高性能石墨烯/聚合物纳米复合材料的研究进展——界面作用力的设计及其影响

石墨烯是一种二维材料,具有极其优异的电学、力学、热学等性能,制备方法简单且价格低廉,可以在高性能聚合物基复合材料中展现无穷魅力.石墨烯在聚合物中的分散状态,以及与基体间的界面作用是构筑高性能石墨烯/聚合物纳米复合材料的关键因素.本文综述了石墨烯/聚合物纳米复合材料的界面作用力,包括氢键、π-π堆栈、共价、配位作用和成核—结晶作用,并总结和评述了这些界面作用力的优缺点和适用范围.最后展望了多种协同作用在构筑强界面作用力的石墨烯/聚合物基纳米复合材料中的应用前景.     

金属核心/高聚物膜复合悬浮相电流变流体材料

针对电流变流体悬浮相材料的开发与研究,根据介质极化原理,设计开发了金属核心/高聚物膜复合悬浮相电流变流体材料,在乳液聚合与微胶囊包覆技术的基础上,制备出了金属核心/高聚物膜复合颗粒.并对这种金属核心/高聚物膜复合颗粒的电流变流体性能进行了测试与研究.从理论和实验上都说明了金属核心/高聚物膜复合悬浮相材料在改善电流变流体力学性能及稳定性方面具有潜力,是可以进一步提高与改进的电流变流体材料.     

高介电性能石墨烯/聚合物纳米复合材料研究进展

石墨烯作为一种新型二维平面纳米材料,表现出许多优异的物理性质.将石墨烯与聚合物复合,利用其独特的结构及物理性质,有望开发一类具有卓越介电性能的纳米复合电介质材料.本文总结了高介电石墨烯/聚合物纳米复合材料这一研究方向的最新进展,重点介绍了石墨烯提高聚合物基体介电性能的基本理论、石墨烯/聚合物界面对复合电介质性能的影响等,并简要展望了这类材料的发展前景.     

石墨烯及其聚合物纳米复合材料

石墨烯是一种新型的二维纳米碳材料,具有优异的机械性能、电性能和热性能等,是聚合物纳米复合材料的理想填料。近年来,石墨烯/聚合物纳米复合材料成为聚合物基纳米复合材料的研究热点。本文对石墨烯及其聚合物纳米复合材料的研究进展进行了综述。首先概述了石墨烯的不同制备方法及石墨烯的共价与非共价改性途径。然后重点总结了石墨烯/聚合物纳米复合材料的常用制备方法及其机械性能、导电性、导热性、耐热性及阻隔性能。最后,对该领域所存在的问题进行了总结,并展望了其发展趋势。     

电化学法制备石墨烯及其复合材料

石墨烯是一种具有优异物理和化学性质的新型二维碳纳米材料,大规模低成本制备高品质石墨烯的方法是其能够得到广泛实际应用的重要前提. 电化学方法可以快捷、绿色无污染、批量制备高质量的石墨烯及其复合材料. 本综述在对石墨烯各种制备方法进行简要比较之后,对近年来石墨烯、石墨烯/无机纳米复合材料、石墨烯/聚合物复合材料以及类石墨烯材料的电化学法制备进展进行介绍并作了展望.     

三维石墨烯-聚合物复合材料制备方法研究进展

石墨烯是一种具有蜂窝状结构的二维纳米碳材料,具有高的比表面积、优异的导电/热性和理想的机械强度,因而被广泛用作聚合物基复合材料的增强填料。将二维石墨烯片构筑成三维石墨烯,既能充分发挥二维石墨烯片的性质,又能具备三维材料的特性。聚合物填充三维石墨烯制备的实心三维石墨烯-聚合物复合材料(Three-Dimensional Graphene-Polymer Composites,3DGPCs),可实现石墨烯在基体中的均匀分散,制备具有优异力学性能的导电、导热复合材料。以石墨烯三维网络为骨架制备的多孔3DGPCs具有高孔隙率、大比表面积和高电子传输能力等特性,可广泛应用于能量存储、环境保护、传感、电磁屏蔽和油污清理等领域。本文综述了3DGPCs的制备方法,并评述了制备3DGPCs所面临的挑战及发展前景。     

具有三维导电网络结构的锡纳米颗粒/石墨烯纳米片复合电极材料的储镁性能研究

镁二次电池具有安全性高、价格低廉等优点,是一种具有潜在应用前景的高能量密度电池体系.目前,镁二次电池的研究重点之一是寻找合适的电极材料.最近,我们通过水热和热处理相结合的方法成功制备了具有三维导电网络结构的锡纳米颗粒/石墨烯纳米片复合电极材料.研究发现,在石墨烯的三维导电网络片层上,均匀分布了粒径小于100 nm的锡纳米颗粒.将锡纳米颗粒/石墨烯纳米片复合材料作为镁二次电池电极材料,当电流密度为15 mA·g^-1和300 mA·g^-1时,首次放电容量分别达到了545.4 mAh·g^-1和238.8 mAh·g^-1,经过150圈后,容量保持率达到了93%,库伦效率为99%,表现出了较高的电化学活性.研究还发现,镁离子嵌入复合材料中形成镁锡合金,当镁离子脱出后,再次形成锡纳米颗粒/石墨烯纳米片复合电极材料,镁离子的脱出和嵌入具有很高的可逆性.这对未来研究设计高性能镁离子电极材料具有十分重要的意义.     

具有三维导电网络结构的锡纳米颗粒/石墨烯纳米片复合电极材料的储镁性能研究（英文）

镁二次电池具有安全性高、价格低廉等优点,是一种具有潜在应用前景的高能量密度电池体系.目前,镁二次电池的研究重点之一是寻找合适的电极材料.最近,我们通过水热和热处理相结合的方法成功制备了具有三维导电网络结构的锡纳米颗粒/石墨烯纳米片复合电极材料.研究发现,在石墨烯的三维导电网络片层上,均匀分布了粒径小于100 nm的锡纳米颗粒.将锡纳米颗粒/石墨烯纳米片复合材料作为镁二次电池电极材料,当电流密度为15 mA·g~(-1)和300 mA·g~(-1)时,首次放电容量分别达到了545.4 mAh·g~(-1)和238.8 mAh·g~(-1),经过150圈后,容量保持率达到了93%,库伦效率为99%,表现出了较高的电化学活性.研究还发现,镁离子嵌入复合材料中形成镁锡合金,当镁离子脱出后,再次形成锡纳米颗粒/石墨烯纳米片复合电极材料,镁离子的脱出和嵌入具有很高的可逆性.这对未来研究设计高性能镁离子电极材料具有十分重要的意义.     

二维材料的一维纳米带

自石墨烯被发现以来,二维材料研究成为一个新的研究热点。当二维材料制备成一维纳米带结构后,由于宽度方向上的限域效应和边缘结构的差异,导致其具有区别于二维材料的独特的电学、光学和磁学性质,因此逐步成为科学家关注的焦点。本文主要介绍了石墨烯、石墨炔、联苯烯、氮化硼、黑磷、过渡金属二硫族化合物等二维材料的一维纳米带的结构、制备方法和性能研究。首先讨论了二维材料制备成一维纳米带后的结构与性能的改变;其次,着重阐述了典型的纳米带制备方法,包括“自上而下”和“自下而上”两种策略,如二维片层刻蚀、打开纳米管、化学合成、化学气相沉积、外延生长及碳纳米管限域生长等方法,实现可控制备指定纳米宽度与具有特定边缘结构的纳米带,最终获得不同于其二维材料本体的特殊性能。最后,总结了不同方法制备纳米带的优缺点,提出了需要克服的困难和挑战,并展望了未来的研究方向,希望能引起国内外同行的广泛关注。     

三维石墨烯材料制备方法的研究进展

石墨烯是由单层碳原子组成的新型二维碳纳米材料,因其众多独特而优异的理化特性,已成为近年来材料科学领域中最耀眼的明星材料。整合二维(2D)石墨烯形成具有微纳米结构的三维(3D)石墨烯材料,可有效调控石墨烯的电学、光学、化学、机械和催化特性。近期研究发现,基于3D石墨烯构建的功能器件在储能、环境、传感及生物分析领域表现出更为突出的性能。因而,制备新型3D石墨烯材料已成为当前石墨烯化学的研究热点。目前3D石墨烯材料的制备方法主要包括溶液自组装、界面自组装、模板介导合成法等。通过改变原材料或制备方法,可以有效调控3D石墨烯柔韧性、多孔性、活性面积、电子传递速度及传质等性能。本文介绍了当前3D石墨烯材料制备方法的研究进展,并简要评述3D石墨烯材料制备研究中所面临的挑战及应用前景。     

Graphene/polymer composites for energy applications

Graphene has wide potential applications in energy-related systems, mainly because of its unique atom-thick two-dimensional structure, high electrical or thermal conductivity, optical transparency, great mechanical strength, inherent flexibility, and huge specific surface area. For this purpose, graphene materials are frequently blended with polymers to form composites, especially when fabricating flexible devices. Graphene/polymer composites have been explored as electrodes of supercapacitors or lithium ion batteries, counter electrodes of dye-sensitized solar cells, transparent conducting electrodes and active layers of organic solar cells, catalytic electrodes, and polymer electrolyte membranes of fuel cells. In this review, we summarize the recent advances on the synthesis and applications of graphene/polymer composites for energy applications. The challenges and prospects in this field have also been discussed. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2013     

Microstructure and viscoelasticity of electrorheological suspensions with hybrid core‐shell microspheres

A novel type of electrorheological (ER) fluids with hybrid microspheres as dispersed phases was prepared and their rheological properties in dynamic and oscillatory modes in the presence of electric field were studied. Hybrid microspheres are new types of inorganic‐organic composites consisting of inorganic hollow cores covered with a thin layer of conjugated polymer poly (3‐octylthiophene)—P₃OT, followed by a polyurethane electrolyte shell of defined thicknesses and controlled (electronic and ionic) conductivities. It has been found that the rate of ER response for the applied electric field of the order of few kV/mm, as well as the recovery time after high shear loads of the novel ER fluids, was significantly improved in comparison to the typical solid electrolyte‐based materials. It has been shown that upon the application of an electric field the suspensions of hybrid microspheres form a gel‐like network structure at low strain region with reasonable rigidity characterized by the domination of G′ moduli over G″ and broad linear viscoelastic range. It was shown that at electric fields as high as 3 kV/mm, the investigated ER materials exhibited predominantly elastic behavior and were able to endure strains up to 3% without significant deformation of the material microstructure. Moreover, the novel ER materials exhibited much faster microstructure recovery after high shear loads in comparison to ER fluids comprising core‐shell composites without poly (3‐octylthiophene) interlayer, which makes them more suitable for the applications requiring immediate response to an external electric field.     

Nanoarchitectured Graphene‐Based Supercapacitors for Next‐Generation Energy‐Storage Applications

Tremendous development in the field of portable electronics and hybrid electric vehicles has led to urgent and increasing demand in the field of high‐energy storage devices. In recent years, many research efforts have been made for the development of more efficient energy‐storage devices such as supercapacitors, batteries, and fuel cells. In particular, supercapacitors have great potential to meet the demands of both high energy density and power density in many advanced technologies. For the last half decade, graphene has attracted intense research interest for electrical double‐layer capacitor (EDLC) applications. The unique electronic, thermal, mechanical, and chemical characteristics of graphene, along with the intrinsic benefits of a carbon material, make it a promising candidate for supercapacitor applications. This Review focuses on recent research developments in graphene‐based supercapacitors, including doped graphene, activated graphene, graphene/metal oxide composites, graphene/polymer composites, and graphene‐based asymmetric supercapacitors. The challenges and prospects of graphene‐based supercapacitors are also discussed.     

ER suspensions of composite core‐shell microspheres with improved sedimentation stability

Electrorheological (ER) fluids are usually suspensions of solid polarizable particles in nonpolar carrier liquids. Such systems are particularly sensitive to the presence of electric fields, which transform them reversibly into solid‐like bodies. Fast (within milliseconds) and fully reversible reaction of ER fluids to electric field is a subject of great interest because of many possible applications in tunable vibration dampers, clutches, valves, or brakes. A novel type of ER fluids with composite microspheres composed of polymer electrolyte shell with defined shell thickness and inorganic hollow cores has been synthesized and tested in the presence of an electric field. It has been found that suspensions with composite grains possessed more stable ER response with temperature and lower power consumption in comparison to their polymer‐based counterparts. ER effect of the prepared fluids was measured and related to the applied electric field and solid phase properties. It has been also shown that suspensions of composite materials exhibited improved long‐term sedimentation stability in comparison to polymer‐based suspensions due to the formation of weak microstructure which suppressed the sedimentation of solid phase in off‐field state. Copyright © 2011 John Wiley & Sons, Ltd.     

Monolithic polyimine vitrimer/graphene aerogel composites

Graphene-polymer composites have attracted great attention as sensing materials due to their tailorable electrical conductivity, physicochemical properties, and sensitivity to geometric and functional changes. Herein, we report the first example of cylindrical monolithic polyimine vitrimer/graphene composites with excellent mechanical, compressive, rehealable and recyclable, and piezoresistive properties via simple infiltration of polymer monomers into the pores of graphene aerogel followed by thermal curing. The composites exhibit excellent durable compressibility (negligible reduction in the compression properties even after 3000 consecutive compression cycles), rapid recovery to the original size upon stress released, high compressive strength (up to 1.2 MPa), and high conductivity (up to 79 S/m). Excellent piezoresistive properties were observed, displaying consistent and reliable change of the electrical resistance with the compression ratio. Furthermore, rehealing with ～100% recovery of the compressive strength and electric conductivity was achieved under mild rehealing conditions, which is highly desired but has rarely been reported for electronic materials. The facile strategy for fabrication of rehealable monolithic polymer/GAs can open new possibilities for the sustainable development of composites with high electrical conductivity for various applications such as sensing, health monitoring, and movement detection.     

功能化石墨烯材料：定义、分类及制备策略

自2004年被成功制备后,石墨烯因其独特迷人的性质在近十几年来备受关注,同时也引发了二维纳米材料的研究热潮。单原子层厚度的二维结构赋予石墨烯非同寻常的光学、电子学、磁学及力学等性质,使得石墨烯在生物学、医学、化学、物理学和环境科学等多个领域展现出极大的应用潜力。制得注意的是,石墨烯在应用时通常需要进行功能化,调节其组成、大小、形状和结构等,以便于加工处理或满足不同的应用需求。石墨烯功能化方法多样,功能化产物也是种类繁多。然而,到目前为止,石墨烯功能化产物并没有系统全面的分类和精确的定义。因此,本文在系统总结现有石墨烯功能化研究的基础上,给出了石墨烯功能化产物的系统分类、各类的精确定义和相应的制备策略,并通过典型示例进行了详细地阐述。石墨烯功能化的产物统称为“功能化石墨烯材料”,分为两类：“功能化石墨烯”和“功能化石墨烯复合材料”。功能化石墨烯材料的制备可由“自上而下”和“自下而上”两种策略实现。制备策略的选择取决于应用需求。系统分类、精确命名和制备策略的归纳必将有助于功能化石墨烯材料的进一步发展。     

A Review on Graphene Oxide Two-dimensional Macromolecules: from Single Molecules to Macro-assembly

Graphene oxide(GO), which consists of two-dimensional(2 D) sp² carbon hexagonal networks and oxygen-contained functional groups, has laid the foundation of mass production and applications of graphene materials. Made by chemical oxidation of graphite, GO is highly dispersible or even solubilized in water and polar organic solvents, which resolves the hard problem of graphene processing and opens a door to wet-processing of graphene. Despite its defects, GO is easy to functionalize, dope, punch holes, cut into pieces, conduct chemical reduction, form lyotropic liquid crystal, and assemble into macroscopic materials with tunable structures and properties as a living building block. GO sheet has been viewed as a single molecule, a particle, as well as a soft polymer material. An overview on GO as a 2 D macromolecule is essential for studying its intrinsic properties and guiding the development of relevant subjects. This review mainly focuses on recent advances of GO sheets, from single macromolecular behavior to macro-assembled graphene material properties. The first part of this review offers a brief introduction to the synthesis of GO molecules. Then the chemical structure and physical properties of GO are presented, as well as its polarity in solvent and rheology behavior. Several key parameters governing the ultimate stability of GO colloidal behavior, including size, p H and the presence of cation in aqueous dispersions, are highlighted. Furthermore, the discovery of GO liquid crystal and functionalization of GO molecules have built solid new foundations of preparing highly ordered, architecture-tunable, macro-assembled graphene materials, including 1 D graphene fibers, 2 D graphene films, and 3 D graphene architectures. The GO-based composites are also viewed and the interactions between these target materials and GO are carefully discussed. Finally, an outlook is provided in this field, where GO is regarded as macromolecules, pointing out the challenges and opportunities that exist in the field. We hope that this review will be beneficial to the understanding of GO in terms of chemical structure,molecular properties, macro-assembly and potential applications, and encourage further development to extend its investigations from basic research to practical applications.     

石墨烯/聚苯胺复合材料的制备及应用

石墨烯/聚苯胺复合材料由于其优异的电学、热学、电化学性能和机械性能等特点,吸引了研究者们的广泛关注。本文对近几年来石墨烯/聚苯胺复合材料的发展状况进行了简单介绍,首先总结了原位聚合法、界面聚合法、自组装法、溶液共混法等不同制备方法对石墨烯/聚苯胺复合材料结构和性能的影响。由于石墨烯/聚苯胺复合材料结合了石墨烯和聚苯胺两者的优点,展现出更加优异的性能,因此本文还对其在超级电容器、传感器、燃料电池、太阳能电池等方面的应用进行了详细介绍。     

基于3d元素掺杂的石墨二炔分子传感材料性能调控

二维碳材料因其独特的性质成为凝聚态物理、纳米电子学、生物医药等领域的前沿研究热点。石墨二炔具有天然的半导体特性及独特的大孔网状结构,在纳米电子器件和生物传感方面比石墨烯更具优势。本文使用第一性原理计算研究了单层石墨二炔的纳米带电子输运性质和及石墨二炔对小分子的吸附。我们考虑用掺杂3d金属原子的方法来增强对分子的吸附力。选择在石墨二炔表面吸附能较大的钪(Sc)、钛(Ti)原子,确定石墨二炔表面Sc、Ti单原子在室温下的稳定性,研究了Sc、Ti掺杂石墨二炔用于分子检测的潜在可能。从能带、载流子浓度等方面全面探讨了Sc、Ti掺杂石墨二炔对甲醛分子(HCHO)的响应。又进一步研究了石墨二炔与氨基酸分子间相互作用,发现色散力在相互作用中占主导地位。研究了吸附氨基酸对石墨二炔电子输运的影响,探讨石墨二炔在生物传感方面的潜在应用。