绿色高效制备电化学性能优异的多孔石墨烯电极材料

电极材料的性能决定超级电容器的储能特性,因此研究优异电极材料的制备方法是提高其储能特性的重要前提。多孔石墨烯(Porous graphene)作为新型的碳材料具有比表面积大、电导率高等优点,是一种理想的双电层电容器电极材料。本工作制备的多孔石墨烯材料微孔和中孔都很发达,孔径分布更为合理,因此其比表面积相较于原始的石墨烯有了很大的提高。经检测该材料的比表面积为1 417.65 m²·g-1,并且能够提供较高的电化学双电层电容,经测试由该材料组装成的扣式超级电容具有31.7 F·g-1的比容量且具有优良的导电特性。此外,在电流密度1 A·g-1下循环10 000次后材料比电容保持率为78%。这些电化学测试结果表明本研究制备的多孔石墨烯在超级电容器的能量存储方面具有较好的应用前景。     

Graphene Emerges as a Versatile Template for Materials Preparation

Graphene and its derivatives are emerging as a class of novel but versatile templates for the controlled preparation and functionalization of materials. In this paper a conceptual review on graphene‐based templates is given, highlighting their versatile roles in materials preparation. Graphene is capable of acting as a low‐dimensional hard template, where its two‐dimensional morphology directs the formation of novel nanostructures. Graphene oxide and other functionalized graphenes are amphiphilic and may be seen as soft templates for formatting the growth or inducing the controlled assembly of nanostructures. In addition, nanospaces in restacked graphene can be used for confining the growth of sheet‐like nanostructures, and assemblies of interlinked graphenes can behave either as skeletons for the formation of composite materials or as sacrificial templates for novel materials with a controlled network structure. In summary, flexible graphene and its derivatives together with an increasing number of assembled structures show great potentials as templates for materials production. Many challenges remain, for example precise structural control of such novel templates and the removal of the non‐functional remaining templates.     

石墨烯包覆分子筛复合电极材料的制备及其性能研究

以4A分子筛(4A)和改进Hummers法制备的氧化石墨烯凝胶(GO)为原料, 按一定质量比进行混合超声分散, 以混合分散液为前驱体煅烧制备了氧化还原石墨烯(RGO)包覆的三维复合4A/RGO电极材料。采用X射线衍射(XRD)、拉曼光谱(Raman)、孔径分析、扫描电子显微镜(SEM)和电化学测试等方法研究了复合材料的结构、形貌及超级电容性能。测试结果表明, 4A均匀地穿插在RGO片层中, 阻止了RGO片层之间相互堆积, 而RGO片层之间相互链接, 形成三维空间导电网络, 提高了复合电极材料的导电性。当GO与4A质量比为1:6时, 复合材料在4 A/g电流密度下比电容可达450 F/g, 在此电流密度下循环800次后, 其比容量保持率为85.7%, 表现出良好的倍率性能和循环稳定性。该4A/RGO复合电极材料超级电容性能优于纯4A或RGO, 可归因于4A和RGO之间的协同效应。     

Monolithic Graphene Trees as Anode Material for Lithium Ion Batteries with High C‐Rates

Monolithically structured reduced graphene oxide (rGO), prepared from a highly concentrated and conductive rGO paste, is introduced as an anode material for lithium ion batteries with high rate capacities. This is achieved by a mixture of rGO paste and the water‐soluble polymer sodium carboxymethylcellulose (SCMC) with freeze drying. Unlike previous 3D graphene porous structures, the monolithic graphene resembles densely branched pine trees and has high mechanical stability with strong adhesion to the metal electrodes. The structures contain numerous large surface area open pores that facilitate lithium ion diffusion, while the strong hydrogen bonding between the graphene layers and SCMC provides high conductivity and reduces the volume changes that occur during cycling. Ultrafast charge/discharge rates are obtained with outstanding cycling stability and the capacities are higher than those reported for other anode materials. The fabrication process is simple and straightforward to adjust and is therefore suitable for mass production of anode electrodes for commercial applications.     

Novel 2D Layered Molybdenum Ditelluride Encapsulated in Few‐Layer Graphene as High‐Performance Anode for Lithium‐Ion Batteries

Molybdenum ditelluride nanosheets encapsulated in few‐layer graphene (MoTe₂/FLG) are synthesized by a simple heating method using Te and Mo powder and subsequent ball milling with graphite. The as‐prepared MoTe₂/FLG nanocomposites as anode materials for lithium‐ion batteries exhibit excellent electrochemical performance with a highly reversible capacity of 596.5 mAh g^?1 at 100 mA g^?1, a high rate capability (334.5 mAh g^?1 at 2 A g^?1), and superior cycling stability (capacity retention of 99.5% over 400 cycles at 0.5 A g^?1). Ex situ X‐ray diffraction and transmission electron microscopy are used to explore the lithium storage mechanism of MoTe₂. Moreover, the electrochemical performance of a MoTe₂/FLG//0.35Li₂MnO₃·0.65LiMn_0.5Ni_0.5O₂ full cell is investigated, which displays a reversible capacity of 499 mAh g^?1 (based on the MoTe₂/FLG mass) at 100 mA g^?1 and a capacity retention of 78% over 50 cycles, suggesting the promising application of MoTe₂/FLG for lithium‐ion storage. First‐principles calculations exhibit that the lowest diffusion barrier (0.18 eV) for lithium ions along pathway III in the MoTe₂ layered structure is beneficial for improving the Li intercalation/deintercalation property.     

Preparation of MoS2‐Coated Three‐Dimensional Graphene Networks for High‐Performance Anode Material in Lithium‐Ion Batteries

A novel composite, MoS₂‐coated three‐dimensional graphene network (3DGN), referred to as MoS₂/3DGN, is synthesized by a facile CVD method. The 3DGN, composed of interconnected graphene sheets, not only serves as template for the deposition of MoS₂, but also provides good electrical contact between the current collector and deposited MoS₂. As a proof of concept, the MoS₂/3DGN composite, used as an anode material for lithium‐ion batteries, shows excellent electrochemical performance, which exhibits reversible capacities of 877 and 665 mAh g^?1 during the 50^th cycle at current densities of 100 and 500 mA g^?1, respectively, indicating its good cycling performance. Furthermore, the MoS₂/3DGN composite also shows excellent high‐current‐density performance, e.g., depicts a 10^th‐cycle capacity of 466 mAh g^?1 at a high current density of 4 A g^?1.     

High Electrocatalytic and Wettable Nitrogen‐Doped Microwave‐Exfoliated Graphene Nanosheets as Counter Electrode for Dye‐Sensitized Solar Cells

In this paper, high electrocatalytic and wettable nitrogen‐doped microwave‐exfoliated graphene (N‐MEG) nanosheets are used as Pt‐free counter electrode (CE) for dye‐sensitized solar cells (DSSCs). A low cost solution‐based process is developed by using cyanamide (NH₂CN) at room temperature and normal pressure. The pyrrolic and pyridinic N atoms are doped into the carbon conjugated lattice to enhance electrocatalytic activity. N‐MEG film having N‐doping active sites and large porosity provides a wettable surface to facilitate electrolyte diffusion so that improves fill factor. Moreover, the control of the air exposure time after completing N‐MEG film is found to be crucial to obtain a reliable N‐MEG CE. A high DSSC efficiency up to 7.18% can be achieved based on N‐MEG CE, which is nearly comparable to conventional Pt CE.     

Polymeric Graphene Bulk Materials with a 3D Cross‐Linked Monolithic Graphene Network

Although many great potential applications are proposed for graphene, till now none are yet realized as a stellar application. The most challenging issue for such practical applications is to figure out how to prepare graphene bulk materials while maintaining the unique two‐dimensional (2D) structure and the many excellent properties of graphene sheets. Herein, such polymeric graphene bulk materials containing three‐dimensional (3D) cross‐linked networks with graphene sheets as the building unit are reviewed. The theoretical research on various proposed structures of graphene bulk materials is summarized first. Then, the synthesis or fabrication of these graphene materials is described, which comprises mainly two approaches: chemical vapor deposition and cross‐linking using graphene oxide directly. Finally, some exotic and exciting potential applications of these graphene bulk materials are presented.     

High Performance of N‐Doped Graphene with Bubble‐like Textures for Supercapacitors

Nitrogen‐doped graphene (NG) with wrinkled and bubble‐like texture is fabricated by a thermal treatment. Especially, a novel sonication‐assisted pretreatment with nitric acid is used to further oxidize graphene oxide and its binding with melamine molecules. There are many bubble‐like nanoflakes with a dimension of about 10 nm appeared on the undulated graphene nanosheets. The bubble‐like texture provides more active sites for effective ion transport and reversible capacitive behavior. The specific surface area of NG (5.03 at% N) can reach up to 438.7 m² g^?1, and the NG electrode demonstrates high specific capacitance (481 F g^?1 at 1 A g^?1, four times higher than reduced graphene oxide electrode (127.5 F g^?1)), superior cycle stability (the capacitance retention of 98.9% in 2 m KOH and 99.2% in 1 m H₂SO₄ after 8000 cycles), and excellent energy density (42.8 Wh kg^?1 at power density of 500 W kg^?1 in 2 m KOH aqueous electrolyte). The results indicate the potential use of NG as graphene‐based electrode material for energy storage devices.     

用于锂离子电池的石墨烯及其复合负极材料的研究进展

石墨烯复合材料因具有高比表面积、高比容量、优异的导电性、显著的化学稳定性,在锂离子电池领域具有巨大的应用前景。在负极复合材料中,石墨烯不仅可以形成导电网络提升复合材料的导电性能,而且还可以缓冲材料在充放电过程中的体积效应,提高了材料的倍率性能和循环寿命,为设计大容量高稳定性的锂离子电池提供了理论保证。因此制备不同组成和结构的石墨烯复合材料是一个非常有价值的课题。对近年来国内外运用不同方法制备不同组成和结构的石墨烯复合材料的研究结果做了综合评述和展望。     

Graphene: An Outstanding Multifunctional Coating for Conventional Materials

As the most significant facilitator of human civilization, materials are eternal jewels in the view of researchers whose brilliance never faded. However, simple conventional materials, which are most commonly used and indispensable today, seem too primitive and insufficiently functional to meet the demands of the future intelligent and informational applications, urging more functions to be integrated. The ideal strategy to achieve the transformations of conventional materials non‐destructively is functionalizing the surface and retaining the original properties at the same time. Graphene, a two‐dimensional material with only atomic‐thickness, has come into the view of the researchers, attributed to its various outstanding properties. In recent years, a large amount of research has been devoted to “wearing” graphene to functionalize the conventional materials, booming a huge “graphene‐X” family. In this concept, representative members are illustrated and their improved functions are demonstrated. Also, the prospects and challenges for this dazzling family are discussed.