On the Synthesis of Carbon Nanofibers and Nanotubes by Microwave Irradiation: Parameters,Catalysts, and Substrates

The microwave (MW)‐assisted synthesis of one dimensional carbon systems is introduced as a promising approach to improve the speed and cost‐effectiveness of the fabrication process. Improved reaction conditions are generated by direct MW heating and synthesis under advanced reaction conditions. The influence of the reaction conditions is investigated and the importance of individual process parameters on the synthesis is discussed. Temperature and pressure data recorded during the irradiation process are analyzed in detail and allow the determination of essential process parameters. This leads to improved reaction conditions, better control of the one‐dimensional carbon nanosystems by tuning the catalyst materials, and allows expanding this approach to initiate the synthesis on a variety of different substrates, such as quartz glass and mica.     

3D Interconnected Porous Carbon Aerogels as Sulfur Immobilizers for Sulfur Impregnation for Lithium‐Sulfur Batteries with High Rate Capability and Cycling Stability

To eliminate capacity‐fading effects due to the loss of sulfur cathode materials as a result of polysulfide dissolution in lithium–sulfur (Li–S) cells, 3D carbon aerogel (CA) materials with abundant narrow micropores can be utilized as an immobilizer host for sulfur impregnation. The effects of S incorporation on microstructure, surface area, pore size distribution, and pore volume of the S/CA hybrids are studied. The electrochemical performance of the S/CA hybrids is investigated using electrochemical impedance spectroscopy, galvanostatical charge–discharge, and cyclic voltammetry techniques. The 3D porous S/CA hybrids exhibit significantly improved reversible capacity, high‐rate capability, and excellent cycling performance as a cathode electrode for Li–S batteries. The S/CA hybrid with an optimal incorporating content of 27% S shows an excellent reversible capacity of 820 mAhg^?1 after 50 cycles at a current density of 100 mAg^?1. Even at a current density of 3.2C (5280 mAg^?1), the reversible capacity of 27%S/CA hybrid can still maintain at 521 mAhg^?1 after 50 cycles. This strategy for the S/CA hybrids as cathode materials to utilize the abundant micropores for sulfur immobilizers for sulfur impregnation for Li–S battery offers a new way to solve the long‐term reversibility obstacle and provides guidelines for designing cathode electrode architectures.     

Flexible Thermoelectric Polymer Composites Based on a Carbon Nanotubes Forest

Polymer‐based composites are of high interest in the field of thermoelectric (TE) materials because of their properties: abundance, low thermal conductivity, and nontoxicity. In applications, like TE for wearable energy harvesting, where low operating temperatures are required, polymer composites demonstrate compatible with the targeted specifications. The main challenge is reaching high TE efficiency. Fillers and chemical treatments can be used to enhance TE performance of the polymer matrix. The combined application of vertically aligned carbon nanotubes forest (VA‐CNTF) is demonstrated as fillers and chemical post‐treatment to obtain high‐efficiency TE composites, by dispersing VA‐CNTF into a poly (3,4‐ethylenedioxythiophene) polystyrene sulfonate matrix. The VA‐CNTF keeps the functional properties even in flexible substrates. The morphology, structure, composition, and functional features of the composites are thoroughly investigated. A dramatic increase of power factor is observed at the lowest operating temperature difference ever reported. The highest Seebeck coefficient and electrical conductivity are 58.7 µV K^?1 and 1131 S cm^?1, respectively. The highest power factor after treatment is twice as high in untreated samples. The results demonstrate the potential for the combined application of VA‐CNTF and chemical post‐treatment, in boosting the TE properties of composite polymers toward the development of high efficiency, low‐temperature, flexible TEs.     

Flexible 3D Porous MoS2/CNTs Architectures with ZT of 0.17 at Room Temperature for Wearable Thermoelectric Applications

Developing materials that possess high electrical conductivities (σ) and Seebeck coefficients (S), low thermal conductivities (κ), and excellent mechanical properties is important to realize practical thermoelectric (TE) devices. Here, 3D hierarchical architectures consisting of hybrid molybdenum disulfide (MoS₂)/carbon nanotubes (CNTs) films are fabricated with the goal of increasing σ and decreasing κ. In these films, perpendicularly orientated CNTs interpenetrate restacked MoS₂ layers to form a 3D architecture, which increases the specific surface area and charge concentration. The MoS₂/20 wt% CNTs film shows high σ (235 ± 5 S?cm^?1), high S (68 ± 2 µV?K^?1), and low κ (19 ± 2 mW?m^?1?K^?1). The corresponding figure of merit (ZT) reaches 0.17 at room temperature, which is 65 times higher than that of pure MoS₂ film. In addition, the MoS₂/20 wt% CNTs film shows a tensile stress of 38.9 MPa, which is an order of magnitude higher than that of a control MoS₂ film. Using the MoS₂/CNTs film as an active material and human body as a heat source, a flexible, wearable TE wristband is fabricated by weaving seven strips of the 3D porous MoS₂/CNTs film. The wristband achieves an output voltage of 2.9 mV and corresponding power output of 0.22 µW at a temperature gradient of about 5 K.     

Fabrication of Low‐Threshold 3D Void Structures inside a Polymer Matrix Doped with Gold Nanorods

We report on a low‐threshold three‐dimensional (3D) void generation inside a polyvinyl‐alcohol (PVA) polymer matrix doped with gold nanorods (NRs) by near infra red femtosecond laser pulses. By matching the laser wavelength to the surface plasmon resonance band of the embedded gold NRs, the void generation threshold could be reduced by one order of magnitude lower than undoped matrix. We discuss physical mechanisms involved in the void generation, where distinction between the decomposition of gold NR or PVA is drawn in single pulse and multiple pulse irradiations. We also demonstrate 3D void recording for applications in 3D optical data storage.     

Highly Stretchable Conductors Integrated with a Conductive Carbon Nanotube/Graphene Network and 3D Porous Poly(dimethylsiloxane)

Here, a novel and facile method is reported for manufacturing a new stretchable conductive material that integrates a hybrid three dimensional (3D) carbon nanotube (CNT)/reduced graphene oxide (rGO) network with a porous poly(dimethylsiloxane) (p‐PDMS) elastomer (pPCG). This reciprocal architecture not only alleviates the aggregation of carbon nanofillers but also significantly improves the conductivity of pPCG under large strains. Consequently, the pPCG exhibits high electrical conductivity with a low nanofiller loading (27 S m^?1 with 2 wt% CNTs/graphene) and a notable retention capability after bending and stretching. The simulation of the mechanical properties of the p‐PDMS model demonstrates that an extremely large applied strain (ε_appl) can be accommodated through local rotations and bending of cell walls. Thus, after a slight decrease, the conductivity of pPCG can continue to remain constant even as the strain increases to 50%. In general, this architecture of pPCG with a combination of a porous polymer substrate and 3D carbon nanofiller network possesses considerable potential for numerous applications in next‐generation stretchable electronics.     

柔性聚合物基材上三维纳米问隙的制作及互连

利用普通的紫外光刻、等离子体刻蚀、剥离和薄膜技术,在生物和半导体技术兼容的柔性聚对二甲苯-C基材上制作出了三维纳米间隙结构.室温下,使用介质电泳的方法对制作的纳米间隙进行材料集成实验.在间距80 nm的间隙电极间,实现了碳纳米管的互连.Ⅰ-Ⅴ特性测试显示,互联后电极之间表现出了较好的线性导电特征.当使用的碳纳米管电泳液...     

Rapid,One‐Step,Digital Selective Growth of ZnO Nanowires on 3D Structures Using Laser Induced Hydrothermal Growth

For functional nanowire based electronics fabrication, conventionally, combination of complex multiple steps, such as (1) chemical vapor deposition (CVD) growth of nanowire, (2) harvesting of nanowire, (3) manipulation and placement of individual nanowires, and (4) integration of nanowire to circuit are necessary. Each step is very time consuming, expensive, and environmentally unfriendly, and only a very low yield is achieved through the multiple steps. As an alternative to conventional complex multistep approach, original findings are presented on the first demonstration of rapid, one step, digital selective growth of nanowires directly on 3D micro/nanostructures by developing a novel approach; laser induced hydrothermal growth (LIHG) without any complex integration of series of multiple process steps such as using any conventional photolithography process or CVD. The LIHG process can grow nanowires by scanning a focused laser beam as a local heat source in a fully digital manner to grow nanowires on arbitrary patterns and even on the non‐flat, 3D micro/nano structures in a safer liquid environment, as opposed to a gas environment. The LIHG process can greatly reduce the processing lead time and simplify the nanowire‐based nanofabrication process by removing multiple steps for growth, harvest, manipulation/placement, and integration of the nanowires. LIHG process can grow nanowire directly on 3D micro/nano structures, which will be extremely challenging even for the conventional nanowire integration processes. LIHG does not need a vacuum environment to grow nanowires but can be performed in a solution environment which is safer and cheaper. LIHG can also be used for flexible substrates such as temperature‐sensitive polymers due to the low processing temperature. Most of all, the LIHG process is a digital process that does not require conventional vacuum deposition or a photolithography mask.     

Iron Oxide Nanoparticle‐Encapsulated CNT Branches Grown on 3D Ozonated CNT Internetworks for Lithium‐Ion Battery Anodes

Multidimensional hierarchical architecturing is a promising chemical approach to provide unique characteristics synergistically integrated from individual nanostructured materials for energy storage applications. Herein, hierarchical complex hybrid architectures of CNT‐on‐OCNT‐Fe are reported, where iron oxide nanoparticles are encapsulated inside carbon nanotube (CNT) branches grown onto the ozone‐treated surface of 3D CNT internetworked porous structures. The activated surface of the 3D ozonated CNT (OCNT) interacts with the iron oxide nanoparticles, resulting in different chemical environments of inner and outer tubes and large surface area. The mixed phases of iron oxide nanoparticles are confined by full encapsulation inside the conductive nanotubes and act as catalysts to vertically grow the CNT branches. This unique hierarchical architecture allows CNT‐on‐OCNT‐Fe to achieve a reasonable capacity of >798 mA h g^?1 at 50 mA g^?1, with outstanding rate capability (≈72% capacity retention at rates from 50 to 1000 mA g^?1) and cyclic stability (>98.3% capacity retention up to 200 cycles at 100 mA g^?1 with a coulombic efficiency of >97%). The improved rate and cyclic capabilities are attributed to the hierarchical porosity of 3D OCNT internetworks, the shielding of CNT walls for encapsulated iron oxide nanoparticles, and a proximate electronic pathway for the isolated nanoparticles.     

High Electroactive Material Loading on a Carbon Nanotube@3D Graphene Aerogel for High‐Performance Flexible All‐Solid‐State Asymmetric Supercapacitors

Freestanding carbon‐based hybrids, specifically carbon nanotube@3D graphene (CNTs@3DG) hybrid, are of great interest in electrochemical energy storage. However, the large holes (about 400 µm) in the commonly used 3D graphene foams (3DGF) constitute as high as 90% of the electrode volume, resulting in a very low loading of electroactive materials that is electrically connected to the carbon, which makes it difficult for flexible supercapacitors to achieve high gravimetric and volumetric energy density. Here, a hierarchically porous carbon hybrid is fabricated by growing 1D CNTs on 3D graphene aerogel (CNTs@3DGA) using a facile one‐step chemical vapor deposition process. In this architecture, the 3DGA with ample interconnected micrometer‐sized pores (about 5 µm) dramatically enhances mass loading of electroactive materials comparing with 3DGF. An optimized all‐solid‐state asymmetric supercapacitor (AASC) based on MnO₂@CNTs@3DGA and Ppy@CNTs@3DGA electrodes exhibits high volumetric energy density of 3.85 mW h cm^?3 and superior long‐term cycle stability with 84.6% retention after 20 000 cycles, which are among the best reported for AASCs with both electrodes made of pseudocapacitive electroactive materials.     

Radially Aligned Porous Carbon Nanotube Arrays on Carbon Fibers: A Hierarchical 3D Carbon Nanostructure for High‐Performance Capacitive Energy Storage

A novel and scalable synthesis approach to produce hierarchically aligned porous carbon nanotube arrays (PCNTAs) on flexible carbon fibers (CFs) is developed. The PCNTAs are obtained by catalytic conversion of ethanol on ZnO nanorod arrays and then reduction‐evaporation of ZnO nanorods, resulting in uniform and controllable wall thicknesses of the final PCNTAs. The 3D arrangement, the diameters, and the lengths of the PCNTAs can be tuned by adjusting the synthesis protocols of the ZnO nanorod arrays. The PCNTAs@CFs exhibit a high specific capacitance of 182 F g^?1 at 40 A g^?1 (188 F g^?1 at 20 A g^?1) in 6 m KOH. The symmetric supercapacitor shows an excellent cycling stability with only 0.0016% loss per cycle after 10 000 continuous cycles at the current density of 12 A g^?1. These excellent electrochemical performances are ascribed to the unique structural design of hierarchical PCNTAs, which provide not only appropriate channels for enhanced electronic and ionic transport but also increased surface area for accessing more electrolyte ions. The structural design and the synthesis approach are general and can be extended to synthesizing a broad range of materials systems.     

High‐Performance Cathode Based on Self‐Templated 3D Porous Microcrystalline Carbon with Improved Anion Adsorption and Intercalation

Dual‐ion batteries (DIBs) have attracted much attention due to their advantages of low cost and especially environmental friendliness. However, the capacities of most DIBs are still unsatisfied (≈100 mAh g^?1) ascribed to the limited capacity of anions intercalation for conventional graphite cathode. In this study, 3D porous microcrystalline carbon (3D‐PMC) was designed and synthesized via a self‐templated growth approach, and when used as cathode for a DIB, it allows both intercalation and adsorption of anions. The microcrystalline carbon is beneficial to obtain capacity originated from anions intercalation, and the 3D porous structure with a certain surface area contributes to anions adsorption capacity. With the synergistic effect, this 3D‐PMC is utilized as cathode and tin as anode for a sodium‐based DIB, which has a high capacity of 168.0 mAh g^?1 at 0.3 A g^?1, among the best values of reported DIBs so far. This cell also exhibits long‐term cycling stability with a capacity retention of ≈70% after 2000 cycles at a high current rate of 1 A g^?1. It is believed that this work will provide a strategy to develop high‐performance cathode materials for DIBs.     

Atomic Layer Deposition Inducing Integration of Co,N Codoped Carbon Sphere on 3D Foam with Hierarchically Porous Structures for Flexible Hydrogen Producing Device

Integration of metal–organic frameworks on deformation tolerant substrates exhibits a promising prospect in flexible electrode applications. A straightforward synthesis utilizing atomic layer deposition pretreating to induce the growth of a zeolitic imidazolate framework‐67 (ZIF‐67) layer on carbon foam (CF), which maintains high ZIF‐67 loading with a hierarchically porous structure and large surface area of 453 m² g^?1 is presented. With a subsequent pyrolysis process, three‐dimensional composite structures are obtained with Co, N codoped carbon spheres attached firmly on the CF framework, and CF bridges the individual carbon spheres to construct a conductive pathway. The composites are used as a flexible electrode for hydrogen production both in acid and alkaline electrolytes. The advances in the composite structure, such as the hierarchically porous structure, large surface area, and high loading of active material, lead to excellent electrochemical performance in terms of low overpotential of 142 mV and low Tafel slope of 73 mV dec^?1 in 0.5 m H₂SO₄. Most importantly, the composite structure with outstanding flexible property shows good catalytic performance under remarkable deformation, and after 100 repeated compression–recovery cycles, the performance degrades slightly. This work provides a new design of flexible electrode, which is promising for the hydrogen production industry.