for fabricating continuous self-supported electrocatalytic electrodes. Tailoring the fiber processing parameters (tension and temperature) can optimize the structural development, thereby achieving good catalytic performance and mechanical integrity. These findings underscore the significance of self-supporting catalysts, offering a general framework for stable, binder-free electrocatalytic electrode design.

Multilayered Composites with Modulus Gradient for Enhanced Pressure-Temperature Sensing Performance.

Highly sensitive and flexible composite sensors with pressure and temperature sensing abilities are of great importance in human motion monitoring, robotic skins, and automobile seats when checking the boarding status. Several studies have been conducted to improve the temperature-pressure sensitivity; however, they require a complex fabrication process for micro-nanostructures, which are material-dependent. Therefore, there is a need to develop the structural designs to improve the sensing abilities. Herein, we demonstrate a flexible composite with an enhanced pressure and temperature sensing performance. Its structural design consists of a multilayered composite construction with an elastic modulus gradient. Controlled stress concentration and distribution induced by a micropatterned structure between the layers improves its pressure and temperature sensing performance. The proposed composite sensor can monitor a wide range of pressure and temperature stimuli and also has potential applications as an automotive seat sensor for simultaneous human temperature detection and occupant weight sensing.

Heat-Dissipation Design and 3D Printing of Ternary Silver Chalcogenide-Based Thermoelectric Legs for Enhancing Power Generation Performance.

Thermoelectric devices have received significant attention because of their potential for sustainable energy recovery. In these devices, a thermal design that optimizes heat transfer and dissipation is crucial for maximizing the power output. Heat dissipation generally requires external active or passive cooling devices, which often suffer from inevitable heat loss and heavy systems. Herein, the design of heat-sink integrated thermoelectric legs is proposed to enhance heat dissipation without external cooling devices, realized by finite element model simulation and 3D printing of ternary silver chalcogenide-based thermoelectric materials. Owing to the self-induced surface charges of the synthesized AgBiSe2 (n-type) and AgSbTe2 (p-type) particles, these particle-based colloidal inks exhibited high viscoelasticity, which enables the creation of complex heat-dissipation architectures via 3D printing. Power generators made from 3D-printed heat-dissipating legs exhibit higher temperature differences and output power than traditional cuboids, offering a new strategy for enhancing thermoelectric power generation.

Abnormally High Graphitic Crystallization of Cellulose Nanocrystals.

Cellulose nanocrystals (CNCs) are currently of great interest for many applications, such as energy storage and nanocomposites, because of their natural abundance. A number of carbonization studies have reported abnormal graphitization behavior of CNCs, although cellulose is generally known as a precursor for hard carbon (nongraphitizable carbon). Herein, we report a spray-freeze-drying (SFD) method for CNCs and a subsequent carbonization study to ascertain the difference in the structural development between the amorphous and crystalline phases. The morphological observation by high-resolution transmission electron microscopy of the carbonized SFD-CNC clearly shows that the amorphous and crystalline phases of CNC are attributed to the formation of hard and soft carbon, respectively. The results of a reactive molecular dynamics (RMD) study also show that the amorphous cellulose phase leads to the formation of fewer carbon ring structures, indicative of hard carbon. In contrast, the pristine crystalline cellulose phase has a higher density and thermal stability, resulting in limited molecular relaxation and the formation of a highly crystalline graphitic structure (soft carbon).

Achieving Both Ultrahigh Electrical Conductivity and Mechanical Modulus of Carbon Films: Templating-Coalescing Behavior of Single-Walled Carbon Nanotube in Polyacrylonitrile.

Promoting the feasibility of carbon films as electrode applications requires sufficient performances in view of both electrical and mechanical properties. Herein, carbon films with ultrahigh electrical conductivity and mechanical modulus are prepared by high temperature carbonization of polyacrylonitrile (PAN)/single-walled carbon nanotube (SWNT) nanocomposites. Achieving both performances is ascribed to remarkable graphitic crystallinity, resulting from the sequential templating-coalescing behavior of concentrated SWNT bundles (B-CNTs). While well-dispersed SWNTs (WD-CNTs) facilitate radial templating according to their tubular geometry, flattened B-CNTs sandwiched between carbonized PAN matrices induce vertical templating, where the former and latter produce concentric and planar crystallizations of the graphitic structure, respectively. After carbonization at 2500 °C with the remaining WD-CNTs as microstructural defects, the flattened B-CNTs coalesce into graphitic crystals by zipping the surrounding matrix, resulting in high crystallinity with the crystal thicknesses of 27.4 and 39.4 nm for the (002) and (10) planes, respectively. For comparison, the graphene oxide (GO) containing carbon films produce a less-ordered graphitic phase owing to irregular templating, despite the geometrical consistency. Consequently, PAN/B-CNT carbon films exhibit exceptional electrical conductivity (40.7 × 104 S m-1 ) and mechanical modulus (38.2 ± 6.4 GPa). Thus, controlling the templating-coalescing behavior of SWNTs is the key for improving final performances of carbon films.

Ultrastrong Hybrid Fibers with Tunable Macromolecular Interfaces of Graphene Oxide and Carbon Nanotube for Multifunctional Applications.

Individual carbon nanotubes (CNT) and graphene have unique mechanical and electrical properties; however, the properties of their macroscopic assemblies have not met expectations because of limited physical dimensions, the limited degree of dispersion of the components, and various structural defects. Here, a state-of-the-art assembly for a novel type of hybrid fiber possessing the properties required for a wide variety of multifunctional applications is presented. A simple and effective multidimensional nanostructure of CNT and graphene oxide (GO) assembled by solution processing improves the interfacial utilization of the components. Flexible GOs are effectively intercalated between nanotubes along the shape of CNTs, which reduces voids, enhances orientation, and maximizes the contact between elements. The microstructure is finely controlled by the elements content ratio and dimensions, and an optimal balance improves the mechanical properties. The hybrid fibers simultaneously exhibit exceptional strength (6.05 GPa), modulus (422 GPa), toughness (76.8 J g-1 ), electrical conductivity (8.43 MS m-1 ), and knot strength efficiency (92%). Furthermore, surface and electrochemical properties are significantly improved by tuning the GO content, further expanding the scope of applications. These hybrid fibers are expected to offer a strategy for overcoming the limitations of existing fibers in meeting the requirements for applications in the fiber industry.

Synthesis of high quality 2D carbide MXene flakes using a highly purified MAX precursor for ink applications.

The practical application of 2D MXenes in electronic and energy fields has been hindered by the severe variation in the quality of MXene products depending on the parent MAX phases, manufacturing techniques, and preparation parameters. In particular, their synthesis has been impeded by the lack of studies reporting the synthesis of high-quality parent MAX phases. In addition, controllable and uniform deposition of 2D MXenes on various large-scale substrates is urgently required to use them practically. Herein, a method of pelletizing raw materials could synthesize a stoichiometric Ti3AlC2 MAX phase with high yield and processability, and fewer impurities. The Ti3AlC2 could be exfoliated into 1-2-atom-thick 2D Ti3C2T x flakes, and their applicability was confirmed by the deposition and additional alignment of the 2D flakes with tunable thickness and electrical properties. Moreover, a practical MXene ink was fabricated with rheological characterization. MXene ink exhibited much better thickness uniformity while retaining excellent electrical performances (e.g., sheet resistance, electromagnetic interference shielding ability) as those of a film produced by vacuum filtration. The direct functional integration of MXenes on various substrates is expected to initiate new and unexpected MXene-based applications.

Cu2Se-based thermoelectric cellular architectures for efficient and durable power generation.

Thermoelectric power generation offers a promising way to recover waste heat. The geometrical design of thermoelectric legs in modules is important to ensure sustainable power generation but cannot be easily achieved by traditional fabrication processes. Herein, we propose the design of cellular thermoelectric architectures for efficient and durable power generation, realized by the extrusion-based 3D printing process of Cu2Se thermoelectric materials. We design the optimum aspect ratio of a cuboid thermoelectric leg to maximize the power output and extend this design to the mechanically stiff cellular architectures of hollow hexagonal column- and honeycomb-based thermoelectric legs. Moreover, we develop organic binder-free Cu2Se-based 3D-printing inks with desirable viscoelasticity, tailored with an additive of inorganic Se82- polyanion, fabricating the designed topologies. The computational simulation and experimental measurement demonstrate the superior power output and mechanical stiffness of the proposed cellular thermoelectric architectures to other designs, unveiling the importance of topological designs of thermoelectric legs toward higher power and longer durability.

Observations on Solution Crystallization of Poly(vinyl alcohol) in the Presence of Single-Wall Carbon Nanotubes.

PVA/SWNT dispersions yield aloe plant-like crystals, where the leaves are single crystals templated by PVA coated SWNT. Longer growth times (≈18 months) lead to hexagonal rod-like crystals. HR-TEM images show evidence that PVA molecules are aligned parallel to the SWNT axis. WAXD, electron diffraction, and HR-TEM observations of these aloe plant and hexagonal crystals suggests evidence for possible PVA-SWNT epitaxy. Wide-angle and electron diffraction data of these crystals also show that the structure seems to mimic the 2D hexagonal crystal packing of SWNT. PVA lattice images and moiré fringes were also observed in the leaf-like crystals.

Defect structure evolution of polyacrylonitrile and single wall carbon nanotube nanocomposites: a molecular dynamics simulation approach.

In this study, molecular dynamics simulations were performed to understand the defect structure development of polyacrylonitrile-single wall carbon nanotube (PAN-SWNT) nanocomposites. Three different models (control PAN, PAN-SWNT(5,5), and PAN-SWNT(10,10)) with a SWNT concentration of 5 wt% for the nanocomposites were tested to study under large extensional deformation to the strain of 100% to study the corresponding mechanical properties. Upon deformation, the higher stress was observed in both nanocomposite systems as compared to the control PAN, indicating effective reinforcement. The higher Young's (4.76 ± 0.24 GPa) and bulk (4.19 ± 0.25 GPa) moduli were observed when the smaller-diameter SWNT(5,5) was used, suggesting that SWNT(5,5) resists stress better. The void structure formation was clearly observed in PAN-SWNT(10,10), while the nanocomposite with smaller diameter SWNT(5,5) did not show the development of such a defect structure. In addition, the voids at the end of SWNT(10,10) became larger in the drawing direction with increasing deformation.

Effect of Interfacial Interaction on the Conformational Variation of Poly(vinylidene fluoride) (PVDF) Chains in PVDF/Graphene Oxide (GO) Nanocomposite Fibers and Corresponding Mechanical Properties.

Poly(vinylidene fluoride) (PVDF)/graphene oxide (GO) nanocomposite fibers were dry-jet wet spun at the GO concentrations of 0, 1, and 2 wt % with respect to the polymer. The as-spun fibers were drawn in the draw ratio (DR) range of 2-6.5, and the correlation between the PVDF chain conformation and the mechanical properties of the fibers upon drawing has been studied by two-dimensional correlation spectroscopy of Fourier-transformed infrared, wide-angle X-ray diffraction, differential scanning calorimetry, and tensile testing. The PVDF/GO nanocomposite fibers exhibited that the mobile PVDF crystals due to the conformational defects and kinks were nucleated because of the polar interaction between PVDF chains and functional groups of GO, whereas the control PVDF fiber showed the conventional conversion of crystal polymorphs (α and γ phases to ß phase). As a result, the nanocomposite fiber showed dramatically improved toughness (enhanced by 1123% at a DR of 2 and 120% at a DR of 6.5) as compared to that of the control fiber. Furthermore, the tensile strength and modulus of the PVDF/GO (2 wt %) fiber were 394 MPa and 4.6 GPa, respectively, whereas those of the control PVDF fiber were 295 MPa and 3.9 GPa, respectively.

Graphene nanoribbons as an advanced precursor for making carbon fiber.

Graphene oxide nanoribbons (GONRs) and chemically reduced graphene nanoribbons (crGNRs) were dispersed at high concentrations in chlorosulfonic acid to form anisotropic liquid crystal phases. The liquid crystal solutions were spun directly into hundreds of meters of continuous macroscopic fibers. The relationship of fiber morphology to coagulation bath conditions was studied. The effects of colloid concentration, annealing temperature, spinning air gap, and pretension during annealing on the fibers' performance were also investigated. Heat treatment of the as-spun GONR fibers at 1500 °C produced thermally reduced graphene nanoribbon (trGNR) fibers with a tensile strength of 378 MPa, Young's modulus of 36.2 GPa, and electrical conductivity of 285 S/cm, which is considerably higher than that in other reported graphene-derived fibers. This better trGNR fiber performance was due to the air gap spinning and annealing with pretension that produced higher molecular alignment within the fibers, as determined by X-ray diffraction and scanning electron microscopy. The specific modulus of trGNR fibers is higher than that of the commercial general purpose carbon fibers and commonly used metals such as Al, Cu, and steel. The properties of trGNR fibers can be further improved by optimizing the spinning conditions with higher draw ratio, annealing conditions with higher pretensions, and using longer flake GONRs. This technique is a new high-carbon-yield approach to make the next generation carbon fibers based on solution-based liquid crystal phase spinning.

Polyethylene crystallization nucleated by carbon nanotubes under shear.

Polyethylene crystallization under shear has been studied in the presence of single-wall, few-wall, and multiwall carbon nanotubes (SWNT, FWNT, and MWNT). Polyethylene crystal d-spacings for (110) and (200) planes in polyethylene/carbon nanotubes (CNT) are smaller than in the control polyethylene without CNT and the polymer chain is oriented along the CNT axis. The single-wall carbon nanotube templated polyethylene crystals do not redissolve in boiling xylenes; instead, the chain morphology transforms to an amorphous conformation but remains oriented along the nanotube axis. SWNT crystal peaks were also observed in polyethylene/SWNT fibers.

Note: Thermal conductivity measurement of individual poly(ether ketone)/carbon nanotube fibers using a steady-state dc thermal bridge method.

Customized engineered fibers are currently being used extensively in the aerospace and automobile industries due to the ability to "design in" specific engineering characteristics. Understanding the thermal conductivity of these new fibers is critical for thermal management and design optimization. In the current investigation, a steady-state dc thermal bridge method (DCTBM) is developed to measure the thermal conductivity of individual poly(ether ketone) (PEK)/carbon nanotube (CNT) fibers. For non-conductive fibers, a thin platinum layer was deposited on the test articles to serve as the heater and temperature sensor. The effect of the platinum layer on the thermal conductivity is presented and discussed. DCTBM is first validated using gold and platinum wires (25 µm in diameter) over a temperature ranging from room temperature to 400 K with ±11% uncertainty, and then applied to PEK/CNT fibers with diverse CNT loadings. At a 28 wt. % CNT loading, the thermal conductivity of fibers at 390 K is over 27 Wm(-1)K(-1), which is comparable to some engineering alloys.