Efficient intersystem crossing and tunable ultralong organic room-temperature phosphorescence via doping polyvinylpyrrolidone with polyaromatic hydrocarbons.

Polymer-based pure organic room-temperature phosphorescent materials have tremendous advantages in applications owing to their low cost, vast resources, and easy processability. However, designing polymer-based room-temperature phosphorescent materials with large Stokes shifts as key requirements in biocompatibility and environmental-friendly performance is still challenging. By generating charge transfer states as the gangplank from singlet excited states to triplet states in doped organic molecules, we find a host molecule (pyrrolidone) that affords charge transfer with doped guest molecules, and excellent polymer-based organic room-temperature phosphorescent materials can be easily fabricated when polymerizing the host molecule. By adding polyaromatic hydrocarbon molecules as electron-donor in polyvinylpyrrolidone, efficient intersystem crossing and tunable phosphorescent from green to near-infrared can be achieved, with maximum phosphorescence wavelength and lifetime up to 757 nm and 3850 ms, respectively. These doped polyvinylpyrrolidone materials have good photoactivation properties, recyclability, advanced data encryption, and anti-counterfeiting. This reported design strategy paves the way for the design of polyvinylpyrrolidone-based room-temperature phosphorescent materials.

Cellulose/GO monolith covered with Pd-Pt bimetallic nanocrystals for continuous-flow catalytic reduction of hexavalent chromium.

Cellulose monolith materials have interconnected open porous structures with very high porosity, making them attractive structures for use as support materials in heterogeneous catalysis applications. In this study, we developed a highly efficient and reusable continuous-flow reactor for Cr(VI) remediation by combining the advantageous features of cellulose monoliths with suitable reinforcement techniques. We fabricated a porous monolithic cellulose/graphene oxide (GO) composite with a continuous three-dimensional skeletal framework using the thermally induced phase separation technique. Pd nanocrystals were synthesized in situ on the surface of the composite monolith, and then converted to porous Pd-Pt bimetallic nanocrystals through a galvanic replacement reaction. This approach eliminated the need for additional reductants and stabilizers, making the process simpler and more environmentally friendly. Under carefully optimized conditions, the cellulose/GO/Pd-Pt nanocomposite monolith exhibited outstanding performance in continuous-flow reactions for Cr(VI) reduction, achieving a maximum conversion rate of 98 %. Moreover, the nanocomposite monolith-based heterogeneous catalyst exhibited remarkable long-term stability, maintaining its catalytic activity even after extended periods of storage in the dried state. These findings highlight the potential of cellulose-based composite monoliths as versatile and robust support materials for heterogeneous catalysis.

Fully Printed, High-Temperature Micro-Supercapacitor Arrays Enabled by a Hexagonal Boron Nitride Ionogel Electrolyte.

The proliferation and miniaturization of portable electronics require energy-storage devices that are simultaneously compact, flexible, and amenable to scalable manufacturing. In this work, mechanically flexible micro-supercapacitor arrays are demonstrated via sequential high-speed screen printing of conductive graphene electrodes and a high-temperature hexagonal boron nitride (hBN) ionogel electrolyte. By combining the superlative dielectric properties of 2D hBN with the high ionic conductivity of ionic liquids, the resulting hBN ionogel electrolyte enables micro-supercapacitors with exceptional areal capacitances that approach 1 mF cm-2 . Unlike incumbent polymer-based electrolytes, the high-temperature stability of the hBN ionogel electrolyte implies that the printed micro-supercapacitors can be operated at unprecedentedly high temperatures up to 180 °C. These elevated operating temperatures result in increased power densities that make these printed micro-supercapacitors particularly promising for applications in harsh environments such as underground exploration, aviation, and electric vehicles. The combination of enhanced functionality in extreme conditions and high-speed production via scalable additive manufacturing significantly broadens the technological phase space for on-chip energy storage.

Enhanced LiMn2O4 Thin-Film Electrode Stability in Ionic Liquid Electrolyte: A Pathway to Suppress Mn Dissolution.

Spinel-type lithium manganese oxide (LiMn2O4) cathodes suffer from severe manganese dissolution in the electrolyte, compromising the cyclic stability of LMO-based Li-ion batteries (LIBs). In addition to causing structural and morphological deterioration to the cathode, dissolved Mn ions can migrate through the electrolyte to deposit on the anode, accelerating capacity fade. Here, we examine single-crystal epitaxial LiMn2O4 (111) thin-films using synchrotron in situ X-ray diffraction and reflectivity to study the structural and interfacial evolution during cycling. Cyclic voltammetry is performed in a wide range (2.5-4.3 V vs Li/Li+) to promote Mn3+ formation, which enhances dissolution, for two different electrolyte systems: an imidazolium ionic liquid containing lithium bis-(trifluoromethylsulfonyl)imide (LiTFSI) and a conventional carbonate liquid electrolyte containing lithium hexafluorophosphate (LiPF6). We find exceptional stability in this voltage range for the ionic liquid electrolyte compared to the conventional electrolyte, which is attributed to the absence of Mn dissolution in the ionic liquid. X-ray reflectivity shows a negligible loss of cathode material for the films cycled in the ionic liquid electrolyte, further confirmed by inductively coupled plasma mass spectrometry and transmission electron microscopy. Conversely, a substantial loss of Mn is found when the film is cycled in the conventional electrolyte. These findings show the significant advantages of ionic liquids in suppressing Mn dissolution in LiMn2O4 LIB cathodes.

Screen-Printable Hexagonal Boron Nitride Ionogel Electrolytes for Mechanically Deformable Solid-State Lithium-Ion Batteries.

Ionogel electrolytes present several benefits for solid-state lithium-ion batteries including nonflammability, favorable electrochemical properties, and high thermal stability. However, limited processing methods are currently available for ionogel electrolytes, restricting their practical applications. Here, we present a screen-printable ionogel electrolyte formulation based on hexagonal boron nitride (hBN) nanoplatelets. To achieve screen-printable rheological properties, hBN nanoplatelets are mixed with an imidazolium ionic liquid in ethyl lactate. Following screen printing, the resulting spatially uniform and mechanically flexible hBN ionogel electrolytes achieve high room-temperature ionic conductivities >1 mS cm-1 and stiff mechanical moduli >1 MPa. These hBN ionogel electrolytes enable the fabrication of fully screen-printed lithium-ion batteries with high cycling stability, rate performance, and mechanical resilience against flexion and external forces, thus providing a robust energy storage solution that is compatible with scalable additive manufacturing.

Layered Heterostructure Ionogel Electrolytes for High-Performance Solid-State Lithium-Ion Batteries.

Ionogel electrolytes based on ionic liquids and gelling matrices offer several advantages for solid-state lithium-ion batteries, including nonflammability, wide processing compatibility, and favorable electrochemical and thermal properties. However, the absence of ionic liquids that are concurrently stable at low and high potentials constrains the electrochemical windows of ionogel electrolytes and thus their high-energy-density applications. Here, ionogel electrolytes with a layered heterostructure are introduced, combining high-potential (anodic stability: >5 V vs Li/Li+ ) and low-potential (cathodic stability: <0 V vs Li/Li+ ) imidazolium ionic liquids in a hexagonal boron nitride nanoplatelet matrix. These layered heterostructure ionogel electrolytes lead to extended electrochemical windows, while preserving high ionic conductivity (>1 mS cm-1 at room temperature). Using the layered heterostructure ionogel electrolytes, full-cell solid-state lithium-ion batteries with a nickel manganese cobalt oxide cathode and a graphite anode are demonstrated, exhibiting voltages that are unachievable with either the high-potential or low-potential ionic liquid alone. Compared to ionogel electrolytes based on mixed ionic liquids, the layered heterostructure ionogel electrolytes enable higher stability operation of full-cell lithium-ion batteries, resulting in significantly enhanced cycling performance.

Printable hexagonal boron nitride ionogels.

Due to its excellent chemical/thermal stability and mechanical robustness, hexagonal boron nitride (hBN) is a promising solid matrix material for ionogels. While bulk hBN ionogels have been employed in macroscopic applications such as lithium-ion batteries, hBN ionogel inks that are compatible with high-resolution printing have not yet been realized. Here, we describe aerosol jet-printable ionogels using exfoliated hBN nanoplatelets as the solid matrix. The hBN nanoplatelets are produced from bulk hBN powders by liquid-phase exfoliation, allowing printable hBN ionogel inks to be formulated following the addition of an imidazolium ionic liquid and ethyl lactate. The resulting inks are reliably printed with variable patterns and controllable thicknesses by aerosol jet printing, resulting in hBN ionogels that possess high room-temperature ionic conductivities and storage moduli of >3 mS cm-1 and >1 MPa, respectively. By integrating the hBN ionogel with printed semiconductors and electrical contacts, fully-printed thin-film transistors with operating voltages below 1 V are demonstrated on polyimide films. These devices exhibit desirable electrical performance and robust mechanical tolerance against repeated bending cycles, thus confirming the suitability of hBN ionogels for printed and flexible electronics.

Phase-Inversion Polymer Composite Separators Based on Hexagonal Boron Nitride Nanosheets for High-Temperature Lithium-Ion Batteries.

By preventing electrical contact between anode and cathode electrodes while promoting ionic transport, separators are critical components in the safe operation of rechargeable battery technologies. However, traditional polymer-based separators have limited thermal stability, which has contributed to catastrophic thermal runaway failure modes that have conspicuously plagued lithium-ion batteries. Here, we describe the development of phase-inversion composite separators based on carbon-coated hexagonal boron nitride (hBN) nanosheets and poly(vinylidene fluoride) (PVDF) polymers that possess high porosity, electrolyte wettability, and thermal stability. The carbon-coated hBN nanosheets are obtained through a scalable liquid-phase shear exfoliation method using ethyl cellulose as a polymer stabilizer and source of the carbon coating following thermal pyrolysis. When incorporated within the PVDF matrix, the carbon-coated hBN nanosheets promote favorable interfacial interactions during the phase-inversion process, resulting in porous, flexible, free-standing composite separators. The unique chemical composition of these carbon-coated hBN separators implies high wettability for a wide range of liquid electrolytes. This combination of high porosity and electrolyte wettability enables enhanced ionic conductivity and lithium-ion battery electrochemical performance that exceeds incumbent polyolefin separators over a wide range of operating conditions. The hBN nanosheets also impart high thermal stability, providing safe lithium-ion battery operation up to 120 °C.

High-Modulus Hexagonal Boron Nitride Nanoplatelet Gel Electrolytes for Solid-State Rechargeable Lithium-Ion Batteries.

Solid-state electrolytes based on ionic liquids and a gelling matrix are promising for rechargeable lithium-ion batteries due to their safety under diverse operating conditions, favorable electrochemical and thermal properties, and wide processing compatibility. However, gel electrolytes also suffer from low mechanical moduli, which imply poor structural integrity and thus an enhanced probability of electrical shorting, particularly under conditions that are favorable for lithium dendrite growth. Here, we realize high-modulus, ion-conductive gel electrolytes based on imidazolium ionic liquids and exfoliated hexagonal boron nitride (hBN) nanoplatelets. Compared to conventional bulk hBN microparticles, exfoliated hBN nanoplatelets improve the mechanical properties of gel electrolytes by 2 orders of magnitude (shear storage modulus ∼5 MPa), while retaining high ionic conductivity at room temperature (>1 mS cm-1). Moreover, exfoliated hBN nanoplatelets are compatible with high-voltage cathodes (>5 V vs Li/Li+) and impart exceptional thermal stability that allows high-rate operation of solid-state rechargeable lithium-ion batteries at temperatures up to 175 °C.

All-Printed, Self-Aligned Carbon Nanotube Thin-Film Transistors on Imprinted Plastic Substrates.

We present a self-aligned process for printing thin-film transistors (TFTs) on plastic with single-walled carbon nanotube (SWCNT) networks as the channel material. The SCALE (self-aligned capillarity-assisted lithography for electronics) process combines imprint lithography with inkjet printing. Specifically, inks are jetted into imprinted reservoirs, where they then flow into narrow device cavities due to capillarity. Here, we incorporate a composite high- k gate dielectric and an aligned conducting polymer gate electrode in the SCALE process to enable a smaller areal footprint than prior designs that yields low-voltage SWCNT TFTs with average p-type carrier mobilities of 4 cm2/V·s and ON/OFF current ratios of 104. Our work demonstrates the promising potential of the SCALE process to fabricate SWCNT-based TFTs with favorable I- V characteristics on plastic substrates.

Enhanced Sensitivity of Patterned Graphene Strain Sensors Used for Monitoring Subtle Human Body Motions.

With the growth of the wearable electronics industry, structural modifications of sensing materials have been widely attempted to improve the sensitivity of sensors. Herein, we demonstrate patterned graphene strain sensors, which can monitor small-scale motions by using the simple, scalable, and solution-processable method. The electrical properties of the sensors are easily tuned via repetition of the layer-by-layer assembly, leading to increment of thickness of the conducting layers. In contrast to nonpatterned sensors, the patterned sensors show enhanced sensitivity and the ability to distinguish subtle motions, such as similar phonations and 81 beats per minute of pulse rate.

All-Printed, Foldable Organic Thin-Film Transistors on Glassine Paper.

All-printed, foldable organic thin-film transistors are demonstrated on glassine paper with a combination of advanced materials and processing techniques. Glassine paper provides a suitable surface for high-performance printing methods, while graphene electrodes and an ion-gel gate dielectric enable robust stability over 100 folding cycles. Altogether, this study features a practical platform for low-cost, large-area, and foldable electronics.

Screen Printing of Highly Loaded Silver Inks on Plastic Substrates Using Silicon Stencils.

Screen printing is a potential technique for mass-production of printed electronics; however, improvement in printing resolution is needed for high integration and performance. In this study, screen printing of highly loaded silver ink (77 wt %) on polyimide films is studied using fine-scale silicon stencils with openings ranging from 5 to 50 µm wide. This approach enables printing of high-resolution silver lines with widths as small as 22 µm. The printed silver lines on polyimide exhibit good electrical properties with a resistivity of 5.5×10(-6) Ω cm and excellent bending tolerance for bending radii greater than 5 mm (tensile strains less than 0.75%).

Highly stretchable and wearable graphene strain sensors with controllable sensitivity for human motion monitoring.

Because of their outstanding electrical and mechanical properties, graphene strain sensors have attracted extensive attention for electronic applications in virtual reality, robotics, medical diagnostics, and healthcare. Although several strain sensors based on graphene have been reported, the stretchability and sensitivity of these sensors remain limited, and also there is a pressing need to develop a practical fabrication process. This paper reports the fabrication and characterization of new types of graphene strain sensors based on stretchable yarns. Highly stretchable, sensitive, and wearable sensors are realized by a layer-by-layer assembly method that is simple, low-cost, scalable, and solution-processable. Because of the yarn structures, these sensors exhibit high stretchability (up to 150%) and versatility, and can detect both large- and small-scale human motions. For this study, wearable electronics are fabricated with implanted sensors that can monitor diverse human motions, including joint movement, phonation, swallowing, and breathing.

High-resolution, high-aspect ratio conductive wires embedded in plastic substrates.

A novel method is presented to fabricate high-resolution, high-aspect ratio metal wires embedded in a plastic substrate for flexible electronics applications. In a sequential process, high-resolution channels connected to low-resolution reservoirs are first created in a thermosetting polymer by imprint lithography. A reactive Ag ink is then inkjet-printed into the reservoirs and wicked into the channels by capillary forces. These features serve as a seed layer for copper deposition inside the channels via electroless plating. Highly conductive wires (>50% bulk metal) with minimum line width and spacing of 2 and 4 µm, respectively, and an aspect ratio of 0.6 are obtained. The embedded wires exhibit good mechanical flexibility, with minimal degradation in electrical performance after thousands of bending cycles.

High-resolution patterning of graphene by screen printing with a silicon stencil for highly flexible printed electronics.

High-resolution screen printing of pristine graphene is introduced for the rapid fabrication of conductive lines on flexible substrates. Well-defined silicon stencils and viscosity-controlled inks facilitate the preparation of high-quality graphene patterns as narrow as 40 µm. This strategy provides an efficient method to produce highly flexible graphene electrodes for printed electronics.

Two-dimensional TiO2 honeycomb structure for enhanced light extraction from polymer light-emitting diodes.

We have demonstrated the preparation of an ordered hole pattern via a simple colloidal assembly technique and a sol-gel process without the use of any special equipment to enhance light extraction from polymer light-emitting diodes (LEDs). From two-dimensional (2D) polystyrene (PS) colloidal crystals, 2D TiO2 honeycomb structures were easily obtained after depositing TiO(x) sol solution onto the colloidal crystals by a doctor blade technique and removing the PS colloidal particles. In order to optimize the thickness of the deposited TiO(x) materials for fabricating 2D TiO2 honeycomb structures, the concentration of the TiO(x) sol solution was controlled. By applying the 2D TiO2 honeycomb structure on the backside of the glass substrate, the efficiency of a polymer LED, compared to the device without the structure, was increased without a significant change in the electroluminescence spectrum. This enhancement is attributed to the improved light extraction, which is due to the suppression of total internal reflection at the interface between the glass substrate and the air.

Foldable graphene electronic circuits based on paper substrates.

Graphene electronic circuits are prepared on paper substrates by using graphene nanoplates and applied to foldable paper-based electronics. The graphene circuits show a small change in conductance under various folding angles and maintain an electronic path on paper substrates after repetition of folding and unfolding. Foldable paper-based applications with graphene circuits exhibit excellent folding stability.

A Case of Obstructive Jaundice Caused by Paradoxical Reaction during Antituberculous Chemotherapy for Abdominal Tuberculosis.

Abdominal tuberculosis is not a rare disease, but obstructive jaundice caused by tuberculosis (tuberculous lymphadenitis, tuberculous enlargement of the head of pancreas, and/or tuberculous stricture of the biliary tree) is rare. We recently experienced a case of obstructive jaundice as a result of paradoxical reaction of periportal tuberculous lymphadenopathy that was treated successfully with corticosteroid and biliary drainage. No similar cases have been reported previously.