3D打印石墨烯制备技术及其在储能领域的应用研究进展

石墨烯优异的力学和物理性能使其成为理想的储能材料。因结构精确可控,易实现规模化制备,3D打印石墨烯材料有望在储能领域得到广泛应用。本文全面综述了3D打印石墨烯制备技术及其在储能领域的应用研究进展。石墨烯墨水的黏度和可打印性是实现石墨烯3D打印的制约因素。实现工艺简单、浓度可控、无黏结剂石墨烯墨水的规模化打印将成为3D打印石墨烯制备技术未来的研究热点。石墨烯超级电容器、锂硫电池、锂离子电池等储能元件一体化打印成型是3D打印石墨烯在储能领域应用的发展方向。     

Metal‐Free Carbon Materials for CO2 Electrochemical Reduction

The rapid increase of the CO₂ concentration in the Earth's atmosphere has resulted in numerous environmental issues, such as global warming, ocean acidification, melting of the polar ice, rising sea level, and extinction of species. To search for suitable and capable catalytic systems for CO₂ conversion, electrochemical reduction of CO₂ (CO₂RR) holds great promise. Emerging heterogeneous carbon materials have been considered as promising metal‐free electrocatalysts for the CO₂RR, owing to their abundant natural resources, tailorable porous structures, resistance to acids and bases, high‐temperature stability, and environmental friendliness. They exhibit remarkable CO₂RR properties, including catalytic activity, long durability, and high selectivity. Here, various carbon materials (e.g., carbon fibers, carbon nanotubes, graphene, diamond, nanoporous carbon, and graphene dots) with heteroatom doping (e.g., N, S, and B) that can be used as metal‐free catalysts for the CO₂RR are highlighted. Recent advances regarding the identification of active sites for the CO₂RR and the pathway of reduction of CO₂ to the final product are comprehensively reviewed. Additionally, the emerging challenges and some perspectives on the development of heteroatom‐doped carbon materials as metal‐free electrocatalysts for the CO₂RR are included.     

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.     

石墨烯/CuO锂离子电池负极材料的研究进展

石墨烯作为一种锂离子电池负极材料表现出优异的电化学性能,但石墨烯在充放电过程中容易团聚,导致其容量衰减特别快。而金属氧化物在充放电过程中体积膨胀大,因此其容量衰减也非常快;另外,金属氧化物的电导率低,导致其倍率性能差。将金属氧化物与石墨烯复合,两者性能互补,石墨烯可提高复合材料的电导率,缓解金属氧化物在充放电过程中的体积效应;金属氧化物可提高复合材料的储锂容量,并能阻止石墨烯在充放电过程中团聚。本文介绍了石墨烯/CuO锂离子电池负极材料的制备方法,分析了石墨烯与氧化铜及其复合材料的储锂机制,展望了石墨烯/CuO锂离子电池负极材料的应用前景,并指出了当前研究中存在的问题。     

Assembly of Foldable 3D Microstructures Using Graphene Hinges

Origami/kirigami-inspired 3D assembly approaches have recently attracted attention for a variety of applications, such as advanced optoelectronic devices and biomedical sensors. The results reported here describe an approach to construct classes of multiple foldable 3D microstructures that involve deformations that typical conductive materials, such as conventional metal films, cannot tolerate. Atomically thin graphene sheets serve as folding hinges during a process of 2D to 3D conversion via a deterministic buckling process. The exceptional mechanical properties of graphene enable the controlled, geometric transformation of a 2D precursor bonded at selective sites on a prestretched elastomer into folded 3D microstructures, in a reversible manner without adverse effects on the electrical properties. Experimental and computational investigations of the folding mechanisms for such types of 3D objects reveal the underlying physics and the dependence of the process on the thickness of the graphene/supporting films that define the hinges.     

Molecular Self‐Assembly on Graphene

The formation of ordered arrays of molecules via self‐assembly is a rapid, scalable route towards the realization of nanoscale architectures with tailored properties. In recent years, graphene has emerged as an appealing substrate for molecular self‐assembly in two dimensions. Here, the first five years of progress in supramolecular organization on graphene are reviewed. The self‐assembly process can vary depending on the type of graphene employed: epitaxial graphene, grown in situ on a metal surface, and non‐epitaxial graphene, transferred onto an arbitrary substrate, can have different effects on the final structure. On epitaxial graphene, the process is sensitive to the interaction between the graphene and the substrate on which it is grown. In the case of graphene that strongly interacts with its substrate, such as graphene/Ru(0001), the inhomogeneous adsorption landscape of the graphene moiré superlattice provides a unique opportunity for guiding molecular organization, since molecules experience spatially constrained diffusion and adsorption. On weaker‐interacting epitaxial graphene films, and on non‐epitaxial graphene transferred onto a host substrate, self‐assembly leads to films similar to those obtained on graphite surfaces. The efficacy of a graphene layer for facilitating planar adsorption of aromatic molecules has been repeatedly demonstrated, indicating that it can be used to direct molecular adsorption, and therefore carrier transport, in a certain orientation, and suggesting that the use of transferred graphene may allow for predictible molecular self‐assembly on a wide range of surfaces.     

石墨烯及复合材料的吸附作用与研究进展

目的概述几种石墨烯及其衍生物吸附材料的研究现状,旨在为石墨烯应用方面提供一定的研究思路。方法通过对近年来国内外相关文献的分析和总结,介绍石墨烯基材料在吸附方面的研究进展,讨论其吸附机理和影响因素。结论由于石墨烯基复合材料的比表面积较大,因此具有良好的吸附性能,可用于污水处理。同时,在包装运输过程如液体产品的外包装发生损坏时,石墨烯基吸附材料可吸附残液,防止污染到其它内装物。     

Entry strategies in an emerging technology: a pilot web-based study of graphene firms

We explore pilot web-based methods to probe the strategies followed by new small and medium-sized technology-based firms as they seek to commercialize emerging technologies. Tracking and understanding the behavior of such early commercial entrants is not straightforward because smaller firms with limited resources do not always widely engage in readily visible and accessible activities such as publishing and patenting. However, many new firms, even if small, present information about themselves that is available online. Focusing on the early commercialization of novel graphene technologies, we introduce a “web scraping” approach to systematically capture information contained in the online web pages of a sample of small and medium-sized high technology graphene firms in the US, UK, and China. We analyze this information and devise measures that gauge how firm specialization in the target technology impacts overall market orientation. Three groups of graphene enterprises are identified which vary by their focus on product development, materials development, and integration into existing product portfolios. Country-level factors are important in understanding these early diverging commercial approaches in the nascent graphene market. We consider management and policy implications of our findings, and discuss the value, including strengths and weaknesses, of web scraping as an additional information source on enterprise strategies in emerging technologies.     

石墨烯均匀分散问题研究进展

具有优良性能的石墨烯常被作为增强体加入基体材料中以改进其性能。研究发现,石墨烯增强复合材料的性质在很大程度上取决于石墨烯在基体中的均匀分散程度。而石墨烯增强体在基体中的均匀分散问题一直是研究的难点,这就限制了石墨烯增强复合材料性能的提升及其开发应用。总结了石墨烯在基体中均匀分散方法的研究进展,并展望了其研究方向及发展趋势。     

从炭纤维的发展看石墨烯产业化进程

简要介绍了碳家族的两种重要的材料——炭纤维和石墨烯的发展历史、结构、性能及制备方法,深入剖析了两种材料的产业化发展特点和区别,探讨了石墨烯产业化进程中的问题,最后从炭纤维的产业化进程得出未来石墨烯要走务实的产业化道路。     

功能性石墨烯改善聚合物介电性能的研究进展

目的对近年来使用改性石墨烯改善聚合物基复合材料介电性能的研究进行总结,指出今后的发展方向。方法总结通过石墨烯改性来改善其在聚合物的分散性和提高聚合物基石墨烯复合材料介电性能的方法;对比石墨烯/聚合物复合材料的复合工艺对其介电常数和介电损耗数值的变化,总结不同的改性方法对复合材料介电性能的影响。结论石墨烯作为一种性能较优的导电填料对材料介电性能影响巨大,然而,由于其物理分散性不好,极大地阻碍了石墨烯改性聚合物基高介电复合材料的发展。通过对石墨烯进行功能化改性修饰可以有效提高聚合物基复合材料的介电性能,这种材料可作为电活性聚合物,在很多需要高介电常数的电介质材料领域,如超级电容器、感应器、驱动器、智能包装和机器人等方面得到应用。     

Fatigue Behavior of Polymer Encapsulated Graphene to Mitigate Interfacial Fatigue Damage

In applications such as flexible electronic devices, graphene, and other 2D materials are frequently in contact with stretchable polymeric substrates. The interface between 2D materials and polymers is dominated by weak van der Waals forces and can eventually degrade due to the frequent dynamic mechanical loads that these devices experience. This can lead to significant local delamination and shear fracture of the 2D materials. Using the polydimethylsiloxane (PDMS) encapsulation method, it is shown that the damage in graphene is significantly mitigated when it is capped during dynamic loading. To track the spread of damage in both encapsulated and nonencapsulated graphene, in situ, cyclic loading is performed. The fundamental process driving this substantial reduction in damage propagation in the 2D lattice is explained by the conventional shear lag model. It is also observed that softer PDMS substrate and capping layer completely mitigate the fatigue damage in graphene for 100 cycles at 10% applied fatigue strain.     

三维石墨烯的制备及其在超级电容器中的应用

目的 三维石墨烯在实际应用中所呈现的性能与其理论模拟结果相差甚远,目前尚无系统的原因分析和改进方法总结,回顾三维石墨烯的发展历程及近几年国内外研究进展是必要的,为三维石墨烯在工业设计和生产制备超级电容器电极活性材料中的应用提供参考.方法 综述三维石墨烯的制备方法,阐述其在超级电容器中应用的研究,针对三维结构塌陷问题的解决办法、杂原子掺杂提高材料整体比电容及石墨烯基电容器的理论模拟等方面进行总结.结果 三维石墨烯的制备方法主要有自组装法和模板法,自组装法还原度普遍较低,电容值一般为100～300 F/g;模板法制备的石墨烯比表面积可达500 m2/g以上;多元素掺杂体系在高电流密度下的电容保持率普遍不足80％;关于分级多孔结构的理论模拟研究不足.结论 制备分级多孔结构的三维石墨烯、多元素掺杂体系理论研究、非对称超级电容器的研究及应用将受到学者的关注.     

Tribochemistry of alcohols and their tribological properties: a review

Recently, alcohols have attracted more attention due to their excellent tribological performance, especially superlubricity under low loads. Alcohol solution, as a liquid lubricant, can easily reach the superlubricity state under low loads because of the formed low shear hydroxylation interfaces induced by the tribochemical reactions. A general picture and its influencing factors have been elucidated, not only at the macroscopic scale but also at the nanoscale, which is sufficient to provide effective guidance for lubrication design and tribology research in engineering. Herein, we provide a review on the recent applications of alcohols in lubrication. In addition, the material transformation caused by alcohols in friction is a key factor affecting the tribological properties. As an important two-dimensional material, the growth mechanisms of graphene are variable, and the most famous is the formation of carbon radicals under the action of metal catalysts. Thus, based on the formation mechanism of carbon friction film (such as amorphous carbon and graphene), the main content of this review also includes the transformation of graphene in alcohol solution friction process.     

Facile preparation of nitrogen-doped reduced graphene oxide as a metal-free catalyst for oxygen reduction reaction

The electronic and chemical properties of reduced graphene oxide (RGO) can be modulated by chemical doping foreign atoms and functional moieties. Nitrogen-doped reduced graphene oxide (N-RGO) is a promising candidate for oxygen reduction reaction (ORR) in fuel cells. However, there are still some challenges in further preparation and modification of N-RGO. In this work, a low-cost industrial material, urea, was chosen to modify RGO by a facile, catalyst-free thermal annealing approach in large scale. The obtained N-RGO, as a metal-free catalyst for oxygen reduction was characterized by XRD, XPS, Raman, SEM, TEM, and electrochemical measurements. It was found that the optimum synthesis conditions were a mass ratio of graphene oxide and urea equal to 1:10 and an annealing temperature of 800 °C. Detailed X-ray photoelectron spectrum analysis of the optimum product shows that the atomic percentage of N-RGO samples can be adjusted up to 2.6 %, and the resultant product can act as an efficient metal-free catalyst, exhibiting enhanced electrocatalytic properties for ORR in alkaline electrolytes. This simple, cost-effective, and scalable approach opens up the possibility for the synthesis of other nitrogen doping materials in gram-scale. It can be applied to various carbon materials for the development of other metal-free efficient ORR catalysts for fuel cell applications, and even new catalytic materials for applications beyond fuel cells.     

石墨烯基导热薄膜的研究进展

随着现代技术的发展,散热和导热已成为制约芯片器件小型化和大功率制造业发展的关键问题之一。由于传统的金属导热材料存在密度大和易氧化等问题,近年来以石墨烯基材料为代表的非金属碳基材料逐渐成为国内外的研究热点。本文综述了近年国内外石墨烯导热薄膜的制备方法及最新研究成果,分析讨论了热处理工艺、晶粒尺寸、薄膜密度及杂质原子和缺陷等对石墨烯导热薄膜性能的影响和物理机理,并对该领域的发展趋势进行了展望。     

Modern reliability assurance of integrated circuits—A strategy based on technology capability assessment and production reproducibility control

Technological innovations provide integrated circuits of increased functionality and complexity, and modern design tools facilitate a new multiplicity of products, such as application-specific products (ASICs). Traditional qualification procedures cannot keep pace with this evolution with respect to requirements of product reliability, ability of qualifying the multiplicity of future products, and market demands for saving cost and time. A further development of a reliability assurance concept, which will be discussed here, considers design tools, basic product elements, materials, manufacturing process and controls as a ‘system’, which has to be qualified with respect to the consistency and efficiency of all of the implemented reliability assurance measures. The concept is based on the manufacturer's ‘system’ knowledge and responsibility. It is compatible with the relevant requirements of ISO 9000 and recent military standard proposals. The procedure is applied to commercial products. The main part of this concept is the qualification of the manufacturing technology. The procedure is organized as a continuous process starting at the concept phase of a new technology and its pilot product. The various steps then follow the development, the pre-series and series production phases. The reliability aspects concentrate on the physical properties of product elements relevant to their stability and endurance, i.e. the potential failure mechanisms and their root causes as reliability risks. Thus a major part of reliability testing for the qualification of the pilot product of a new technology can be performed without the use of the final product version. The benefits derivable from this approach are savings in time and cost as well as the capability to handle future product multiplicity.     

Programmed Synthesis of Freestanding Graphene Nanomembrane Arrays

Freestanding graphene membranes are unique materials. The combination of atomically thin dimensions, remarkable mechanical robustness, and chemical stability make porous and non‐porous graphene membranes attractive for water purification and various sensing applications. Nanopores in graphene and other 2D materials have been identified as promising devices for next‐generation DNA sequencing based on readout of either transverse DNA base‐gated current or through‐pore ion current. While several ground breaking studies of graphene‐based nanopores for DNA analysis have been reported, all methods to date require a physical transfer of the graphene from its source of production onto an aperture support. The transfer process is slow and often leads to tears in the graphene that render many devices useless for nanopore measurements. In this work, we report a novel scalable approach for site‐directed fabrication of pinhole‐free graphene nanomembranes. Our approach yields high quality few‐layer graphene nanomembranes produced in less than a day using a few steps that do not involve transfer. We highlight the functionality of these graphene devices by measuring DNA translocation through electron‐beam fabricated nanopores in such membranes.     

Production of stable amorphous form by means of spray drying

Spray drying is a very useful method for manufacturing of amorphous solid materials. This is mainly due to the possibility of fast solvent evaporation that leads to a rapid transformation of solution to a solid state. Besides evaporation kinetics, there are various process parameters that influence physical and chemical characteristics of such obtained material. The possibility of obtaining a stable amorphous structure of the active pharmaceutical ingredient in a spray dryer was examined. A solution of the hydrochloride crystalline structure of the active pharmaceutical ingredient in a mixture of water and acetonitrile was dried at different temperatures and flowrates of nitrogen used for atomization, as well as the flowrates of the solution. The influence of the process conditions on the properties of the product was analyzed. The final dried products were characterized and identified with a variety of analytical and physical methods. The results showed that a stable amorphous structure of the high purity active pharmaceutical ingredient is obtained, and that the optimal conditions of the process are defined. The amorphous structure is stable at temperatures below 200°C when it is transformed into a new crystal structure. Conditions of high relative air humidity lead to partial transformation.     

Laser‐Induced Graphene: From Discovery to Translation

Laser‐induced graphene (LIG) is a 3D porous material prepared by direct laser writing with a CO₂ laser on carbon materials in ambient atmosphere. This technique combines 3D graphene preparation and patterning into a single step without the need for wet chemical steps. Since its discovery in 2014, LIG has attracted broad research interest, with several papers being published per month using this approach. These serve to delineate the mechanism of the LIG‐forming process and to showcase the translation into many application areas. Herein, the strategies that have been developed to synthesize LIG are summarized, including the control of LIG properties such as porosity, composition, and surface characteristics, and the advancement in methodology to convert diverse carbon precursors into LIG. Taking advantage of the LIG properties, the applications of LIG in broad fields, such as microfluidics, sensors, and electrocatalysts, are highlighted. Finally, future development in biodegradable and biocompatible materials is briefly discussed.