石墨及石墨/双马来酰亚胺减摩树脂复合材料的XRD研究

利用X射线衍射对鳞片石墨、可膨胀石墨、膨胀石墨和纳米石墨薄片以及石墨 /双马来酰亚胺、纳米石墨薄片 /双马来酰亚胺减摩复合材料进行了研究,探讨它们之间在结构上的关系以及以复合材料中双马来酰亚胺预聚体对石墨层间距的影响.实验结果表明:可膨胀石墨中插层剂的插入除了增大石墨层间距外,还减小相邻插层剂未插入的石墨层间距;膨胀石墨的结构除了保留强度很弱的石墨特征峰外,还有大量强度极其微弱、层间距大小不一的峰;超声波对膨胀石墨的结构有整合、均匀化作用;双马来酰亚胺预聚体不能插入鳞片石墨层间,而能插入纳米石墨薄片的层间.     

Facile synthesis of highly conductive polyaniline/graphite nanocomposites

A facile process for the synthesis of exfoliated graphite and polyaniline/graphite (PANI/graphite) nanocomposite was developed. Graphite nanosheets were prepared via the microwave irradiation and sonication from synthesized expandable graphite. The nanocomposites were fabricated via in situ polymerization of aniline monomer in the presence of graphite nanosheets. The nanoscale dispersion of graphite sheets was evidenced by the SEM and TEM examinations. According to the electrical conductivity test, the conductivity of the final PANI/graphite nanocomposites were dramatically increased compared with pristine PANI. From the thermogravimetric analysis, the introduction of graphite exhibits a beneficial effect on the thermal stability of PANI.     

Synthesis and characterization of polyaniline/graphite conducting nanocomposites

A new method for the synthesis of exfoliated graphite and polyaniline (PANI)/graphite nanocomposites was developed. Exfoliated graphite nanosheets were prepared through the microwave irradiation and sonication of synthesized expandable graphite. The nanocomposites were fabricated via the in situ polymerization of the monomer at the presence of graphite nanosheets. The as-synthesized graphite nanosheets and PANI/graphite nanocomposite materials were characterized with Fourier transform infrared spectroscopy, scanning electron microscopy, transmission electron microscopy, and thermogravimetric analysis (TGA). The conductivity of the PANI/graphite nanocomposites was dramatically increased over that of pure PANI. TGA indicated that the incorporation of graphite greatly improved the thermal stability of PANI. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 1972–1978, 2004     

PMMA／石墨导电复合材料的制备与表征

以可膨化石墨为原料,高温处理得到膨化石墨,再经过超声处理,得到纳米薄片石墨。将得到的纳米薄片石墨与甲基丙烯酸甲酯单体在超声作用下预聚,灌模,得到块状的聚甲基丙烯酸甲酯(PMMA)/石墨复合材料。用扫描电子显微镜(SEM)、透射电子显微镜(TEM)、选区电子衍射SAD、红外、热重等分析仪器表征了纳米石墨薄片及PMMA/石墨复合材料。测试了复合材料的力学、电学性能,发现在室温下该复合材料的渗滤阀值为1.3%(wt),且保证石墨含量在1.4%(wt)时,即可保证复合材料具有良好的电学和力学性能。     

The preparation of porous graphite and its application in lithium ion batteries as anode material

Graphite is the most widely used anode material for lithium ion batteries (LIBs). However, the performance of graphite is limited by its slow charging rates. In this work, porous graphite was successfully prepared by nickel-catalyzed gasification. The existence of the pores and channels in graphite particles can greatly increase the number of sites for Li-ion intercalation-deintercalation in graphite lattice and reduce the Li-ion diffusion distance, which can greatly facilitate the rapid diffusion of lithium ions; meanwhile, the pores and channels can act as buffers for the volume change of the graphite in charging-discharging processes. As a result, the prepared graphite with pores and channels exhibits excellent cycling stability at high rate as anode materials for LIBs. The porous graphite offers better cycling performance than pristine graphite, retaining 81.4 % of its initial reversible capacity after 1500 cycles at 5 C rates. The effective synthesis strategy might open new avenues for the design of high-performance graphite materials. The porous graphite anode material is proposed in applications of high rate charging Li-ion batteries for electric vehicles.     

膨胀石墨制备方法的研究进展

综述了膨胀石墨制备方法的研究现状,重点阐述了两种常用制备方法:（1）以天然鳞片石墨为原料,先经氧化制得可膨胀石墨,再经膨化处理得膨胀石墨;（2）将氧化和膨胀同时进行的爆炸法。分析了不同制备方法的优劣。并对膨胀石墨的制备工艺进行了展望。参考文献48篇。     

粒度对石墨负极材料嵌锂性能的影响

研究了不同粒径（13～80 μm）石墨材料作为锂离子电池负极材料的嵌锂性能.结果表明，石墨粒度大小对嵌锂性能有明显影响，石墨的不可逆容量随着粒径的减小而逐渐增大，当粒径从80 μm减小到13 μm时，其不可逆容量增大了10％.而对可逆容量来说，随着粒径的减小，可逆容量逐渐增大;当粒径减小到20 μm时，可逆容量达到最大;再进一步减小石墨颗粒的粒径，可逆容量则随之减小.这表明石墨颗粒过大或过小都不利于锂离子的可逆脱嵌，只有合适的粒度才能最大限度地可逆脱嵌锂离子.根据不同粒度石墨的比表面的变化趋势，阐述了嵌锂性能随粒度变化的原因.     

Fluorination of treated carbon

Graphite fluoride is classified into (C₂F)n and (CF)n types from the structure and composition. Both compounds have such unique physicochemical properties as low surface energy, solid lubricating characteristics, and oxidizing ability. However, a long reaction time is required to completely fluorinate graphite and moreover, the decomposition reaction of the product causes the lowering of the yields.In this paper, the effect of the pretreatments of the starting material on the fluorination will be reported on the following methods.1) Fluorination of Exfoliated Graphite Obtained by Heat-treatment of Graphite Lamellar Compound.The exfoliated graphite was obtained by the immersion of graphite into the mixed solution of sulfuric acid and hydrogen peroxide and subsequent heat-treatment. It has both much large surface area and larger lattice strain than that of the original graphite.The exfoliated graphite was much faster fluorinated than the original graphite. The dissociation of fluorine molecules to atoms was found to be a rate-determining step in the formation of graphite fluoride from the exfoliated graphite, whereas the process of diffusion of fluorine molecules was the rate-determining step in the fluorination of the original graphite.2) Fluorination of Residual Carbon Formed upon Pyrolysis of Graphite Fluoride.Graphite fluoride decomposes to carbon and some perfluorocarbons of low molecular weight at high temperature above 600 °C. The residual carbon was amorphous in analogy with petroleum coke or carbon black, but had smaller interlayer spacing and larger specific surface area due to its microporous structure than these amorphous carbonsThe rate of the direct fluorination of residual carbon at a room temperature was comparable to that of active carbon, and the graphite fluoride obtained from the residual carbon has a similar high thermostability to that of graphite fluoride obtained from graphite at a high temperature under an atmosphere of fluorine gas. Upon direct fluorination of the residual carbon a more crystalline graphite fluoride was obtained even at a low temperature than the case of petroleum coke and carbon black. It is interesting that the fluorination of the residual carbon leads to the formation of crystalline graphite fluoride in high yield.     

Formation of Protective Coatings on Graphite by a Microspark Oxidation Method

Models, mechanisms, and criteria of formation of protective coatings on graphite by a microspark oxidation method (MSO) are considered. It is established that a prerequisite for the graphite MSO is the deposition of a barrier film of a valve metal oxide at the graphite surface. Optimum regimes of the graphite MSO in aqueous solutions of sodium aluminate are determined. Protective coatings on graphite comprising α-phase aluminum oxide are obtained. It is concluded that the graphite MSO should be viewed as a version of MSO of metals, which involves the electrochemical deposition (at high voltages that cause the anode to microspark) of oxide films consisting of electrolyte components on graphite, as opposed to a version of MSO of metals, which involves the formation of an anodic film consisting of electrolyte components and the intrinsic oxide.     

Ni-P-C复合材料的制备及其电催化产氢性能研究

通过化学镀技术制备了亚微米级的Ni-P镀层石墨粉复合粉体新材料(即Ni-PC).采用扫描电子显微镜、X-射线能谱仪、X-射线粉末衍射仪对Ni-P-C复合粉体分别进行表面形貌分析、表面成分分析和物相分析.通过对Ni-P-C材料电极进行电解水析氢、循环伏安和Tafel极化等电化学测试,研究对比了Ni-P-C(石墨)材料与试剂石墨粉体以及纯Ni电极的电化学催化产氢性能.结果表明:利用化学镀技术成功地在石墨粉体表面镀上了一层亚微米级且均匀、致密的非晶态Ni-P合金.Ni-P-C(石墨)复合电极材料析氢能力强,具有良好的电化学活性.     

Electrochemical investigation of lithium intercalation into graphite from molten lithium chloride

Lithium reduction at a graphite electrode in molten lithium chloride was studied at temperatures from 650 to 900 °C using cyclic voltammetry and chronoamperometry. It was found that, during cathodic polarization, lithium intercalation into graphite occurred before deposition of metallic lithium started. This process was confirmed to be rate-controlled by the diffusion of lithium in the graphite. When the cathodic polarization potential was more negative than that for metallic lithium deposition, exfoliation of graphite particles from the electrode surface was observed. This was caused by fast and excessive accumulation of lithium intercalated into the graphite, which produced mechanical stress too high for the graphite matrix to accommodate. The erosion process was abated once the graphite surface was covered by a continuous layer of liquid lithium. These results are of relevance to the mechanism of carbon nanotube and nanoparticle formation by electrochemical synthesis in molten lithium chloride.     

Reversible Insertion of Mg-Cl Superhalides in Graphite as a Cathode for Aqueous Dual-Ion Batteries

Oxidative anion insertion into graphite in an aqueous environment represents a significant challenge in the construction of aqueous dual-ion batteries. In dilute aqueous electrolytes, the oxygen evolution reaction (OER) dominates the anodic current before anions can be inserted into the graphite gallery. Herein, we report that the reversible insertion of Mg-Cl superhalides in graphite delivers a record-high reversible capacity of 150 mAh g⁻¹ from an aqueous deep eutectic solvent comprising magnesium chloride and choline chloride. The insertion of Mg-Cl superhalides in graphite does not form staged graphite intercalation compounds; instead, the insertion of Mg-Cl superhalides makes the graphite partially turbostratic.     

基体石墨的孔隙结构及其对单质Ag扩散的影响

高温气冷堆燃料元件的基体石墨是一种多孔复合材料,是燃料元件的主要组成部分,其结构影响燃料元件的性能和裂变产物在燃料元件中的扩散。 本文利用压汞法表征基体石墨的孔隙结构,并讨论了基体石墨制备工艺中最大压制压强与热处理过程对孔隙结构的影响。 结果表明,基体石墨大孔孔径分布为6001900 nm,高温热处理使基体石墨的总孔隙率、中值孔径、大孔孔容均减小;基体石墨热处理样品的大孔孔容随最大压制压强的增加而呈线性减少,热处理过程单质Ag在石墨基体中的扩散速度与大孔孔容变化具有正相关性。     

聚乙烯在石墨表面结晶的分子动力学模拟

采用分子动力学方法模拟了聚乙烯在石墨(001)表面的吸附和结晶过程;直观的给出了聚乙烯链被石墨(001)面吸附并诱导形成有序的片层晶体的过程;发现结晶温度对得到的有序结构中的聚乙烯链相对石墨表面的特定取向有影响(300 K和600 K时的取向方向不同);表面覆盖率影响聚乙烯吸附层的厚度,对取向的方向无影响.     

Thermal conductivity of exfoliated graphite nanocomposites

Since the late 1990’s, research has been reported where intercalated, expanded, and/or exfoliated graphite nanoflakes could also be used as reinforcements in polymer systems. The key point to utilizing graphite as a platelet nanoreinforcement is in the ability to exfoliate graphite using Graphite Intercalated Compounds (GICs). Natural graphite is still abundant and its cost is quite low compared to the other nano–size carbon materials, the cost of producing graphite nanoplatelets is expected to be ~$5/lb. This is significantly less expensive than single wall nanotubes (SWNT) (>$45000/lb) or vapor grown carbon fiber (VGCF) ($40–50/lb), yet the mechanical, electrical, and thermal properties of crystalline graphite flakes are comparable to those of SWNT and VGCF. The use of exfoliated graphite flakes (xGnP) opens up many new applications where electromagnetic shielding, high thermal conductivity, gas barrier resistance or low flammability are required. A special thermal treatment was developed to exfoliate graphite flakes for the production of nylon and high density polypropylene nanocomposites. X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM) were used to assess the degree of exfoliation of the graphite platelets and the morphology of the nanocomposites. The thermal conductivity of these composites was investigated by three different methods, namely, by DSC, modified hot wire, and halogen flash lamp methods. The addition of small amounts of exfoliated graphite flakes showed a marked improvement in thermal and electrical conductivity of the composites.     

Electrochemical synthesis and physical-chemical characterization of the low-oxidized graphite fluoroxide materials

A process of anodic oxidation of purified natural graphite in aqueous 11-45% HF solutions has been studied at constant voltages 5-7 V. New types of low-oxidized graphite fluoroxide materials (FOG-E) were isolated, prepared under electrochemical synthesis conditions only. Electrochemical oxidation of graphite should include in a first step the reaction of evolving oxygen and O-containing groups with surface carbon atoms on graphite particles and a subsequent formation of C-OH bonds, and in a second step, a partial substitution of the latter groups into C-F groups. Chemical and physical-chemical study of FOG-E showed that they are multiphasic materials. The low-oxidized graphite fluoroxide materials are excellent precursors for the preparation of thermally expanded graphite (TEG).     

Synthesis, structure and composition of an expanding form of metallized graphite

Synthesis, graphite structure and composition of an expanding form of nickel-plated and copper-clad graphite were investigated. Expanded flakes were obtained by thermal treatment at 800°C. Structure of metallized graphite was studied by electron microscopy.     

X-ray spectroscopy study of lithiated graphite obtained by thermal deposition of lithium

X-ray photoelectron spectroscopy (XPS), X-ray emission spectroscopy (XES), and near edge X-ray absorption fine structure (NEXAFS) spectroscopy are used for in situ studies of the electronic structure of lithiated natural graphite produced by thermal deposition of lithium upon graphite in a vacuum. By XPS and NEXAFS spectroscopy it is found that lithium vapor thermal deposition results in the formation of a lithiated graphite surface layer and a change in its electronic structure. Based on the quantum chemical simulation of the experimental СK_α XES spectrum of lithiated graphite, it is found that lithium atoms are located mostly on the edges of graphite crystallites. Atomic force microscopy reveals that the size of natural graphite flakes varies from 50 nm to 200 nm.     

Platinum Nanosheets Intercalated into Natural and Artificial Graphite Powders

Insertion of sheet-type platinum particles (platinum nanosheets) between graphite layers was achieved by a thermal treatment of a mixture of platinum chloride (IV) and graphite powder (natural graphite or artificial graphite) under 0.3 MPa of chlorine at 723 K, followed by the treatment under 40 kPa of hydrogen pressure. Similar platinum nanosheets, which were 1–3 nm in thickness and 100–500 nm in width and had a number of hexagonal holes and edges with 120° angle, were formed between the layers of both natural graphite or artificial graphite; however, their location in the graphite layers depended on the type of graphite used. A number of platinum nanosheets were observed in the edge region of natural graphite particles which have flat surface. On the other hand, a number of platinum nanosheets were found inside and away from the edge of the artificial graphite particles especially in the vicinity of the cracks. Both the platinum nanosheet-containing artificial and natural graphite samples showed high selectivity to cinnamyl alcohol in cinnamaldehyde hydrogenation under supercritical carbon dioxide conditions, while spherical platinum particles, which were located on the surface of natural and artificial graphite, showed lower selectivity.     

Electrochemical and spectroscopic characterization of quinone functionalized exfoliated graphite.

Natural graphite was exfoliated by thermal decomposition of graphite-bisulfate intercalation compound. Oxidative/reductive pre-treatment of exfoliated graphite was subsequently carried out to introduce various functional groups on the graphite surface. The resulting material was covalently modified with redox active quinones. The covalent modification was effected through oxygen containing functional groups formed on the graphite surface. The modified exfoliated graphite was characterized by infra-red (FTIR) and X-ray photoelectron spectroscopy (XPS). Electrochemical characterization of the pressed pellets of the modified graphite showed that the modification occurred at the edge sites. These electrodes were found to be very stable and the surface renewal was simply accomplished by polishing the surface using SiC emery sheets. Application of the benzoquinone modified electrode for the electrocatalysis of ascorbic acid oxidation was demonstrated.