Centrifugal-Gravity-Enforced Deposition of MXene Electrodes for High-Performance and Ultrastable Microsupercapacitors.

Two-dimensional (2D) transition metal carbides, known as MXenes, have captured much attention for their excellent electrical conductivity and electrochemical capability. However, the susceptibility of MXenes to oxidation, particularly Ti3C2Tx transforming into titanium dioxide upon exposure to ambient air, hinders their utilization for extended operational life cycles. This work introduces a simple and straightforward method for producing ultrathin MXene electrode films tailored for energy storage applications, employing centrifugal-gravity force. Our approach significantly suppresses the oxidation phenomenon that arises in MXene materials and also effectively prevents the recrystallization of potentially residual LiF during the film formation. Additionally, the utilization of this MXene electrode in an all-solid-state microsupercapacitor (MSC) with an interdigitated pattern demonstrates an exceptionally improved and stable electrochemical performance. This includes a high volumetric capacitance of approximately 467 F cm-3, an energy density of around 65 mWh cm-3, and impressive long-term cycle stability, retaining about 94% capacity after 10 000 cycles. Moreover, a downsized MSC device exhibits remarkable mechanical durability, retaining over 98% capacity even when folded and sustaining stability over extended periods. Therefore, we believe that this study provides valuable insights for advancing highly integrated energy storage devices, ensuring exceptional electrochemical efficiency and prolonged functionality in diverse environments, whether ambient or humid.

Effective Approach for Fabricating Highly Precise High-Curvature Structural Patterns via Air-Bubble Induction.

Developing a new master mold-based patterning technology that can be used to accurately, precisely, and uniformly create large-area micropatterns while controlling the micropatterns of curved structures is essential for promoting innovative developments in various application fields. This study develops a new top-down lithographic process that can effectively produce structural patterns with high curvatures by growing isolated microbubbles in the master pattern holes. The isolated air-pocket lithography (IAL) we developed is based on the controlled behavior of micrometer-sized air pockets trapped between the grooves of the master pattern and the curable polymer. We successfully fabricated a concave array polydimethylsiloxane (PDMS) film and a convex array polymer film. In addition, the IAL mechanism was proven by confirming the expansion process of micrometer-sized air pockets trapped between the deep groove of the silicon master pattern and the PDMS coating film by using optical microscopy images. We successfully obtained complex three-dimensional structural patterns containing both 3D hollow spherical concave and ring-shaped two-dimensional convex patterns. This simple, fast, and effective high-curvature patterning technique is expected to provide innovative solutions for future applications such as nanoelectronics, optical devices, displays, and photovoltaics.

Highly Air-Stable, Flexible, and Water-Resistive 2D Titanium Carbide MXene-Based RGB Organic Light-Emitting Diode Displays for Transparent Free-Form Electronics.

Flexible see-through displays are considered to be the next generation smart display, providing improved information flow, safety, situational awareness, and overall user experience in smart windows, automotive displays, glass-form biomedical displays, and augmented reality systems. 2D titanium carbides (MXenes) are promising material as electrodes of the transparent and flexible displays due to their high transparency, metallic conductivity, and flexibility. However, current MXene-based devices have insufficient air stability and lack engineering schemes to develop matrix-addressable display forms with sufficient pixels to display information. Here, we develop an ultraflexible and environmentally stable MXene-based organic light-emitting diode (OLED) display by combining high performance MXene electrodes, flexible OLEDs, and ultrathin and functional encapsulation systems. The MXene material was synthesized and used to fabricate a highly reliable MXene-based OLED that can stably operate in air condition for over 2000 h, endure repetitive bending deformation of 1.5 mm radius, and maintain environmental stability for 6 h when exposed to wet surroundings. The RGB MXene-based OLEDs were fabricated, (1691 cd m-2 at 40.4 mA cm-2 for red, 1377 cd m-2 at 4.26 mA cm-2 for green, and 1475 cd m-2 at 18.6 mA cm-2 for blue) and a matrix-addressable transparent OLED display was demonstrated that could display letters and shapes.

CdS/TiO2 nano hybrid heterostructured materials for superior hydrogen production and gas sensor applications.

In efforts to minimize environmental pollution and carbon-based gas emissions, photocatalytic hydrogen production and sensing applications at ambient temperature are important. This research reports on the development of new 0D/1D materials based on TiO2 nanoparticles grown onto CdS hetersturctured nanorods via two-stage facile synthesis. The titanate nanoparticles when loaded onto CdS surfaces at an optimized concentration (20 mM), exhibited superior photocatalytic hydrogen production (21.4 mmol/h/gcat). The optimized nanohybrid was recycled for 6 cycles up to 4 h, indicating its excellent stabity for a prolonged period. Also, the photoelectrochemical water oxidation in alkaline medium was investigated to offer the optimized CRT-2 composite with 1.91 mA/cm2@0.8 V vs. RHE (0 V vs. Ag/AgCl) that was used for effective room-temperature NO2 gas detection exhibiting a higher response (69.16%) to NO2 (100 ppm) at room temperature at the lowest detection limit of ∼118 ppb than the pristine counterparts. Further, NO2 gas sensing performance of CRT-2 sensor was increased using UV light (365 nm) activation energy. Under the UV light, the sensor exhibited a remarkable gas sensing response quick response/recovery times (68/74), excellent long-term cycling stability, and significant selectivity to NO2 gas. Due to high porosity and surface area values of CdS (5.3), TiO2 (35.5), and CRT-2 (71.5 m2/g), excellent photocatalytic H2 production and gas sensing of CRT-2 is ascribed to morphology, synergistic effect, improved charge generation, and separation. Overall, 1D/0D CdS@TiO2 is proved to be an efficient material for hydrogen production and gas detection.

Catalyst-free synthesis of sub-5 nm silicon nanowire arrays with massive lattice contraction and wide bandgap.

The need for miniaturized and high-performance devices has attracted enormous attention to the development of quantum silicon nanowires. However, the preparation of abundant quantities of silicon nanowires with the effective quantum-confined dimension remains challenging. Here, we prepare highly dense and vertically aligned sub-5 nm silicon nanowires with length/diameter aspect ratios greater than 10,000 by developing a catalyst-free chemical vapor etching process. We observe an unusual lattice reduction of up to 20% within ultra-narrow silicon nanowires and good oxidation stability in air compared to conventional silicon. Moreover, the material exhibits a direct optical bandgap of 4.16 eV and quasi-particle bandgap of 4.75 eV with the large exciton binding energy of 0.59 eV, indicating the significant phonon and electronic confinement. The results may provide an opportunity to investigate the chemistry and physics of highly confined silicon quantum nanostructures and may explore their potential uses in nanoelectronics, optoelectronics, and energy systems.

Two-stage amplification of an ultrasensitive MXene-based intelligent artificial eardrum.

We report an artificial eardrum using an acoustic sensor based on two-dimensional MXene (Ti3C2Tx), which mimics the function of a human eardrum for realizing voice detection and recognition. Using MXene with a large interlayer distance and micropyramid polydimethylsiloxane arrays can enable a two-stage amplification of pressure and acoustic sensing. The MXene artificial eardrum shows an extremely high sensitivity of 62 kPa-1 and a very low detection limit of 0.1 Pa. Notably, benefiting from the ultrasensitive MXene eardrum, the machine-learning algorithm for real-time voice classification can be realized with high accuracy. The 280 voice signals are successfully classified for seven categories, and a high accuracy of 96.4 and 95% can be achieved by the training dataset and the test dataset, respectively. The current results indicate that the MXene artificial intelligent eardrum shows great potential for applications in wearable acoustical health care devices.

Non-Equilibrium Sodiation Pathway of CuSbS2.

Binary metal sulfides have been explored as sodium storage materials owing to their high theoretical capacity and high stable cyclability. Nevertheless, their relative high charge voltage and relatively low practical capacity make them less attractive as an anode material. To resolve the problem, addition of alloying elements is considerable. Copper antimony sulfide is investigated as a representative case. In this study, we do not only perform electrochemical characterization on CuSbS2, but also investigate its nonequilibrium sodiation pathway employing in-/ex situ transmission electron microscopy, in situ X-ray diffraction, and density functional theory calculations. Our finding provides valuable insights on sodium storage into ternary metal sulfide including an alloying element.

Fabrication of junction-free Cu nanowire networks via Ru-catalyzed electroless deposition and their application to transparent conducting electrodes.

Over the past few years, metal nanowire networks have attracted attention as an alternative to transparent conducting oxide materials such as indium tin oxide for transparent conducting electrode applications. Recently, electrodeposition of metal on nanoscale template is widely used for formation of metal network. In the present work, junctionless Cu nanowire networks were simply fabricated on a substrate by forming a nanostructured Ru with 80 nm width as a seed layer, followed by direct electroless deposition of Cu. By controlling the density of Ru nanowires or the electroless deposition time, we readily achieve desired transmittance and sheet resistance values ranging from ∼1 kΩ sq-1at 99% to 9 Ω sq-1at 89%. After being transferred to flexible substrates, the nanowire networks exhibited no obvious increase in resistance during 8000 cycles of a bending test to a radius of 2.5 mm. The durability was verified by evaluation of its heating performance. The maximum temperature was greater than 180 °C at 3 V and remained constant after three repeated cycles and for 10 min. Transmission electron microscopy and x-ray diffraction studies revealed that the adhesion between the electrolessly deposited Cu and the seed Ru nanowires strongly influenced the durability of the core-shell structured nanowire-based heaters.

Scalable Superior Chemical Sensing Performance of Stretchable Ionotronic Skin via a π-Hole Receptor Effect.

Skin-attachable gas sensors provide a next-generation wearable platform for real-time protection of human health by monitoring environmental and physiological chemicals. However, the creation of skin-like wearable gas sensors, possessing high sensitivity, selectivity, stability, and scalability (4S) simultaneously, has been a big challenge. Here, an ionotronic gas-sensing sticker (IGS) is demonstrated, implemented with free-standing polymer electrolyte (ionic thermoplastic polyurethane, i-TPU) as a sensing channel and inkjet-printed stretchable carbon nanotube electrodes, which enables the IGS to exhibit high sensitivity, selectivity, stability (against mechanical stress, humidity, and temperature), and scalable fabrication, simultaneously. The IGS demonstrates reliable sensing capability against nitrogen dioxide molecules under not only harsh mechanical stress (cyclic bending with the radius of curvature of 1 mm and cyclic straining at 50%), but also environmental conditions (thermal aging from -45 to 125 °C for 1000 cycles and humidity aging for 24 h at 85% relative humidity). Further, through systematic experiments and theoretical calculations, a π-hole receptor mechanism is proposed, which can effectively elucidate the origin of the high sensitivity (up to parts per billion level) and selectivity of the ionotronic sensing system. Consequently, this work provides a guideline for the design of ionotronic materials for the achievement of high-performance and skin-attachable gas-sensor platforms.

Graphitic Nanocup Architectures for Advanced Nanotechnology Applications.

The synthesis of controllable hollow graphitic architectures can engender revolutionary changes in nanotechnology. Here, we present the synthesis, processing, and possible applications of low aspect ratio hollow graphitic nanoscale architectures that can be precisely engineered into morphologies of (1) continuous carbon nanocups, (2) branched carbon nanocups, and (3) carbon nanotubes-carbon nanocups hybrid films. These complex graphitic nanocup-architectures could be fabricated by using a highly designed short anodized alumina oxide nanochannels, followed by a thermal chemical vapor deposition of carbon. The highly porous film of nanocups is mechanically flexible, highly conductive, and optically transparent, making the film attractive for various applications such as multifunctional and high-performance electrodes for energy storage devices, nanoscale containers for nanogram quantities of materials, and nanometrology.

Large-Area 2D-MXene Nanosheet Assemblies Using Langmuir-Schaefer Technique: Wrinkle formation.

The formation of uniform sheets of exfoliated MXene over a large area is important for improving their performance in practical applications. In this study, the Langmuir-Schaefer technique was employed to deposit uniform MXene sheets on a solid substrate and control the morphological structure over a large area. At the liquid-gas interface, MXene flakes were densely compressed into nanosheets with minimal gaps between them at 20 mN/m. Through further compression, the wrinkle morphologies of MXene sheets tend to be perpendicularly aligned to the compression direction. These wrinkle structures were also exhibited when MXene sheets were mixed in equal proportions with graphene oxide sheets. Owing to the close correlation of the morphologies of MXene films with the performance of MXene-based materials, the technique employed in this study can provide a route for applications requiring wrinkled MXene, ranging from nanoelectronic devices to energy storage materials, such as supercapacitors and battery electrodes.

CO2-Oxidized Ti3C2Tx-MXenes Components for Lithium-Sulfur Batteries: Suppressing the Shuttle Phenomenon through Physical and Chemical Adsorption.

Lithium-sulfur (Li-S) batteries are one of the main challenges facing Li-ion technology because the insulating nature of sulfur and the shuttle phenomenon of dissolved lithium polysulfides (LPSs) in liquid electrolytes result in critical problems, including low Coulombic efficiency, loss of active material, and rapid capacity decay. Here, we oxidized delaminated transition metal carbides (MXenes) using CO2 (Oxi-d-MXenes) and used them as both cathode electrode with sulfur and modified separator coated onto the glass fiber without a conductive material and binder to suppress the diffusion of LPSs. Oxi-d-MXenes annealed at 900 °C using CO2 gas formed perfectly converted rutile-TiO2 nanocrystalline particles on their two-dimensional sheets. Li-S batteries fabricated with the Oxi-d-MXenes cathode and the Oxi-d-MXenes-modified separator exhibited high Coulombic efficiency (nearly 99%) and retained a capacity of about 900 mAh g-1 after 300 cycles at a current density of 1C. These results were attributed to the chemical and physical adsorption between the Oxi-d-MXenes and the LPSs. Our results imply that Oxi-d-MXenes prepared by the CO2 treatment exhibit physical and electrochemical properties that enhance the performance of Li-S batteries.

Hierarchical Self-Assembly of Perylene Diimide (PDI) Crystals.

Controlling molecular self-assembly of organic semiconductors is a key factor in enhancing the performance of organic electronics and optoelectronics. However, unlike various p-type organic semiconductors, it has proven elusive to control molecular self-assembly with about tens of nm dimensions using n-type organic semiconductors including perylene diimide (PDI), which is the most promising alternative to fullerene derivatives, without using an additional synthetic method or additives, thus far. Here, we developed a simple self-assembling method for the hierarchical self-assembly of PDI crystals with nanometer-to-micrometer scale features using pristine PDI-C8 without using an additional synthetic method or additive. Interestingly, we observed crystalline and optical properties of self-assembled PDI crystals depending on their size and structural features. In addition, we fabricated p-n junctions composed of PDI and poly(3-hexylthiophene) (P3HT), where the p-n junctions had coassembled and blended nanomorphologies, and confirmed that coassembled nanomorphologies enabled more effective energy transfer than the blended nanomorphologies.

Characterization of Flagellar Filaments and Flagellin through Optical Microscopy and Label-Free Nanopore Responsiveness.

In this study, we investigated the translocation characteristics of flagellar filaments (Salmonella typhimurium) and flagellin subunits through silicon nitride nanopores in tandem with optical microscopy analysis. Even though untagged flagella are dark to the optical method, the label-free nature of the nanopore sensor allows it to characterize both tagged (Cy3) and pristine forms of flagella (including real-time developments). Flagella were depolymerized to flagellin subunits at ∼65 °C (most commonly reported temperature), ∼70 °C, ∼75 °C, and ∼80 °C to investigate the effect of temperature (Tdepol) on depolymerization. The change in conductance (ΔG) profiles corresponding to Tdepol ∼65 °C and ∼70 °C were bracketed within the flagellin monomer profile whereas those of ∼75 °C and ∼80 °C extended beyond this profile, suggesting a change to the native protein state. The molecular radius calculated from the excluded electrolyte volume of flagellin through nanopore-based ΔG characteristics for each Tdepol of ∼65 °C, ∼70 °C, ∼75 °C, and ∼80 °C yielded ∼4.2 ± 0.2 nm, ∼4.3 ± 0.3 nm, ∼4.1 ± 0.2 nm, and ∼4.7 ± 0.5 nm, respectively. This, along with ΔG (plateaued values) and translocation time profiles, points to the possibility of flagellin misfolding at ∼80 °C.

Flexible Two-Dimensional Ti3C2 MXene Films as Thermoacoustic Devices.

MXenes have attracted great attention for their potential applications in electrochemical and electronic devices due to their excellent characteristics. Traditional sound sources based on the thermoacoustic effect demonstrated that a conductor needs to have an extremely low heat capacity and high thermal conductivity. Hence, a thin MXene film with a low heat capacity per unit area (HCPUA) and special layered structure is emerging as a promising candidate to build loudspeakers. However, the use of MXenes in a sound source device has not been explored. Herein, we have successfully prepared sound source devices on an anodic aluminum oxide (AAO) and a flexible polyimide (PI) substrates by using the prepared Ti3C2 MXene nanoflakes. Due to the larger interlayer distance of MXene, the MXene-based sound source device has a higher sound pressure level (SPL) than that of graphene of the same thickness. High-quality Ti3C2 MXene nanoflakes were fabricated by selectively etching the Ti3AlC2 powder. The as-fabricated MXene sound source device on an AAO substrate exhibits a higher SPL of 68.2 dB (f = 15 kHz) and has a very stable sound spectrum output with frequency varying from 100 Hz to 20 kHz. A theoretical model has been built to explain the mechanism of the sound source device on an AAO substrate, matching well with the experimental results. Furthermore, the MXene sound source device based on a flexible PI substrate has been attached to the arms, back of the hand, and fingers, indicating an excellent acoustic wearability. Then, the MXene film is packaged successfully into a commercial earphone case and shows an excellent performance at high frequencies, which is very suitable for human audio equipment.

Pulverization-Tolerance and Capacity Recovery of Copper Sulfide for High-Performance Sodium Storage.

Finding suitable electrode materials is one of the challenges for the commercialization of a sodium ion battery due to its pulverization accompanied by high volume expansion upon sodiation. Here, copper sulfide is suggested as a superior electrode material with high capacity, high rate, and long-term cyclability owing to its unique conversion reaction mechanism that is pulverization-tolerant and thus induces the capacity recovery. Such a desirable consequence comes from the combined effect among formation of stable grain boundaries, semi-coherent boundaries, and solid-electrolyte interphase layers. The characteristics enable high cyclic stability of a copper sulfide electrode without any need of size and morphological optimization. This work provides a key finding on high-performance conversion reaction based electrode materials for sodium ion batteries.

Interfacial Assembly of Ultrathin, Functional MXene Films.

MXenes are a prominent family of two-dimensional materials because of their metallic conductivity and abundant surface functionalities. Although MXenes have been extensively studied as bulk particles or free-standing films, thin and transparent films are needed for optical, optoelectronic, sensing, and other applications. In this study, we demonstrate a facile method to fabricate ultrathin (∼10 nm), Ti3C2Tx MXene films by an interfacial assembly technique. The self-assembling behavior of MXene flakes resulted in films with a high stacking order and strong plane-to-plane adherence, where optimal films of 10 nm thickness displayed a low sheet resistance of 310 Ω/□. By using surface tension, films were transferred onto various types of planar and curved substrates. Moreover, multiple films were consecutively transferred onto substrates from a single batch of solution, showing the efficient use of the material. When the films were utilized as gas sensing channels, a high signal-to-noise ratio, up to 320, was observed, where the gas response of films assembled from small MXene flakes was 10 times larger than that from large flakes. This work provides a facile and efficient method to allow MXenes to be further exploited for thin-film applications.

Enhanced Selectivity of MXene Gas Sensors through Metal Ion Intercalation: In Situ X-ray Diffraction Study.

Gas molecules are known to interact with two-dimensional (2D) materials through surface adsorption where the adsorption-induced charge transfer governs the chemiresistive sensing of various gases. Recently, titanium carbide (Ti3C2T x) MXene emerged as a promising sensing channel showing the highest sensitivity among 2D materials and unique gas selectivity. However, unlike conventional 2D materials, MXenes show metallic conductivity and contain interlayer water, implying that gas molecules will likely interact in a more complex way than the typical charge transfer model. Therefore, it is important to understand the role of all factors that may influence gas sensing. Here, we studied the gas-induced interlayer swelling of Ti3C2T x MXene thin films and its influence on gas sensing performance. In situ X-ray diffraction was employed to simultaneously measure dynamic swelling behavior where Ti3C2T x MXene films displayed selective swelling toward ethanol vapor over CO2 gas. Results show that the controlling sodium ion concentration in the interlayers is highly important in tuning the swelling behavior and gas sensing performance. The degree of swelling matched well with the gas response intensity, and the highest gas selectivity toward ethanol vapor was achieved for Ti3C2T x sensing channels treated with 0.3 mM NaOH, which also displayed the largest amount of swelling. Our results demonstrate that controlling the interlayer transport of Ti3C2T x MXene is essential for enhancing the selective sensing of gas molecules.

An investigation into the factors governing the oxidation of two-dimensional Ti3C2 MXene.

Two-dimensional (2D) transition metal carbides (MXenes) exhibit outstanding performances in many applications, such as energy storage, optoelectronics, and electrocatalysts. However, colloidal solutions of Ti3C2Tx MXene flakes deteriorate rapidly under ambient conditions due to the conversion of the titanium carbide to titanium dioxide. Here, we discuss the dominant factors influencing the rate of oxidation of Ti3C2Tx MXene flakes, and present guidelines for their storage with the aim of maintaining the intrinsic properties of the as-prepared material. The oxidation stability of the Ti3C2Tx flakes is dramatically improved in a system where water molecules and temperature were well-controlled. It was found that aqueous solutions of Ti3C2Tx MXene can be chemically stable for more than 39 weeks when the storage temperature (-80 °C) is sufficiently low to cease the oxidation processes. It was also found that if the Ti3C2Tx flakes are dispersed in ethanol, the degradation process can be significantly delayed even at 5 °C. Moreover, the oxidation stability of the Ti3C2Tx flakes is dramatically improved in both cases, even in the presence of oxygen-containing atmosphere. We demonstrate practical applications of our approach by employing Ti3C2Tx in a gas sensor showing that when oxidation is inhibited, the device can retain the original electrical properties after 5 weeks of storage.