电动汽车用La-Fe-B储氢合金的制备与电化学性能研究

研究了石墨烯含量对储氢合金物相组成和电化学性能的影响。结果表明,不同石墨烯含量储氢合金都主要由La₃Ni₁₃B₂、LaNi₅和（Fe,Ni）相组成,La₃Ni₁₃B₂和（Fe,Ni）相晶胞体积会随着石墨烯含量增加而增大,LaNi₅相晶胞体积会随着石墨烯含量增加而减小。当石墨烯质量分数从0%增加至6%时,储氢合金的最大放电容量先增加后减小,在石墨烯质量分数为4%时取得储氢合金放电容量最大值（288.5 mA·h/g）,且当循环周期为100次时,石墨烯质量分数为4%和6%的储氢合金的放电容量仍然高于未添加石墨烯的储氢合金。相同温度下,添加石墨烯的储氢合金的放电容量都高于未添加石墨烯的储氢合金,且石墨烯质量分数为4%的储氢合金具有最大放电容量。随着石墨烯质量分数从0%增加至6%,储氢合金的电荷转移电阻先减小后增大、电流密度和扩散系数先增大后减小,在石墨烯质量分数为4%时取得电荷转移电阻最小值、电流密度和扩散系数最大值,适宜的石墨烯添加量为4%。     

Graphene wrapped copper–nickel nanospheres on highly conductive graphene film for use as counter electrodes of dye-sensitized solar cells

A novel architecture of graphene wrapped copper–nickel (Cu–Ni) nanospheres (NSs)/graphene film was proposed to be TCO- and Pt-free counter electrode (CE) with high electrocatalytic activity for dye-sensitized solar cells (DSSCs). The novel architecture CE is composed of highly conductive graphene film, Cu–Ni alloy NSs and the wrapping graphene on the surface of alloy NSs. The graphene film as an electrically conductive layer was synthesized by chemical vapor deposition (CVD) on the insulating SiO₂ substrate, and graphene wrapped Cu–Ni alloy catalyst NSs on the graphene film were in situ formed by the reduction of Cu–Ni acetate and graphene growth using CVD. The graphene wrapped Cu–Ni NSs/graphene film CE shows much superior electrocatalytic activity, compared with graphene film, and the power conversion efficiency of 5.46% was achieved in DSSC devices, which is close to that of Pt/FTO electrode (6.19%). Therefore, the novel architecture of graphene wrapped Cu–Ni NSs/graphene film CE may be used as Pt- and TCO-free CEs for low-cost, high performance DSSCs.     

Optical Biosensor Based on Graphene and Its Derivatives for Detecting Biomolecules

Graphene and its derivatives show great potential for biosensing due to their extraordinary optical, electrical and physical properties. In particular, graphene and its derivatives have excellent optical properties such as broadband and tunable absorption, fluorescence bursts, and strong polarization-related effects. Optical biosensors based on graphene and its derivatives make nondestructive detection of biomolecules possible. The focus of this paper is to review the preparation of graphene and its derivatives, as well as recent advances in optical biosensors based on graphene and its derivatives. The working principle of face plasmon resonance (SPR), surface-enhanced Raman spectroscopy (SERS), fluorescence resonance energy transfer (FRET) and colorimetric sensors are summarized, and the advantages and disadvantages of graphene and its derivatives applicable to various types of sensors are analyzed, and the methods of surface functionalization of graphene and its derivatives are introduced; these optical biosensors can be used for the detection of a range of biomolecules such as single cells, cellular secretions, proteins, nucleic acids, and antigen-antibodies; these new high-performance optical sensors are capable of detecting changes in surface structure and biomolecular interactions with the advantages of ultra-fast detection, high sensitivity, label-free, specific recognition, and the ability to respond in real-time. Problems in the current stage of application are discussed, as well as future prospects for graphene and its biosensors. Achieving the applicability, reusability and low cost of novel optical biosensors for a variety of complex environments and achieving scale-up production, which still faces serious challenges.     

Recent advances on graphene microstructure engineering for propellant-related applications

As a special polymeric composite and military-strategic material, composite solid propellant has attracted extensive attention and efforts to improve its performances. Graphene been regarded as an ideal material to enhance the performances of propellants, because of its excellent physical and chemical properties, such as ultra-strong strength, large specific surface area, remarkable thermal conductivity, and phenomenal electrical performance. Moreover, the microstructure engineering based on graphene has been demonstrated to reveal effective influences on the composites. Recently, many new advances have been developed in microstructure engineering of graphene for propellant-related applications. In this article, we first present an overview of the main synthesis methods of graphene. Subsequently, these new advances are reviewed, discussed, and summarized carefully. Finally, the application prospects of microstructure engineering of graphene in the propellant field are proposed.     

Graphene nanosheets based on controlled exfoliation process for enhanced lithium storage in lithium-ion battery

A facile and rapid approach was used for the fabrication of chemically derived graphene nanosheets based on the reduction of graphite oxide (GO) in tube furnace assembly at different temperatures. The morphologies, microstructures, specific surface areas and other features of GO and graphene nanosheets were characterized. Structure characterization indicates that the platelet thickness of graphene nanosheets obtained at 300 °C was 1.62 nm, which corresponds to an approximately 5 layers stacking of the monoatomic graphene nanosheets. Electrochemical performances of the as-prepared graphene nanosheets were performed, the result of which could prove the above observation that graphene nanosheets (5 layers) obtained at 300 °C actually displayed the most remarkable electrochemical performances: the first discharge and charge capacities of graphene nanosheets were as high as 2137 mAh/g and 994 mAh/g, respectively, and after 100 cycles graphene nanosheets still possessed a high capacity of 478 mAh/g.     

Focusing on energy and optoelectronic applications: a journey for graphene and graphene oxide at large scale

Carbon is the only element that has stable allotropes in the 0th through the 3rd dimension, all of which have many outstanding properties. Graphene is the basic building block of other important carbon allotropes. Studies of graphene became much more active after the Geim group isolated "free" and "perfect" graphene sheets and demonstrated the unprecedented electronic properties of graphene in 2004. So far, no other individual material combines so many important properties, including high mobility, Hall effect, transparency, mechanical strength, and thermal conductivity. In this Account, we briefly review our studies of bulk scale graphene and graphene oxide (GO), including their synthesis and applications focused on energy and optoelectronics. Researchers use many methods to produce graphene materials: bottom-up and top-down methods and scalable methods such as chemical vapor deposition (CVD) and chemical exfoliation. Each fabrication method has both advantages and limitations. CVD could represent the most important production method for electronic applications. The chemical exfoliation method offers the advantages of easy scale up and easy solution processing but also produces graphene oxide (GO), which leads to defects and the introduction of heavy functional groups. However, most of these additional functional groups and defects can be removed by chemical reduction or thermal annealing. Because solution processing is required for many film and device applications, including transparent electrodes for touch screens, light-emitting devices (LED), field-effect transistors (FET), and photovoltaic devices (OPV), flexible electronics, and composite applications, the use of GO is important for the production of graphene. Because graphene has an intrinsic zero band gap, this issue needs to be tackled for its FET applications. The studies for transparent electrode related applications have made great progress, but researchers need to improve sheet resistance while maintaining reasonable transparency. Proposals for solving these issues include doping or controlling the sheet size and defects, and theory indicates that graphene can match the overall performance of indium tin oxide (ITO). We have significantly improved the specific capacitance in graphene supercapacitor devices, though our results do not yet approach theoretical values. For composite applications, the key issue is to prevent the restacking of graphene sheets, which we achieved by adding blocking molecules. The continued success of graphene studies will require further development in two areas: (1) the large scale and controlled synthesis of graphene, producing different structures and quantities that are needed for a variety of applications and (2) on table applications, such as transparent electrodes and energy storage devices. Overall, graphene has demonstrated performance that equals or surpasses that of other new carbon allotropes. These features, combined with its easier access and better processing ability, offer the potential basis for truly revolutionary applications and as a future fundamental technological material beyond the silicon age.     

Free-standing graphene on microstructured silicon vertices for enhanced field emission properties

Controlled deposition of graphene in different orientations relative to the substrate is challenging and majority of existing deposition methods lead to sheets that lay flat on the substrate surface, limiting the potential applications in which the exposed sheet surface area and the atomically thin edges of graphene are exploited. Here we describe a simple and general solution-based methodology for the fabrication of random arrays of free-standing few-layer graphene (FLG) flakes on micro-spikes engraved on Si substrates. This should greatly benefit applications using free-standing graphene, such as in energy storage/conversion devices and bright electron sources. As a proof of concept, it is shown that the FLG sheets protruding on the top of micro-spikes are good electron emitters with turn-on fields as low as 2.3 V μm(-1) and field enhancement of few thousands. The emission performance and long-term stability achieved by this hierarchical deposition process are superior to that of planar graphene sheets and demonstrate promise for applications. Mechanisms leading to formation of free-standing FLG flakes are discussed.     

A new molecular model for water adsorption on graphitized carbon black

Adsorption of water on graphitized carbon black at various temperatures has been studied with a new molecular model of graphitized carbon black using Monte Carlo simulation. The model is a collection of graphene layers, modelled by the Steele potential, and a number of phenol groups forming clusters of various sizes which are placed randomly at the graphene edge sites to give an O/C ratio of 0.006. The results are compared with experimental data reported by Kiselev et al. [1] in 1968 for a range of temperatures, and for the first time a reconciliation between the experimental data and simulation has been successfully achieved. The simulation results show that water adsorbs preferentially around the functional groups to form clusters, which then grow and merge at the edges of the graphene layers, rather than adsorbing onto the basal planes of the graphene because the electrostatic interactions (hydrogen bonding) between water molecules are stronger than the basal plane–water dispersion interactions.     

石墨烯在复合防腐涂层中的应用研究进展

基于石墨烯和氧化石墨烯不同的改性方法综述了石墨烯在防腐复合涂层中应用的研究进展,探讨了石墨烯防腐蚀机理,论述了石墨烯和氧化石墨稀复合防腐涂层的合成方法。其中石墨烯的改性方法有：原位改性石墨烯、电化学沉积方法和原位还原氧化石墨烯,而氧化石墨稀的改性方法包括有机改性剂改性氧化石墨烯、无机改性剂改性氧化石墨烯和微胶囊技术改性氧化石墨;并对石墨烯复合防腐涂层的发展前景进行了展望。     

自支撑石墨烯炭膜的制备及气体分离性能

通过溶剂蒸发法得到聚酰胺酸（PAA）与氧化石墨烯（GO）的复合石墨烯膜,并经600℃炭化制备了具有良好柔韧性的仿贝壳珍珠层结构的自支撑石墨烯炭膜。通过X射线衍射和场发射扫描电镜对薄膜微观结构进行表征,并测试不同PAA固含量制备的石墨烯炭膜对CO₂和CH₄的分离性能。结果表明,炭化后,GO被还原成石墨烯,呈层状堆叠,堆叠的层间填充了空穴和残炭;石墨烯炭膜的CO₂渗透通量和CO₂/CH₄分离理想选择性随PAA加入量增加,CO₂通量最高可达824 barrer,此时CO₂/CH₄理想选择性达38.9。石墨烯层骨架和碳分子筛构成石墨烯炭膜的气体传输通道,本研究成果为柔性自支撑气体分离炭膜的制备开辟了新思路。     

Synthesis of silver nanoprisms on reduced graphene oxide for high-performance catalyst

We developed a facile hydrothermal method to synthesize Ag nanoprism on reduced graphene oxide (rGO) with the assistance of sodium alginate (SA). It was found that most of the Ag nanoparticles have {111} external facets which are parallel to the (0001) of the reduced graphene oxide matrix and thus the Ag nano-particles have shown a triangle morphology. When used as a catalyst in the oxidation of hydroquinone, the obtained SA–Ag–rGO showed an outstanding performance: the catalytic rate constant of the hybrid is more than 12 times higher than that of Ag spherical particles on graphene sheets.     

Synthesis of transfer-free graphene films on dielectric substrates with controllable thickness via an in-situ co-deposition method for electrochromic devices

The solutions and polymer supported materials in graphene transfer process would introduce lots of containments, defects and wrinkles, which weakens the performance of graphene. Herein, an in-situ co-deposition method is carried out to obtain transfer-free graphene films with controllable thickness on several dielectric substrates. The amorphous carbon (carbon source) and copper (catalyst) are co-deposited on dielectric substrates. Followed by an in-situ annealing process, the amorphous carbon is transformed to few-layer graphene. High co-deposition temperature could promote the decomposition of Cu(acac)₂ precursors, leading to the controllable thickness of amorphous carbon layer in Cu@C films. Finally, 3-, 5-, 8- and 10- layers graphene films with transmittance of up to 93.5% and square resistance of 0.8 kΩ·sq^?1 are obtained and a high-performance electrochromic device is fabricated using 3 layers graphene films as electrodes. The “color” and “bleach” time of the electrochromic device is 16.6 s and 6.8 s with the transmittance of 26.8% and 79.7% separately. This method paves an alternative way for the batch production of transfer-free graphene film as electrode materials.     

A review study on the recent advances in developing the heteroatom-doped graphene and porous graphene as superior anode materials for Li-ion batteries

Graphene materials, with their distinctively fascinating physicochemical properties, have been receiving great attention as favorable anode materials for use in Li-ion batteries (LIBs). However, the high affinity of graphene nanosheets to restack and agglomerate during electrode assembly reduces the deliverable specific capacity due to the limited available surface area and active sites for Li-ion storage. Furthermore, the high aspect ratio of graphene nanosheets could result in long transport pathways for Li-ions and consequently limiting the rate performance. These drawbacks can be significantly improved via the functionalization of graphene by various heteroatoms and also the formation of porous graphene, adding unique beneficial properties to the inherent characteristics of graphene. Here, a comprehensive review of porous and/or heteroatom doped graphene anode materials for LIBs is presented, which summarizes in detail the main recent literature from their procedure, optimum synthesis parameters, relevant mechanisms, and the obtained morphology/structure to their electrochemical performance as the LIBs anode. Finally, the research gaps are proposed. This review will promote the basic understanding and further development of porous and/or doped graphene materials as anodes for LIBs.     

用于水质净化的氧化石墨烯膜研究进展

氧化石墨烯膜具有超高的水通量、可控的层间距以及卓越的分离性能,这些优异的特性使氧化石墨烯膜有望成为新一代膜材料并用于水环境中物质的精确分离。对氧化石墨烯膜的研究已经取得了许多重要的成果,本文系统地阐述了用于水质净化的氧化石墨烯膜的结构特性和构效关系,总结了氧化石墨烯膜典型的制备方法,重点介绍了氧化石墨烯膜的改性方式,概述了氧化石墨烯膜在多种水环境中的应用,总结并展望了氧化石墨烯膜的发展方向,为设计和合成高性能氧化石墨烯膜用于水质净化提供新的思路。     

Investigation on Performance of PDMS-Graphene/PES Hybrid Membrane for Pervaporative Separation of Phenol from Aqueous Streams

The pervaporative performances of pristine polydimethylsiloxane (PDMS) membrane and modified one by hybridizing with graphene nanosheets (PDMS-G) were evaluated for phenol removal from aqueous solutions. The incorporation of hydrophobic graphene nanosheets could enhance the process performance. The optimum performance was determined at 0.2 wt% crosslinker concentration and 0.2 wt% graphene content with a significant improvement in the separation factor up to 42.35. The enhanced separation factor can be attributed to optimized interfacial free volume in the structure of the membranes and formation of π-π interactions between graphene and phenol. The effects of operating parameters on separation performance were also evaluated.     

Research progress of graphene oxide membrane for water purification

Graphene oxide membranes have ultra-high water flux, controllable interlayer spacing and excellent separation properties. These outstanding characteristics make graphene oxide membranes promising to be a new generation of membrane materials and used for the precise separation of substances in the water environment. At present, researchers have performed numerous studies on graphene oxide membranes and achieved breakthrough results, including the transfer behavior of water in the membrane, the separation mechanism of the membrane and the preparation methods of the membrane, etc. However, there is still a lack of comprehensive understanding of graphene oxide membranes. This review systematically described the structural properties and structure-effect relationships of graphene oxide membrane, and summarized the typical preparation methods. In terms of the challenges faced by graphene oxide membrane in practical application, we focused on the existing modification methods of graphene oxide membrane. The applications of graphene oxide membrane in various water environments were also discussed. Finally, the future development of graphene oxide membrane was summarized and prospected. The aim of this paper is to provide novel ideas for the design and synthesis of high-performance graphene oxide membranes for water purification.     

Graphene transfer: key for applications

The first micrometer-sized graphene flakes extracted from graphite demonstrated outstanding electrical, mechanical and chemical properties, but they were too small for practical applications. However, the recent advances in graphene synthesis and transfer techniques have enabled various macroscopic applications such as transparent electrodes for touch screens and light-emitting diodes (LEDs) and thin-film transistors for flexible electronics in particular. With such exciting potential, a great deal of effort has been put towards producing larger size graphene in the hopes of industrializing graphene production. Little less than a decade after the first discovery, graphene now can be synthesized up to 30 inches in its diagonal size using chemical vapour deposition methods. In making this possible, it was not only the advances in the synthesis techniques but also the transfer methods that deliver graphene onto target substrates without significant mechanical damage. In this article, the recent advancements in transferring graphene to arbitrary substrates will be extensively reviewed. The methods are categorized into mechanical exfoliation, polymer-assisted transfer, continuous transfer by roll-to-roll process, and transfer-free techniques including direct synthesis on insulating substrates.     

Strategies for interfacial localization of graphene/polyethylene-based cocontinuous blends for electrical percolation

We have investigated melt blending approaches to interfacial localization of few-layer graphene in cocontinuous polymer blends with polyethylene as one of the components. When linear low-density polyethylene (LLDPE)/polypropylene (PP) or high-density polyethylene (HDPE)/polylactic acid (PLA) and graphene were mixed all together, graphene preferred polyethylene over PP or PLA. When PP and graphene were premixed and blended with polyethylene, some graphene was trapped at the blend interface but not enough to cover the large interfacial area. In contrast, an ultralow electrical percolation was achieved (< 0.1 vol%) in HDPE/PLA blend due to smaller interfacial area. In another approach, polystyrene was added as a tertiary minor component to HDPE/PLA blends. This continuous interfacial layer containing graphene led to a low electrical percolation threshold (< 0.2 vol%). From these investigations, we suggest general ways to reduce a percolation threshold by kinetic control of the morphology of cocontinuous polymer blends.     

Graphene/silver nanowire sandwich structures for transparent conductive films

We report a simple graphene/silver nanowire (AgNW)/graphene sandwich structure that can be used to prepare highly transparent conductive films; the electrical conductivity of this structure is superior to those of pure AgNW or graphene/AgNW films. Upon increasing the graphene content, the ratio of the direct current (DC) conductivity to the optical conductivity of the three-layer graphene/AgNW/graphene film increased from 4.7 to 44, primarily as a result of connecting and clipping effects. At low contents of AgNW, the graphene played a role of connecting the AgNWs, thereby increasing the DC conductivity by nearly seven orders of magnitude relative to that of pure AgNW films; when the AgNW content was high, the DC conductivity was also enhanced, by 23.8-fold. Observing the second-order zone-boundary phonons, the enhancement in conductivity resulted mainly from tighter contact between the AgNWs, arising from restacking of the top and bottom graphene sheets.     

涂层中石墨烯应用及标准化研究进展

石墨烯作为当下新材料研究热点,其结构与性能研究及其产业化发展持续升温,其应用已在各行各业中占有了一席之地。但市场上流通的石墨烯产品质量不一,有的甚至给石墨烯产业带来了负效应。而随着石墨烯产业化的高速发展,石墨烯相关标准化工作的开展重要性、紧迫性越来越显著。为了促进石墨烯的应用研究及标准化工作开展,本文对石墨烯的结构特性、涂层中石墨烯的应用及标准化研究情况进行介绍,并对石墨烯材料未来发展做出展望。