Bioinspired Graphene‐Based Nanocomposites and Their Application in Flexible Energy Devices

Graphene is the strongest and stiffest material ever identified and the best electrical conductor known to date, making it an ideal candidate for constructing nanocomposites used in flexible energy devices. However, it remains a great challenge to assemble graphene nanosheets into macro‐sized high‐performance nanocomposites in practical applications of flexible energy devices using traditional approaches. Nacre, the gold standard for biomimicry, provides an excellent example and guideline for assembling two‐dimensional nanosheets into high‐performance nanocomposites. This review summarizes recent research on the bioinspired graphene‐based nanocomposites (BGBNs), and discusses different bioinspired assembly strategies for constructing integrated high‐strength and ‐toughness graphene‐based nanocomposites through various synergistic effects. Fundamental properties of graphene‐based nanocomposites, such as strength, toughness, and electrical conductivities, are highlighted. Applications of the BGBNs in flexible energy devices, as well as potential challenges, are addressed. Inspired from the past work done by the community a roadmap for the future of the BGBNs in flexible energy device applications is depicted.     

Carbon Nanotube–Multilayered Graphene Edge Plane Core–Shell Hybrid Foams for Ultrahigh‐Performance Electromagnetic‐Interference Shielding

Materials with an ultralow density and ultrahigh electromagnetic‐interference (EMI)‐shielding performance are highly desirable in fields of aerospace, portable electronics, and so on. Theoretical work predicts that 3D carbon nanotube (CNT)/graphene hybrids are one of the most promising lightweight EMI shielding materials, owing to their unique nanostructures and extraordinary electronic properties. Herein, for the first time, a lightweight, flexible, and conductive CNT–multilayered graphene edge plane (MLGEP) core–shell hybrid foam is fabricated using chemical vapor deposition. MLGEPs are seamlessly grown on the CNTs, and the hybrid foam exhibits excellent EMI shielding effectiveness which exceeds 38.4 or 47.5 dB in X‐band at 1.6 mm, while the density is merely 0.0058 or 0.0089 g cm^?3, respectively, which far surpasses the best values of reported carbon‐based composite materials. The grafted MLGEPs on CNTs can obviously enhance the penetration losses of microwaves in foams, leading to a greatly improved EMI shielding performance. In addition, the CNT–MLGEP hybrids also exhibit a great potential as nano‐reinforcements for fabricating high‐strength polymer‐based composites. The results provide an alternative approach to fully explore the potentials of CNT and graphene, for developing advanced multifunctional materials.     

Hybrids of carbon nanotubes and graphene/graphene oxide

This paper reviews recent progress in hybrids based on carbon nanotubes (CNTs) and graphene (G) or graphene oxide (GO). The combination of CNTs, including single-walled (SW), double-walled (DW) and multi-walled (MW), and G or GO resulted in various hybrids. CNTs–G/GO hybrid thin films are usually prepared by using solution/suspension casting and layer-by-layer (LbL) deposition, free-standing sheets are fabricated by using vacuum filtration and 3D hierarchical structures are produced by using chemical vapor deposition (CVD). CNTs–G/GO hybrids have also been used as fillers to fabricate polymer composites with synergistic effects. The composites have significantly improved electrical, mechanical and thermal properties, which make them very useful for various potential applications, such as transparent electrodes replacing ITO, electrodes for supercapacitors, lithium-ion batteries and dye-sensitized solar cells.     

Cover Picture: Synthesis of a Self‐Assembled Hybrid of Ultrananocrystalline Diamond and Carbon Nanotubes (Adv. Mater. 12/2005)

The cover shows self‐assembled hybrids of ultrananocrystalline diamond (UNCD) and carbon nanotubes (CNTs). These hybrids were successfully prepared by their simultaneous growth within an argon‐rich Ar/CH₄ plasma, in work reported on p. 1496 by Carlisle and co‐workers. Various methods demonstrated the coexistence of UNCD and CNTs, and the capability of controlling the relative fraction and configuration of UNCD and CNTs in the hybrid material. This new synthesis pathway enables the development of new nanocarbons with unique mechanical, tribological, and electrochemical properties.     

Recent Progress in Graphene‐Based Noble‐Metal Nanocomposites for Electrocatalytic Applications

The fast industrialization process has led to global challenges in the energy crisis and environmental pollution, which might be solved with clean and renewable energy. Highly efficient electrochemical systems for clean‐energy collection require high‐performance electrocatalysts, including Au, Pt, Pd, Ru, etc. Graphene, a single‐layer 2D carbon nanosheet, possesses many intriguing properties, and has attracted tremendous research attention. Specifically, graphene and graphene derivatives have been utilized as templates for the synthesis of various noble‐metal nanocomposites, showing excellent performance in electrocatalytic‐energy‐conversion applications, such as the hydrogen evolution reaction and CO₂ reduction. Herein, the recent progress in graphene‐based noble‐metal nanocomposites is summarized, focusing on their synthetic methods and electrocatalytic applications. Furthermore, some personal insights on the challenges and possible future work in this research field are proposed.     

Synergistic effects from graphene and carbon nanotubes enable flexible and robust electrodes for high-performance supercapacitors

Flexible and lightweight energy storage systems have received tremendous interest recently due to their potential applications in wearable electronics, roll-up displays, and other devices. To manufacture such systems, flexible electrodes with desired mechanical and electrochemical properties are critical. Herein we present a novel method to fabricate conductive, highly flexible, and robust film supercapacitor electrodes based on graphene/MnO(2)/CNTs nanocomposites. The synergistic effects from graphene, CNTs, and MnO(2) deliver outstanding mechanical properties (tensile strength of 48 MPa) and superior electrochemical activity that were not achieved by any of these components alone. These flexible electrodes allow highly active material loading (71 wt % MnO(2)), areal density (8.80 mg/cm(2)), and high specific capacitance (372 F/g) with excellent rate capability for supercapacitors without the need of current collectors and binders. The film can also be wound around 0.5 mm diameter rods for fabricating full cells with high performance, showing significant potential in flexible energy storage devices.     

The Regulating Role of Carbon Nanotubes and Graphene in Lithium‐Ion and Lithium–Sulfur Batteries

The ever‐increasing demands for batteries with high energy densities to power the portable electronics with increased power consumption and to advance vehicle electrification and grid energy storage have propelled lithium battery technology to a position of tremendous importance. Carbon nanotubes (CNTs) and graphene, known with many appealing properties, are investigated intensely for improving the performance of lithium‐ion (Li‐ion) and lithium–sulfur (Li–S) batteries. However, a general and objective understanding of their actual role in Li‐ion and Li–S batteries is lacking. It is recognized that CNTs and graphene are not appropriate active lithium storage materials, but are more like a regulator: they do not electrochemically react with lithium ions and electrons, but serve to regulate the lithium storage behavior of a specific electroactive material and increase the range of applications of a lithium battery. First, metrics for the evaluation of lithium batteries are discussed, based on which the regulating role of CNTs and graphene in Li‐ion and Li–S batteries is comprehensively considered from fundamental electrochemical reactions to electrode structure and integral cell design. Finally, perspectives on how CNTs and graphene can further contribute to the development of lithium batteries are presented.     

氧化锌/石墨烯纳米复合材料制备技术的研究进展

氧化锌/石墨烯纳米复合材料在储能、光电材料与器件、光催化剂等方面具有广阔的应用前景,其所含元素无毒无害,储量丰富,适用于溶剂热法、超声空化法、电化学沉积等低成本非真空制备方法,故氧化锌/石墨烯复合材料近来成为复合材料领域研究热点之一。综述了氧化锌/石墨烯复合材料的多种制备方法,讨论了各制备方法的工艺特点与不足,分析了不同制备方法对氧化锌/石墨烯纳米复合材料形貌与性能的影响,展望了其未来工业化规模制备的发展趋势。     

Multiscale fiber-reinforced thermoplastic composites incorporating carbon nanotubes: A review

This article reviews recent literature on hierarchical thermoplastic-based composites that simultaneously incorporate carbon nanotubes (CNTs) and conventional microscale fibers, and discusses the structure–property relationships of the resulting hybrids. The mixing of multiple and multiscale constituents enables the preparation of materials with new or improved properties due to synergistic effects. By exploiting the outstanding mechanical, thermal and electrical properties of CNTs, a new generation of multifunctional high-performance composites suitable for a wide variety of applications can be developed.     

Multifunctional Heterogeneous Carbon Nanotube Nanocomposites Assembled by DNA‐Binding Peptide Anchors

Although carbon nanotubes (CNTs) are remarkable materials with many exceptional characteristics, their poor chemical functionality limits their potential applications. Herein, a strategy is proposed for functionalizing CNTs, which can be achieved with any functional group (FG) without degrading their intrinsic structure by using a deoxyribonucleic acid (DNA)‐binding peptide (DBP) anchor. By employing a DBP tagged with a certain FG, such as thiol, biotin, and carboxyl acid, it is possible to introduce any FG with a controlled density on DNA‐wrapped CNTs. Additionally, different types of FGs can be introduced on CNTs simultaneously, using DBPs tagged with different FGs. This method can be used to prepare CNT nanocomposites containing different types of nanoparticles (NPs), such as Au NPs, magnetic NPs, and quantum dots. The CNT nanocomposites decorated with these NPs can be used as reusable catalase‐like nanocomposites with exceptional catalytic activities, owing to the synergistic effects of all the components. Additionally, the unique DBP–DNA interaction allows the on‐demand detachment of the NPs attached to the CNT surface; further, it facilitates a CNT chirality‐specific NP attachment and separation using the sequence‐specific programmable characteristics of oligonucleotides. The proposed method provides a novel chemistry platform for constructing new functional CNTs suitable for diverse applications.     

Carbon Nanotubes for Dye‐Sensitized Solar Cells

As one type of emerging photovoltaic cell, dye‐sensitized solar cells (DSSCs) are an attractive potential source of renewable energy due to their eco–friendliness, ease of fabrication, and cost effectiveness. However, in DSSCs, the rarity and high cost of some electrode materials (transparent conducting oxide and platinum) and the inefficient performance caused by slow electron transport, poor light‐harvesting efficiency, and significant charge recombination are critical issues. Recent research has shown that carbon nanotubes (CNTs) are promising candidates to overcome these issues due to their unique electrical, optical, chemical, physical, as well as catalytic properties. This article provides a comprehensive review of the research that has focused on the application of CNTs and their hybrids in transparent conducting electrodes (TCEs), in semiconducting layers, and in counter electrodes of DSSCs. At the end of this review, some important research directions for the future use of CNTs in DSSCs are also provided.     

Review of functionalization,structure and properties of graphene/polymer composite fibers

Fibrous materials usually have good mechanical, heat-resistant, acid-resistant, alkali-resistant and moisture regained properties which originate from its composition, condensed structure and crosslinking styles. However, these materials often lack of good electrical conductivity, flame retardance, anti-static and anti-radiation properties which are desired for varied specific applications. Graphene, as a new emerging nanocarbon material, has some unique properties including superb thermal and electrical conductivity, strong mechanical and anti-corrosive property, extremely high surface area etc. Therefore, graphene has attracted extensive interests in recent years. Upon modification with graphene, fibers exhibit a number of enhanced or new properties such as adsorption performance, anti-bacteria, hydrophobicity and conductivity which are beneficial for broader applications. In this review, the strategies to modify the fibers with graphene and the corresponding effects on the fibers as well as the relevant applications in varied areas were discussed.     

Laser‐Induced Graphene Formation on Wood

Wood as a renewable naturally occurring resource has been the focus of much research and commercial interests in applications ranging from building construction to chemicals production. Here, a facile approach is reported to transform wood into hierarchical porous graphene using CO₂ laser scribing. Studies reveal that the crosslinked lignocellulose structure inherent in wood with higher lignin content is more favorable for the generation of high‐quality graphene than wood with lower lignin content. Because of its high electrical conductivity (≈10 Ω per square), graphene patterned on wood surfaces can be readily fabricated into various high‐performance devices, such as hydrogen evolution and oxygen evolution electrodes for overall water splitting with high reaction rates at low overpotentials, and supercapacitors for energy storage with high capacitance. The versatility of this technique in formation of multifunctional wood hybrids can inspire both research and industrial interest in the development of wood‐derived graphene materials and their nanodevices.     

In Situ Coupling of CoP Polyhedrons and Carbon Nanotubes as Highly Efficient Hydrogen Evolution Reaction Electrocatalyst

Hydrogen evolution reaction (HER) from water electrolysis is an attractive technique developed in recent years for cost‐effective clean energy. Although considerable efforts have been paid to create efficient catalysts for HER, the development of an affordable HER catalyst with superior performance under mild conditions is still highly desired. In this work, metal–organic frameworks (MOFs)‐templated strategy is proposed for in situ coupling of cobalt phosphide (CoP) polyhedrons nanoparticles and carbon nanotubes (CNTs). Due to the synergistic catalytic effect between CoP polyhedrons and CNTs, the as‐prepared CoP–CNTs hybrids show excellent HER performance. The resultant CoP–CNTs demonstrate excellent HER activity in 0.5 m H₂SO₄ with Tafel slope of 52 mV dec^?1, small onset overpotential of ≈64 mV, and a low overpotential of ≈139 mV at 10 mA cm^?2. Additionally, the catalyst also manifests superior durability in acid media. Considering the structure diversity of MOFs, the strategy presented here can be extended for synthesizing other well‐defined metal phosphides–CNTs hybrids, which may be used in the fields of catalysis, energy conversion and storage.     

Graphene Oxide,Highly Reduced Graphene Oxide,and Graphene: Versatile Building Blocks for Carbon‐Based Materials

Isolated graphene, a nanometer‐thick two‐dimensional analog of fullerenes and carbon nanotubes, has recently sparked great excitement in the scientific community given its excellent mechanical and electronic properties. Particularly attractive is the availability of bulk quantities of graphene as both colloidal dispersions and powders, which enables the facile fabrication of many carbon‐based materials. The fact that such large amounts of graphene are most easily produced via the reduction of graphene oxide—oxygenated graphene sheets covered with epoxy, hydroxyl, and carboxyl groups—offers tremendous opportunities for access to functionalized graphene‐based materials. Both graphene oxide and graphene can be processed into a wide variety of novel materials with distinctly different morphological features, where the carbonaceous nanosheets can serve as either the sole component, as in papers and thin films, or as fillers in polymer and/or inorganic nanocomposites. This Review summarizes techniques for preparing such advanced materials via stable graphene oxide, highly reduced graphene oxide, and graphene dispersions in aqueous and organic media. The excellent mechanical and electronic properties of the resulting materials are highlighted with a forward outlook on their applications.     

Flow-induced properties of nanotube-filled polymer materials

Carbon nanotubes (CNTs) are under intense investigation in materials science owing to their potential for modifying the electrical conductivity sigma, shear viscosity eta, and other transport properties of polymeric materials. These particles are hybrids of filler and nanoscale additives because their lengths are macroscopic whereas their cross-sectional dimensions are closer to molecular scales. The combination of extended shape, rigidity and deformability allows CNTs to be mechanically dispersed in polymer matrices in the form of disordered 'jammed' network structures. Our measurements on representative network-forming multiwall nanotube (MWNT) dispersions in polypropylene indicate that these materials exhibit extraordinary flow-induced property changes. Specifically, sigma and eta both decrease strongly with increasing shear rate, and these nanocomposites exhibit impressively large and negative normal stress differences, a rarely reported phenomenon in soft condensed matter. We illustrate the practical implications of these nonlinear transport properties by showing that MWNTs eliminate die swell in our nanocomposites, an effect crucial for their processing.     

Direct Growth of Polyaniline Chains from N‐Doped Sites of Carbon Nanotubes

Polymer grafting from graphitic carbon materials has been pursued for several decades. Unfortunately, currently available methods mostly rely on the harsh chemical treatment of graphitic carbons which causes severe degradation of chemical structure and material properties. A straightforward growth of polyaniline chain from the nitrogen (N)‐doped sites of carbon nanotubes (CNTs) is presented. N‐doping sites along the CNT wall nucleate the polymerization of aniline, which generates seamless hybrids consisting of polyaniline directly grafted onto the CNT walls. The resultant materials exhibit excellent synergistic electrochemical performance, and can be employed for charge collectors of supercapacitors. This approach introduces an efficient route to hybrid systems consisting of conducting polymers directly grafted from graphitic dopant sites.     

Hierarchical 3D All‐Carbon Composite Structure Modified with N‐Doped Graphene Quantum Dots for High‐Performance Flexible Supercapacitors

Flexible supercapacitors have shown enormous potential for portable electronic devices. Herein, hierarchical 3D all‐carbon electrode materials are prepared by assembling N‐doped graphene quantum dots (N‐GQDs) on carbonized MOF materials (cZIF‐8) interweaved with carbon nanotubes (CNTs) for flexible all‐solid‐state supercapacitors. In this ternary electrode, cZIF‐8 provides a large accessible surface area, CNTs act as the electrical conductive network, and N‐GQDs serve as highly pseudocapactive materials. Due to the synergistic effect and hierarchical assembly of these components, N‐GQD@cZIF‐8/CNT electrodes exhibit a high specific capacitance of 540 F g^?1 at 0.5 A g^?1 in a 1 m H₂SO₄ electrolyte and excellent cycle stability with 90.9% capacity retention over 8000 cycles. The assembled supercapacitor possesses an energy density of 18.75 Wh kg^?1 with a power density of 108.7 W kg^?1. Meanwhile, three supercapacitors connected in series can power light‐emitting diodes for 20 min. All‐solid‐state N‐GQD@cZIF‐8/CNT flexible supercapacitor exhibits an energy density of 14 Wh kg^?1 with a power density of 89.3 W kg^?1, while the capacitance retention after 5000 cycles reaches 82%. This work provides an effective way to construct novel electrode materials with high energy storage density as well as good cycling performance and power density for high‐performance energy storage devices via the rational design.     

Electrochemical performance of conducting polymer and its nanocomposites prepared by chemical vapor phase polymerization method

In this work, conducting polymers poly(3,4-ethylenedioxythiophene) (PEDOT), PEDOT/carbon nanotubes (CNTs), and PEDOT/reduced graphene oxide (RGO) were prepared via an in situ chemical vapor phase polymerization (VPP) process. Experiment results showed that PEDOT and PEDOT nanocomposites were uniformly constructed in oxidant and oxidant nanocomposite films through a modifying template effect. The VPP PEDOT and its nanocomposites were built on aluminium film as supercapaitor electrode materials and electrochemical capacitive properties were investigated by using cycle voltammetry and charge/discharge techniques. The VPP PEDOT exhibited a specific capacitance of 92 F/g at a current density of 0.2 A/g. The VPP PEDOT composites consisting of CNTs and RGO displayed specific capacitances of 137 and 156 F/g, respectively, at the same current density. For VPP nanocomposites, more than 80 % of initial capacitance was retained after 1,000 charge/discharge cycles, suggesting a good cycling stability for electrochemical electrode materials. The good capacitive performance of the conducting polymer nanocomposites are contributed to the synergic effect of the two components.     

Freestanding 3D Graphene–Nickel Encapsulated Nitrogen‐Rich Aligned Bamboo Like Carbon Nanotubes for High‐Performance Supercapacitors with Robust Cycle Stability

3D hierarchical structures are reported based on graphene–nickel encapsulated nitrogen‐rich aligned bamboo like carbon nanotubes, which show not only high‐performance supercapacitance behavior but also a great robust cyclic stability. A facile synthesis route is developed of 2D nickel oxide decorated functionalized graphene nanosheets (2D‐NiO‐f:GNSs) hybrids and 3D nitrogen doped bamboo‐shaped carbon nanotubes (NCNTs) vertically standing on the functionalized graphene nanosheets (3D‐NCNT@f:GNSs) by using a thermal decomposition method. The chemical reduction and morphology‐dependent electrochemical response are investigated. The enhanced specific capacitance of 3D‐NCNT@f:GNSs as compared to that of 2D‐NiO‐f:GNSs suggests the synergistic effects and indicates the importance of energy storage and superior long‐term cycling performance that are achieved. This 3D‐NCNT@f:GNSs hybrid shows a remarkable cycling stability with a maximum power density of 12.32 kW kg⁻¹ and maximum energy density of 109.13 Wh kg⁻¹ due to the good connection of NCNT and f:GNSs. This unique 3D nano network architecture enables the availability of large surface areas of NCNT, thus endowing the nanohybrids with high specific capacitance and excellent reusability.