One-step preparation of graphene nanosheets via ball milling of graphite and the application in lithium-ion batteries

An improved method for mass production of good-quality graphene nanosheets (GNs) via ball milling pristine graphite with dry ice is presented. We also report the enhanced performance of these GNs as working electrode in lithium-ion batteries (LIBs). In this improved method, the decrease of necessary ball milling time from 48 to 24 h and the increase of Brunauer–Emmett–Teller surface area from 389.4 to 490 m²/g might be resulted from the proper mixing of stainless steel balls with different diameters and the optimization of agitation speed. The as-prepared GNs are investigated in detail using a number of techniques, such as scanning electron microscope, atomic force microscope, high-resolution transmission electron microscopy, selected area electron diffraction, X-ray diffractometer, and Fourier transform infrared spectroscopic. To demonstrate the potential applications of these GNs, the performances of the LIBs with pure Fe₃O₄ electrode and Fe₃O₄/graphene (Fe₃O₄/G) composite electrode were carefully evaluated. Compared to Fe₃O₄-LIBs, Fe₃O₄/G-LIBs exhibited prominently enhanced performance and a reversible specific capacity of 900 mAh g^?1 after 5 cycles at 100 and 490 mAh g^?1 after 5 cycles at 800 mA g^?1. The improved cyclic stability and enhanced rate capability were also obtained.     

研磨溶液对改性石墨矿表面性质及微观结构的影响

使用行星式球磨机对石墨矿粉(G)进行湿法球磨改性,以硅烷偶联剂Si-69为改性剂,考察了球磨溶液对石墨矿粉微观结构和表面性质的影响,然后将改性石墨矿粉填充到丁苯橡胶中,考察了改性石墨/丁苯胶复合材料的力学性能及微观结构.结果表明,球磨溶液不同,改性石墨矿粉的微观结构和表面性质有所不同.以异丙醇为球磨溶液的改性石墨矿粉(...     

Synthesis of Composite Nanosheets of Graphene and Boron Nitride and Their Lubrication Application in Oil

Composite nanosheets of graphene and boron nitride have been produced in large quantities for the first time using high‐energy ball milling in ammonia gas as an exfoliation agent. The anti‐wear properties of the composite nanosheets as a lubricant additive are investigated via a four‐ball method. The results show that the composite nanosheets are exfoliated from the commercial graphite and h‐BN powders and combined into graphene/BN composite nanosheets during the ball milling process. The composite nanosheets formed have diameters larger than 200 nm and consist of heterostructures of approximately 10 monolayers of graphene and BN. The composite nanosheets exhibit better wear resistance and friction reduction properties than the homogeneous nanosheets because of the stronger interaction between graphene and BN nanosheets, which can effectively improve the anti‐wear properties of mineral base oil as a lubricant additive.

     

石墨微片/环氧复合防腐涂料的制备及防腐机制

以水性环氧乳液（EP emulsion）及其固化剂为基体,加入石墨微片（GNs）制备防腐涂料,并分析防腐机制。通过盐雾时间测试发现GNs用量为EP emulsion中EP质量的4%时,其耐盐雾时间最长为240 h,同时其200 h划十字线的腐蚀距离低于市售Fe₂O₃/EP涂料。从GNs/EP emulsion复合防腐涂料漆膜表面的SEM图像可以发现,GNs分散的越均匀,涂膜的防腐能力越强。通过Tafel极化曲线发现,该含量漆膜具有腐蚀电位高和腐蚀电流小的特点,这是由GNs在环氧树脂中均匀分布形成微观电容提高树脂介电常数,进而提高漆膜电荷储存能力,减弱电子移动能力而实现的,并借助Nyquist曲线及漆膜断面的SEM图像,建立等效电路及石墨微电容防腐模型。研究发现,GNs/EP emulsion防腐涂料的防腐机制是通过借助GNs的化学稳定性对水和氧气的物理隔绝作用以及通过微电容的形成减弱电子移动能力的电化学作用共同实现。     

Preparation and Surface Characterization of Highly Ordered Polymer/Graphite Nanosheet Composites

Graphite nanosheets obtained from sonicating expanded graphite were coated chemically with magnetite nanoparticles. The modified graphite nanosheets were dispersed in epoxy or unsaturated polyester prepolymer, and subjected to a magnetic field before the suspension solidified. Composites with graphite nanosheets of highly ordered alignment have been prepared via the described approach. Several techniques, including X-ray diffraction (XRD), scanning electron microscopy (SEM), and optical microscopy were used to characterize the modified graphite nanosheets and the polymer/graphite nanosheet composites.     

Ball‐Mill‐Exfoliated Graphene: Tunable Electrochemistry and Phenol Sensing

A simple wet ball‐milling method for exfoliating pristine graphite to graphene nanosheets is proposed. The surfactant of cetyltrimethyl ammonium bromide is utilized to greatly improve the exfoliation efficiency of graphene nanosheets. Variation of the ball‐milling time is an efficient way to control the size and thickness of graphene nanosheets, as well as the level of edge defects. With an increase of ball‐milling time, superior electrochemical reactivity is imparted owing to enlarged active area and increased catalytic ability. The obtained graphene nanosheets are sensitive for electrochemical oxidation of phenols (e.g., hydroquinone, p‐chlorophenol, and p‐nitrophenol), and thus qualified for the simultaneous sensing of trace level of phenols. The detection limits of simultaneous monitoring of hydroquinone, p‐chlorophenol, and p‐nitrophenol are as low as 0.017, 0.024, and 0.42 mg L^?1, respectively. The proposed strategy thus opens up a new way to tune electrochemistry of graphene materials as well as to design their new applications.     

Evidences of Rubber Grafting on Activated Carbon Surfaces Containing Fullerene‐like Structures

Abstract

It is shown that graphite is converted into an high disordered carbon black by prolonged ball milling. The kinetics of this transformation has been followed by powder x‐ray diffraction, measurements of the crystallinity and of the surface area. Ball milling is able to introduce an high concentration of defective sites in the pristine graphite including the fullerene‐like structures. By mixing with natural rubber both the pristine and the ball‐milled graphite, it is shown by bound rubber measurements that the amount of rubber grafted (chemically linked) on the pristine graphite surface is negligible but reaches a very high level in the ball‐milled graphite. Similarly, ball‐milling of N660 carbon black causes a deep activation of its surface activity which can be measured by a significant increase in the bound rubber level and in the amount of grafted rubber in comparison to the pristine N660 sample. The bound rubber measurement has been performed also on a natural rubber masterbatch with extracted fullerene carbon black (EFCB). Also in this case extremely high levels of rubber grafting have been achieved in comparison to graphite. It is discussed and demonstrated that the fullerene‐like nanostructures in carbon blacks play a key role in the formation of bound rubber phenomenon and in grafting natural rubber on carbon black surface.     

石墨/TiO2复合光催化剂的制备和性能

以石墨和纯的TiO₂为原料,采用球磨工艺制备了石墨/TiO₂复合光催化剂。使用XRD、SEM、TEM、XPS和DRS等手段对其性能进行了表征。以甲基橙为模拟污染物,研究了石墨掺入量、球磨时间对复合光催化剂光催化活性的影响。结果表明,石墨/TiO₂复合光催化剂具有锐钛矿结构,球磨后TiO₂(101)面的衍射峰宽化并右移,TiO₂成为200 nm左右的不规则球状颗粒,在其表面均匀分布着石墨。TiO₂晶粒的Ti-O键的结合能变高,且表面有缺陷产生,使其在可见光区具有显著的吸收。石墨掺入量为5%、球磨时间为12 h的石墨/TiO₂样品对甲基橙具有优异的光催化降解效果,在70 min的降解时间内甲基橙的降解去除率可达95.08%。石墨/TiO₂复合光催化剂的光催化反应速率常数k为0.043035 min^-1,是纯TiO₂的2.64倍。     

Preparation and characterization of foamed polyurethane/silicone rubber/graphite nanocomposite as radio frequency wave absorbing material: The role of interfacial compatibilization

A novel method for the preparation of radio frequency (RF) wave absorber polyurethane foam (PU) has been developed by impregnation of PU foam in n-hexane solution of room temperature vulcanizing (RTV) silicone rubber (SR) hybridized with graphite nanosheets (GNs) called doping solution. Extent of the GNs dispersion was optimized by the incorporation of a specific type of bifunctional compatibilizer. Insulator to conductive transition threshold as well as electromagnetic wave absorption characteristics of the fabricated nanocomposites was shown to be dependent upon the compatibilizer functionality. All PU/SR/GN nanocomposites generated from bifunctional compatibilizer exhibited higher electrical conductivity with enhanced permittivity implying enhanced formation of conductive networks by GN platelets. Permittivity of the PU/SR/GN nanocomposite based on bifunctional compatibilizer showed to be higher than uncompatibilized counterpart. Electromagnetic reflection loss behavior of the PU/SR/GN nanocomposites exhibited a non-linear correlation with the electrical conductivity. Although all PU/SR/GN prepared nanocomposites exhibited electromagnetic wave reflection loss behavior, but this revealed to be affected by the GN level as well as the size and dispersion state of the graphite nanosheets.     

超声波和修饰剂及预聚体对石墨层间结构的影响

利用X射线衍射(XRD)、扫描电镜(SEM)和傅立叶红外光谱仪(FT-IR)研究修饰剂、超声波和双马来酰亚胺(BMI)预聚体对纳米石墨薄片的石墨层间结构的影响,结果表明:超声波对膨胀石墨层间距结构的影响,因石墨层间距大小而不同,且超声波并没有破坏膨胀石墨的层状结构;修饰剂和双马来酰亚胺的预聚体可插入纳米石墨薄片中层间距较大的层间,但此层间距的石墨薄片较少,因此插入量也较少,可认为修饰剂或树脂的"插层"主要是插入纳米石墨薄片的网状孔隙内部.     

新型纳米铜/石蜡/膨胀石墨温敏复合材料的制备及性能

采用高能球磨法制备纳米铜/石蜡/膨胀石墨温敏复合材料,用扫描电镜(SEM)、高分辨透射电镜(TEM)对复合材料的微观形貌进行了表征,并测试了复合材料的膨胀性、温敏性和稳定性。结果表明,石蜡对铜粒的包覆效果良好,球磨98 h的复合颗粒近似球形,粒径约为100 nm。纳米铜/石蜡复合颗粒嵌入膨胀石墨的网络孔隙中。膨胀石墨使复合材料的膨胀性降低,改善其温敏性能,并使复合材料在高于相变温度下保持较高的稳定性。     

球磨法制备锂离子液流电池石墨负极浆料的性能研究

采用球磨法制备锂离子液流电池所用的石墨负极浆料,并对石墨负极浆料的颗粒形貌、电导率、比容量性能及循环性能进行研究。结果表明:导电添加剂的加入有助于提高电极浆料的悬浮稳定性;球磨过程可以降低石墨和导电添加剂混合粉体的电阻率,球料比达到5∶1时即可实现较好的球磨效果,但球料比不宜过高,否则会造成石墨材料层状结构的破坏,影响电极浆料性能的稳定性。提高石墨和导电添加剂的含量可以在电极浆料中形成稳定的导电网络结构,使可逆比容量提高;在保证电极浆料可流动的情况下,可逆比容量可大于40mAh/g。石墨负极浆料的容量损失主要发生在首次充放电过程中,随着循环次数的增加,容量损耗的速率降低,第5次循环以后容量趋于稳定。     

细粒级掺杂石墨材料的制备及其出气特性的研究

通过球磨分散方法制备了细粒级掺杂石墨 ,采用SEM、EDX、TEM、XRD等手段分析了材料微观结构 ,并对其性能作了初步研究。研究表明 :当原始粉粒径小于 10 0nm时 ,材料具有高的热导率和优良的物理机械性能 (抗弯强度为 116MPa) ,与粗晶石墨材料相比 ,细晶石墨材料在电子束辐照前的出气性能与其基本相同。而辐照之后 ,细晶石墨材料释放的H2 、H2 O、CO ,特别是CO2 的量远远少于粗晶石墨材料释放的量     

Polymorphic transformation and powder characteristics of TiO2 during high energy milling

Many studies have indicated that the reactivity of reactants can be enhanced greatly by mechanical activation through high energy ball milling. To understand this enhanced reactivity, the polymorphic transformation and the evolution of the powder characteristics of TiO₂ and graphite mixtures during high energy ball milling was investigated using various analytical instruments. It was found that polymorphic transformation of anatase to srilankite and rutile took place during milling. Furthermore, amorphization of crystalline phases and crystallization of the amorphous phase occurred at the same time during milling. High energy milling also led to ultrafine crystallites, large specific surface areas, and substantial amounts of defects in the powder particles. Effects of the graphite addition and the milling temperature on the polymorphic transformation and the evolution of the powder characteristics were also investigated. It was proposed that the polymorphic transformation of TiO₂ during milling could be explained in terms of the temperature-pressure phase diagram if the temperature rise and high pressure at the collision site were taken into consideration.     

Synthesis of TiC by controlled ball milling of titanium and carbon

Titanium and carbon powder mixtures with compositions of Ti_100−x C _x (x = 50, 40, 30) were milled under a helium atmosphere using a magneto ball mill. Controlled ball milling was performed in a higher energy impact mode and a lower energy shearing mode. For Ti₅₀C₅₀ and Ti₆₀C₄₀ powder mixtures milled in impact mode, TiC was formed via a mechanically-induced self-propagating reaction (MSR). When milling Ti₇₀C₃₀ in impact mode, the reaction to form TiC proceeded gradually as milling progressed; indicating that, for milling conditions that lead to the formation of TiC via MSR, a minimum carbon content is required to sustain the self-propagating reaction to form TiC. Milling in shearing mode resulted in the gradual formation of TiC during milling. This study found that increasing the carbon content of the starting powder mixture slowed the milling process. Replacing the activated carbon starting powder with high purity graphite was found to have little effect on the ignition time; indicating that the slowing of the milling process is not due to graphite acting as a lubricant during milling. Rather, this slowing of the milling process is most likely due to an increased carbon content resulting in an increase in the volume of the powder mixture. This would have a similar effect during milling to decreasing the ball:powder weight ratio (BPR), which is known to slow the milling process.     

Numerical and experimental investigations on new jar designs for high efficiency planetary ball milling

The internal shape of planetary ball mill jars was modified to increase the efficiency of the milling process. Four new jar designs are presented, where obstacles on the surface of a traditional cylindrical jar modify the ratio of normal-to-tangential transferred mechanical action, thus improving the comminution of the mill charge and reducing the process time. Multibody dynamics simulations, validated by operando video recordings of the process, were employed to investigate modified ball motion regimes promoting the increase of the number of high-energy impacts. Moreover, experimental grinding of calcium fluoride powder was performed to assess the effect of milling time and jar-to-plate velocity ratio, through the evaluation of size and microstrain of the end product deduced from X-ray diffraction line profile analysis.     

Thermoelectric properties of graphene nanosheets-modified polyaniline hybrid nanocomposites by an in situ chemical polymerization

A hybrid material of polyaniline protonated with hydrochloric acid and conductive graphene nanosheets (PANi/GNs) has been prepared by an in situ chemical polymerization method. The interactions between PANi and GNs in the hybrid composites are investigated by utilizing XRD, FT-IR, UV–vis and Raman. It is found that the PANi are adsorbed on the surface of the GNs, and the morphology of PANi transforms from twist structure to extended structure after the GNs are introduced. The thermoelectric (TE) properties of PANi/GNs composites have been investigated in the range from 323 K to 453 K. The electrical conductivity and the Seebeck coefficient of PANi/GNs composites are obviously higher than those of the PANi, while the thermal conductivity of the composites still keeps relatively low values even with high GNs content, resulting in the increase in dimensionless figure of merit (ZT). A highest ZT value of 1.95 × 10⁻³ has been obtained for the composite containing 30 wt % GNs at 453 K, which is about 70 times higher than that obtained from the PANi.     

Spark Plasma Sintered Hydroxyapatite/Graphite Nanosheet and Hydroxyapatite/Multiwalled Carbon Nanotube Composites: Mechanical and in Vitro Cellular Properties

Hyroxyapatite (HA) and its nanocomposites reinforced with 0.5, 1, 1.5, and 2 wt% graphite nanosheets (GNs) and multi‐walled carbon nanotubes (MWNTs) are fabricated by means of spark plasma sintering (SPS) process. The effects of MWNT and GN additions on the morphology, mechanical behavior, cell adhesion, and biocompatibility of HA were studied. Three‐point‐bending test shows that the bending strength of MWNT/HA nanocomposites increases with increasing MWNT content. However, the bending strength of GN/HA nanocomposites initially increases by adding 0.5 wt% GN, and then decreases markedly as the filler content increases. Cell culture and viability test results demonstrate that the GNs with diameters of several micrometers retard osteoblast cell adhesion and proliferation on the GN/HA nanocomposite. In contrast, the addition of 2 wt% MWNT to HA is beneficial to promote osteoblast adhesion and proliferation, thereby enhancing the biocompatibility of MWNT/HA nanocomposite.     

锂离子电池Si/C复合负极材料的合成与性能

采用球磨-热解工艺制备了Si/C复合负极材料。研究了球磨时间对Si/C复合负极材料结构和电化学性能的影响,并分析了电极的失效机理。研究结果表明,通过球磨可以将纳米硅颗粒均匀分散于石墨基体材料表面,同时,葡萄糖热解后形成的无定形碳使两者紧密结合。球磨3h合成的材料具有最优的电化学性能。以100mA/g的电流密度放电,首次放电容量达到1340mAh/g,首次充放电效率为75.6%,循环50次后,容量保持率为34.2%。     

Mechanism and kinetics of mechanically induced transformation of titanium and titanium hydride: Effect of reaction medium on microstructure, morphology and hydrogen-uptake properties

The stimulating effect of graphite addition on hydrogen sorption/desorption properties of titanium activated under ball milling and titanium hydride activated or prepared under ball milling is studied using X-ray diffraction, scanning and transmission electron microscopy, and temperature-programmed reaction/desorption techniques. The formation of microporous carbon matrix containing randomly distributed titanium or titanium hydride fragments of several nm in size is found to be the major effect of graphite addition. This kind of morphology allows the hydrogen transport to titanium or from titanium hydride surfaces without hindrances and improves titanium-hydrogen interaction through modifying the titanium surface and subsurface layers by interstitial C atoms.