9 research outputs found

    Scalable Production of Few-Layer Boron Sheets by Liquid-Phase Exfoliation and Their Superior Supercapacitive Performance

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    Although two-dimensional boron (B) has attracted much attention in electronics and optoelectronics due to its unique physical and chemical properties, in-depth investigations and applications have been limited by the current synthesis techniques. Herein, we demonstrate that high-quality few-layer B sheets can be prepared in large quantities by sonication-assisted liquid-phase exfoliation. By simply varying the exfoliating solvent types and centrifugation speeds, the lateral size and thickness of the exfoliated B sheets can be controllably tuned. Additionally, the exfoliated few-layer B sheets exhibit excellent stability and outstanding dispersion in organic solvents without aggregates for more than 50 days under ambient conditions, owing to the presence of a solvent residue shell on the B sheet surface that provides excellent protection against air oxidation. Moreover, we also demonstrate the use of the exfoliated few-layer B sheets for high-performance supercapacitor electrode materials. This as-prepared device exhibits impressive electrochemical performance with a wide potential window of up to 3.0 V, excellent energy density as high as 46.1 Wh/kg at a power density of 478.5 W/kg, and excellent cycling stability with 88.7% retention of the initial specific capacitance after 6000 cycles. This current work not only demonstrates an effective strategy for the synthesis of the few-layer B sheets in a controlled manner but also makes the resulting materials promising for next-generation optoelectronics and energy storage applications

    Facile Synthesis of Millimeter-Scale Vertically Aligned Boron Nitride Nanotube Forests by Template-Assisted Chemical Vapor Deposition

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    There is an increasing amount of research interest in synthesizing boron nitride nanotubes (BNNTs) as well as BN coatings to be used for various applications due to their outstanding mechanical, electrical, and thermal properties. However, vertically aligned (VA) BNNTs are difficult to synthesize and the longest VA-BNNTs achieved to date are up to several tens of microns. Here, we report the synthesis of over millimeters long multiwalled BN coated carbon nanotubes (BN/CNT) and BNNT forests via a facile and effective two-step route involving template-assisted chemical vapor deposition at a relatively low temperature of 900 °C and a subsequent annealing process. The as-prepared BN/CNTs and BNNTs retain the highly ordered vertically aligned structures of the CNT templates as identified by scanning electron microscopy. The structure and composition of the resulting products were studied using transmission electron microscopy, electron energy-loss spectroscopy, X-ray photoelectron spectroscopy, Raman spectroscopy, Fourier transform infrared spectroscopy, and thermogravimetric analysis. This versatile BN coating technique and the synthesis of millimeter-scale BN/CNTs and BNNTs pave the way for new applications especially where the aligned geometry of the NTs is essential such as for field-emission, interconnects, and thermal management

    Supercompressible Coaxial Carbon Nanotube@Graphene Arrays with Invariant Viscoelasticity over −100 to 500 °C in Ambient Air

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    Vertically aligned carbon nanotube (CNT) arrays have been recognized as promising cushion materials because of their superior thermal stability, remarkable compressibility, and viscoelastic characteristics. However, most of the previously reported CNT arrays still suffer from permanent shape deformation at only moderate compressive strains, which considerably restricts their practical applications. Here, we demonstrate a facile strategy of fabricating supercompressible coaxial CNT@graphene (CNT@Gr) arrays by using a two-step route involving encapsulating polymer layers onto plastic CNT arrays and subsequent annealing processes. Notably, the resulting CNT@Gr arrays are able to almost completely recover from compression at a strain of up to 80% and retain ∼80% recovery even after 1000 compression cycles at a 60% strain, demonstrating their excellent compressibility. Furthermore, they possess outstanding strain- and frequency-dependent viscoelastic responses, with storage modulus and damping ratio of up to ∼6.5 MPa and ∼0.19, respectively, which are nearly constant over an exceptionally broad temperature range of −100 to 500 °C in ambient air. These supercompressibility and temperature-invariant viscoelasticity together with facile fabrication process of the CNT@Gr arrays enable their promising multifunctional applications such as energy absorbers, mechanical sensors, and heat exchangers, even in extreme environments

    Trimethylamine Borane: A New Single-Source Precursor for Monolayer h‑BN Single Crystals and h‑BCN Thin Films

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    Due to their exceptional chemical and thermal stabilities as well as electrically insulating property, atomically thin hexagonal boron nitride (h-BN) films have been identified as a promising class of dielectric substrate and encapsulation material for high-performance two-dimensional (2D) heterostructure devices. Herein, we report a facile chemical vapor deposition synthesis of large-area atomically thin h-BN including monolayer single crystals and C-doped h-BN (h-BCN) films utilizing a relatively low-cost, commercially available trimethylamine borane (TMAB) as a single-source precursor. Importantly, pristine 2D h-BN films with a wide band gap of ∼6.1 eV can be achieved by limiting the sublimation temperature of TMAB at 40 °C, while C dopants are introduced to the h-BN films when the sublimation temperature is further increased. The h-BCN thin films displayed band gap narrowing effects as identified by an additional shoulder at 205 nm observed in their absorbance spectra. Presence of N–C bonds in the h-BCN structures with a doping concentration of ∼2 to 5% is confirmed by X-ray photoelectron spectroscopy. The inclusion of low C doping in the h-BN films is expected to result in constructive enhancement to its mechanical properties without significant alteration to its electrically insulating nature. This study provides new insights into the design and fabrication of large-area atomically thin h-BN/h-BCN films toward practical applications and suggests that the range of precursors can be potentially extended to other anime borane complexes as well

    Control of Nanoplane Orientation in voBN for High Thermal Anisotropy in a Dielectric Thin Film: A New Solution for Thermal Hotspot Mitigation in Electronics

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    High anisotropic thermal materials, which allow heat to dissipate in a preferential direction, are of interest as a prospective material for electronics as an effective thermal management solution for hot spots. However, due to their preferential heat propagation in the in-plane direction, the heat spreads laterally instead of vertically. This limitation makes these materials ineffective as the density of hot spots increases. Here, we produce a new dielectric thin film material at room temperature, named vertically ordered nanocrystalline h-BN (voBN). It is produced such that its preferential thermally conductive direction is aligned in the vertical axis, which facilitates direct thermal extraction, thereby addressing the increasing challenge of thermal crosstalk. The uniqueness of voBN comes from its h-BN nanocrystals where all their basal planes are aligned in the direction normal to the substrate plane. Using the 3ω method, we show that voBN exhibits high anisotropic thermal conductivity (TC) with a 16-fold difference between through-film TC and in-plane TC (respectively 4.26 and 0.26 W·m<sup>–1</sup>·K<sup>–1</sup>). Molecular dynamics simulations also concurred with the experimental data, showing that the origin of this anisotropic behavior is due to the nature of voBN’s plane ordering. While the consistent vertical ordering provides an uninterrupted and preferred propagation path for phonons in the through-film direction, discontinuity in the lateral direction leads to a reduced in-plane TC. In addition, we also use COMSOL to simulate how the dielectric and thermal properties of voBN enable an increase in hot spot density up to 295% compared with SiO<sub>2</sub>, without any temperature increase

    High-Density 3D-Boron Nitride and 3D-Graphene for High-Performance Nano–Thermal Interface Material

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    Compression studies on three-dimensional foam-like graphene and h-BN (3D-C and 3D-BN) revealed their high cross-plane thermal conductivity (62–86 W m<sup>–1</sup> K<sup>–1</sup>) and excellent surface conformity, characteristics essential for thermal management needs. Comparative studies to state-of-the-art materials and other materials currently under research for heat dissipation revealed 3D-foam’s improved performance (20–30% improved cooling, temperature decrease by Δ<i>T</i> of 44–24 °C)

    Growth of Large Single-Crystalline Two-Dimensional Boron Nitride Hexagons on Electropolished Copper

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    Hexagonal-boron nitride (h-BN) or “white graphene” has many outstanding properties including high thermal conductivity, high mechanical strength, chemical inertness, and high electrical resistance, which open up a wide range of applications such as thermal interface material, protective coatings, and dielectric in nanoelectronics that easily exceed the current advertised benefits pertaining to the graphene-based applications. The development of h-BN films using chemical vapor deposition (CVD) has thus far led into nucleation of triangular or asymmetric diamond shapes on different metallic surfaces. Additionally, the average size of the triangular domains has remained relatively small (∼0.5 μm<sup>2</sup>) leading to a large number of grain boundaries and defects. While the morphology of Cu surfaces for CVD-grown graphene may have impacts on the nucleation density, domain sizes, thickness, and uniformity, the effects of the decreased roughness of Cu surface to develop h-BN films are unknown. Here, we report the growth and characterization of novel large area h-BN hexagons using highly electropolished Cu substrate under atmospheric pressure CVD conditions. We found that the nucleation density of h-BN is significantly reduced while domain sizes increase. In this study, the largest hexagonal-shape h-BN domain observed is 35 μm<sup>2</sup>, which is an order of magnitude larger than a typical triangular domain. As the domains coalesce to form a continuous film, the larger grain size offers a more pristine and smoother film with lesser grain boundaries induced defects

    Biocompatible Hydroxylated Boron Nitride Nanosheets/Poly(vinyl alcohol) Interpenetrating Hydrogels with Enhanced Mechanical and Thermal Responses

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    Poly­(vinyl alcohol) (PVA) hydrogels with tissue-like viscoelasticity, excellent biocompatibility, and high hydrophilicity have been considered as promising cartilage replacement materials. However, lack of sufficient mechanical properties is a critical barrier to their use as load-bearing cartilage substitutes. Herein, we report hydroxylated boron nitride nanosheets (OH-BNNS)/PVA interpenetrating hydrogels by cyclically freezing/thawing the aqueous mixture of PVA and highly hydrophilic OH-BNNS (up to 0.6 mg/mL, two times the highest reported so far). Encouragingly, the resulting OH-BNNS/PVA hydrogels exhibit controllable reinforcements in both mechanical and thermal responses by simply varying the OH-BNNS contents. Impressive 45, 43, and 63% increases in compressive, tensile strengths and Young’s modulus, respectively, can be obtained even with only 0.12 wt% (OH-BNNS:PVA) OH-BNNS addition. Meanwhile, exciting improvements in the thermal diffusivity (15%) and conductivity (5%) can also be successfully achieved. These enhancements are attributed to the synergistic effect of intrinsic superior properties of the as-prepared OH-BNNS and strong hydrogen bonding interactions between the OH-BNNS and PVA chains. In addition, excellent cytocompatibility of the composite hydrogels was verified by cell proliferation and live/dead viability assays. These biocompatible OH-BNNS/PVA hydrogels are promising in addressing the mechanical failure and locally overheating issues as cartilage substitutes and may also have broad utility for biomedical applications, such as drug delivery, tissue engineering, biosensors, and actuators

    Concentric and Spiral Few-Layer Graphene: Growth Driven by Interfacial Nucleation vs Screw Dislocation

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    Spiral growth of various nanomaterials including some two-dimensional (2D) transition metal dichalcogenides had recently been experimentally realized using chemical vapor deposition (CVD). However, such growth that is driven by screw dislocation remained elusive for graphene and is rarely discussed because of the use of metal catalysts. In this work, we show that formation of few-layer graphene (FLG) with a spiral structure driven by screw dislocation can be obtained alongside FLG having a concentric layered structure formed by interfacial nucleation (nucleation at the graphene/Cu interface) using Cu-catalyzed ambient pressure CVD. Unlike commonly reported FLG grown by interfacial nucleation where the second layer is grown independently beneath the first, the growth of a spiral structure adopts a top growth mechanism where the top layers are an extension from the initial monolayer which spirals around an axial dislocation in self-perpetuating steps. Since the same atomic orientation is preserved, the subsequent spiraling layers are stacked in an oriented AB-stacked configuration. This contrasts with FLG formed by interfacial nucleation where turbostratic stacking of the entire adlayer may exist. In both growth scenarios, the second layer (either top or bottom) can grow across the grain boundaries of the initial monolayer domains, forming partial regions with turbostratic stacking configuration due to weak interlayer van der Waals interactions. The unique interlayer coupling of FLG spirals, which enable superior conductivity along the normal of the 2D crystal with spiraling trajectories, are expected to have new and interesting nanoscale applications
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