Highly Stable Heating Fibers of Ti3C2Tx MXene and Polyacrylonitrile via Synergistic Thermal Annealing.

Nanohybrid assemblies provide an effective platform for integrating the intrinsic properties of individual components into microscale fibers. In this study, a novel approach for creating mechanically and environmentally stable MXene fibers through the synergistic assembly of MXene and polyacrylonitrile (PAN), is introduced. Unlike fibers generated via a conventional stabilization process, which relies on air-based stabilization to transform the PAN molecules into ring structures fundamental to carbon fibers, the hybrid fibers are annealed in an Ar atmosphere. This unique approach suggests MXene can serve as an oxygen provider that is essential for stabilizing PAN. As a result, significantly improved interfiber compactness is achieved and the oxidation stability of MXene is enhanced under atmospheric conditions. The resulting fibers exhibit exceptional stability, even after extended exposure to high humidity and elevated temperatures. This highlights the suitability of the thermally annealed MXene-PAN (T-MX-PAN) fibers as robust electric heating elements. Notably, these fibers consistently generate heat over 1800 bending cycles. When integrated into fabrics, they demonstrate the capability to generate sufficient heat for melting ice and rapid evaporation. This study highlights the potential of T-MX-PAN fibers as next-generation wearable heaters and offers valuable insights into advancing wearable technology in demanding environments.

Sustainable 3D printing by reversible salting-out effects with aqueous salt solutions.

Achieving a simple yet sustainable printing technique with minimal instruments and energy remains challenging. Here, a facile and sustainable 3D printing technique is developed by utilizing a reversible salting-out effect. The salting-out effect induced by aqueous salt solutions lowers the phase transition temperature of poly(N-isopropylacrylamide) (PNIPAM) solutions to below 10 °C. It enables the spontaneous and instant formation of physical crosslinks within PNIPAM chains at room temperature, thus allowing the PNIPAM solution to solidify upon contact with a salt solution. The PNIPAM solutions are extrudable through needles and can immediately solidify by salt ions, preserving printed structures, without rheological modifiers, chemical crosslinkers, and additional post-processing steps/equipment. The reversible physical crosslinking and de-crosslinking of the polymer through the salting-out effect demonstrate the recyclability of the polymeric ink. This printing approach extends to various PNIPAM-based composite solutions incorporating functional materials or other polymers, which offers great potential for developing water-soluble disposable electronic circuits, carriers for delivering small materials, and smart actuators.

Surface nitrided MXene sheets with outstanding electroconductivity and oxidation stability.

Two-dimensional Ti3C2Tx MXenes are promising candidates for a wide range of film- or fiber-based devices owing to their solution processability, high electrical conductivity, and versatile surface chemistry. The surface terminal groups (Tx) of MXenes can be removed to increase their inherent electrical performance and ensure chemical stability. Therefore, understanding the chemical evolution during the removal of the terminal groups is crucial for guiding the production, processing, and application of MXenes. Herein, we investigate the effect of chemical modification on the electron-transfer behavior during the removal of the terminal groups by annealing Ti3C2Tx MXene single sheets under argon (Ar-MXene) and ammonia gas (NH3-MXene) conditions. Annealing in ammonia gas results in surface nitridation of MXenes and preserves the electron-abundant Ti3C2 structure, whereas annealing MXene single sheets in Ar gas results in the oxidation of the titanium layers. The surface-nitrided MXene film exhibits an electrical conductivity two times higher than that of the Ar-MXene film. The oxidation stability is quantified by calculating the oxidation rate constants for severe reactions with H2O2. The surface-nitrided MXene is 13 times more stable than Ar-MXene. The investigation of MXene single sheets provides fundamental insights that are valuable for designing electrically conductive and chemically stable MXenes.

Impermeable Graphene Skin Increases the Heating Efficiency and Stability of an MXene Heating Element.

A Joule heater made of emerging 2D nanosheets, i.e., MXene, has the advantage of low-voltage operation with stable heat generation owing to its highly conductive and uniformly layered structure. However, the self-heated MXene sheets easily get oxidized in warm and moist environments, which limits their intrinsic heating efficiencies. Herein, an ultrathin graphene skin is introduced as a surface-regulative coating on MXene to enhance its oxidative stability and Joule heating efficiency. The skin layer is deposited on MXene using a scalable solution-phased layer-by-layer assembly process without deteriorating the excellent electrical conductivity of the MXene. The graphene skin comprises narrow and hydrophobic channels, which results in ≈70 times higher water impermeability of the hybrid film of graphene and MXene (GMX) than that of the pristine MXene. A complementary electrochemical analysis confirms that the graphene skin facilitates longer-lasting protection than conventional polymer coatings owing to its tortuous pathways. In addition, the sp2 planar carbon surface with a low heat loss coefficient improves the heating efficiency of the GMX, indicating that this strategy is promising for developing adaptive heating materials with a tractable voltage range and high Joule heating efficiency.

Grafting Behavior of Amine Ligands for Surface Modification of MXene.

Surface modification to improve the oxidation stability and dispersibility of MXene in diverse organic media is a facile strategy for broadening its application. Among the various ligands that can be grafted on the MXene surface, oleylamine (OAm), with amine functionalities, is an advantageous candidate owing to its strong interactions and commercial viability. OAms are grafted onto MXene through covalent bonds induced by nucleophilic reactions and H bonds in liquid interface reactions at room temperature. In addition, this grafting behavior of the ligand was characterized by a reduction in the slope with an increase in the ligand concentration (Cl), confirming that the OAms were grafted via Langmuir-like behavior, and the monolayer of OAms was developed via two distinct steps (I: lying-down phase; II: ordered monolayer). MXene nanosheets modified by OAm (OAm-MX) are highly dispersible in a wide range of organic solvents owing to the alkyl chain of the OAms, which induces hydrophobic properties on the surface of MXene. The OAm-MX dispersion exhibits outstanding oxidation and dispersion stability and remarkable coating performance on a wide range of substrates owing to their excellent solution processability. Therefore, this study provides fundamental insights into the adsorption behavior and interaction between amine ligands and MXene nanosheets for the surface chemistry of MXene.

Microstructure-Controlled Polyacrylonitrile/Graphene Fibers over 1 Gigapascal Strength.

Controlling the microstructures in fibers, such as crystalline structures and microvoids, is a crucial challenge for the development of mechanically strong graphene fibers (GFs). To date, although GFs graphitized at high temperatures have exhibited high tensile strength, GFs still have limited the ultimate mechanical strength owing to the presence due to the structural defects, including the imperfect alignment of graphitic crystallites and the presence of microsized voids. In this study, we significantly enhanced the mechanical strength of GF by controlling microstructures of fibers. GF was hybridized by incorporating polyacrylonitrile (PAN) in the graphene oxide (GO) dope solution. In addition, we controlled the orientation of the inner structure by applying a tensile force at 800 °C. The results suggest that PAN can act as a binder for graphene sheets and can facilitate the rearrangement of the fiber's microstructure. PAN was directionally carbonized between graphene sheets due to the catalytic effect of graphene. The resulting hybrid GFs successfully displayed a high strength of 1.10 GPa without undergoing graphitization at extremely high temperatures. We believe that controlling the alignment of nanoassembled structure is an efficient strategy for achieving the inherent performance characteristics of graphene at the level of multidimensional structures including films and fibers.

Highly Electroconductive and Mechanically Strong Ti3C2Tx MXene Fibers Using a Deformable MXene Gel.

Self-assembly of two-dimensional MXene sheets is used in various fields to create multiscale structures due to their electrical, mechanical, and chemical properties. In principle, MXene nanosheets are assembled by molecular interactions, including hydrogen bonds, electrostatic interactions, and van der Waals forces. This study describes how MXene colloid nanosheets can form self-supporting MXene hydrogels. Three-dimensional network structures of MXene gels are strengthened by reinforced electrostatic interactions between nanosheets. Stable gel networks are beneficial for fabricating highly aligned fibers because MXene gel can endure structural deformation. During wet spinning of highly concentrated MXene colloids in a coagulation bath, MXene sheets can be transformed into perfectly aligned fibers under a mechanical drawing force. Oriented MXene fibers exhibit a 1.5-fold increase in electrical conductivity (12 504 S cm-1) and Young's modulus (122 GPa) compared with other fibers. The oriented MXene fibers are expected to have widespread applications, including electrical wiring and signal transmission.

Large-scale wet-spinning of highly electroconductive MXene fibers.

Ti3C2Tx MXene is an emerging class of two-dimensional nanomaterials with exceptional electroconductivity and electrochemical properties, and is promising in the manufacturing of multifunctional macroscopic materials and nanomaterials. Herein, we develop a straightforward, continuously controlled, additive/binder-free method to fabricate pure MXene fibers via a large-scale wet-spinning assembly. Our MXene sheets (with an average lateral size of 5.11 µm2) are highly concentrated in water and do not form aggregates or undergo phase separation. Introducing ammonium ions during the coagulation process successfully assembles MXene sheets into flexible, meter-long fibers with very high electrical conductivity (7,713 S cm-1). The fabricated MXene fibers are comprehensively integrated by using them in electrical wires to switch on a light-emitting diode light and transmit electrical signals to earphones to demonstrate their application in electrical devices. Our wet-spinning strategy provides an approach for continuous mass production of MXene fibers for high-performance, next-generation, and wearable electronic devices.

Room-Temperature, Highly Durable Ti3C2Tx MXene/Graphene Hybrid Fibers for NH3 Gas Sensing.

Graphene-based fibers (GFs) have aroused enormous interest in portable, wearable electronics because of their excellent mechanical flexibility, electrical conductivity, and weavability, which make them advantageous for wearable electronic devices. Herein, we report the development of metal binder-free Ti3C2Tx MXene/graphene hybrid fibers by a scalable wet-spinning process. These hybrid fibers exhibit excellent mechanical and electrical properties for applications in flexible wearable gas sensors. The synergistic effects of electronic properties and gas-adsorption capabilities of MXene/graphene allow the created fibers to show high NH3 gas sensitivity at room temperature. The hybrid fibers exhibited significantly improved NH3 sensing response (ΔR/R0 = 6.77%) compared with individual MXene and graphene. The hybrid fibers also showed excellent mechanical flexibility with a minimal fluctuation of resistance of ±0.2% and low noise resistance even after bending over 2000 cycles, enabling gas sensing during deformation. Furthermore, flexible MXene/graphene hybrid fibers were woven into a lab coat, demonstrating their high potential for wearable devices. We envisage that these exciting features of 2D hybrid materials will provide a novel pathway for designing next-generation portable wearable gas sensors.