由二种烟煤制备碳纳米管的探索性研究

以一种中国烟煤和一种新西兰烟煤为原料,采用电孤等离子体法制备碳纳米管。碳纳米管及其副产物富勒烯烟灰的表征采用扫描电镜（SEM）和红外光谱（FT－IR）等技术。结果表明：电弧放电时的缓冲气体压力对碳纳米管的产率影响很大;在一定的缓冲气压下电极间电流和电极间距各存在一最佳值。在He气压力为0.0665MPa、工作电流为40A条件下进行电弧放电,阴极上棒状沉积物的内芯中碳纳米管含量高达75％以上。基于实验结果,讨论了以煤为原料用电弧等离子体法制备碳纳米管过程中的工艺参数对碳纳米管生长的影响。     

Preparation and electrochemical performance of manganese oxide/carbon nanotubes composite as a cathode for rechargeable lithium battery with high power density

Manganese oxide/carbon nanotubes (MO/CNTs) composite was prepared by hydrothermally reducing KMnO₄ with CNTs, where the used CNTs are of dual role, i.e., they serve as reductant during reaction and the remaining CNTs act as conducting agent in the composite. This composite was characterized by X-ray diffraction and scanning electron microscopy techniques. In addition, the electrochemical performances of the composite were investigated, which suggested an excellent rate-capability of this material; e.g., it delivered a high discharge capacity as 131 mAh g^− 1 at a high current density of 4 A g^− 1 (20 C), and high capacity at low discharge current density, e.g., about 209 mAh g^− 1 at 0.2 C rate. Therefore, such a MO/CNTs composite is promising in high power application of lithium battery and electrochemical capacitor.     

尖锐端头碳纳米管的制备与场发射特性

采用氢电弧法制备了尖锐端头的碳纳米管,获得了具有三种特殊形貌的尖端,即锥形、颈缩形和铅笔状尖端.该特殊彤貌的彤成可归因于在原料中加入硅粉进而形成的结构缺陷.研究了所得碳纳米管的场发射特性,发现其阈值电场较低,仅为3.75V/mm;场发射电流密度可高达～1.6×105A/cm2;且场发射稳定性好.以上优异的场发射性能归结于该碳纳米管具有良好的结构完整性和独特的尖端结构特征.

Abstract：

Carbon nanotubes (CNTs)with sharp tips were synthesized by a hydrogen arc discharge method. Three unusual morphologies,i.e. ,a cone-shaped tip,a suddenly-shrinking tip,and a pencil point-like tip were observed. These novel tip structures are considered to be related to the addition of a small amount of silicon powder in the raw material,which may introduce structural defects in the CNTs. The field emission properly of the sharp-tip CNTs was investigated,and a low threshold electric field of 3.75 V/m,a high field emission current density of ～1.6× 105 A/cm2,and a good emission stability were demonstrated. The superior field emission performance of the CNTs can be attributed to their good crystallinity and unique tip structures.     

碳纳米管/微膨石墨复合负极材料的制备及电化学性能研究

通过对两种天然鳞片石墨进行微膨胀处理得到微膨石墨,然后以微膨石墨为基体采用化学气相沉积(CVD)法于微膨石墨的孔洞结构中原位生长碳纳米管,制备了碳纳米管/微膨石墨复合负极材料.电化学测试结果表明两种复合材料分别具有443和477 mAh/g的首次可逆容量.两种复合材料在0.2C倍率下循环充放电30次后容量均能保持95%以上;在1C下循环充放电50次后,可逆容量分别稳定在259和195 mAh/g.微膨胀处理形成的微纳米级孔洞以及原位碳纳米管的网络结构,提供了更多的储锂空间,并能够有效地缓冲电极材料在充放电时的体积变化;电解质溶液浸润在纳米孔洞中,有利于缩短锂离子的扩散路径,提高倍率循环性能;同时原位生长的类似常春藤形的碳纳米管可以起到桥梁的作用,避免"孤岛"的形成,增强了复合材料的导电性能.     

CNTs添加对MmMn0.4Co0.7Al0.3Ni3.4贮氢合金负极性能的影响

对商用MmMn_0.4Co_0.7Al_0.3Ni_3.4贮氢合金中添加多壁碳纳米管(CNTs)、Ni的电化学性能进行了研究.结果表明,CNTs的加入可以提高电极的放电容量和初始活化性能,合金中添加CNTs、CNTs+Ni的电极完全活化只需11个循环,其最大放电容量分别为255、271mAh/g.而添加Ni的电极则需24个循环才达到最大容量(245mAh/g);合金中添加CNTs、CNTs+Ni的电极具有更高的放电平台和更好的高倍率放电性能(HRD),在1000mAh/g放电电流下,添加CNTs、CNTs+Ni、Ni以及未添加电极的HRD值依次为80.5%、83.9%、66.9%和62.4%,线性极化和电化学阻抗测试表明,CNTs的加入可有效减少欧姆电阻、提高电极表面的电荷迁移速率,更有利于在大电流下进行放电.     

Synthesis of carbon nanotubes by swirled floating catalyst chemical vapour deposition method

A series of developments have been made in synthesizing Carbon Nanotubes (CNTs) by Catalytic Vapour Deposition (CVD) methods since its discovery as a possible route to the large scale and high quality production of CNTs. In this study, CNTs were synthesized continuously in a swirled floating catalytic chemical vapour deposition reactor using acetylene as carbon source, ferrocene as catalyst, with argon and hydrogen as carrier gases within the temperature range of 900-1050 degrees C. The effects of pyrolysis temperature, acetylene flow rate, hydrogen flow rate, and ratio of flow of acetylene to hydrogen on the rate of production of CNTs were investigated. The CNTs produced were purified with dilute nitric acid and the nature and quality of the CNTs were analysed by TEM, Raman spectrometer, EDX, and TGA. Results obtained revealed that a mixture of single and multi wall carbon nanotubes were produced continuously with a maximum yield rate of 0.31 g/min at 1000 degrees C and a flow ratio of acetylene to hydrogen of one to five.     

Towards the large-scale synthesis of carbon nanotubes in fluidised beds

Carbon nanotubes (CNTs) are a form of crystalline carbon with extraordinary properties, making them valuable in a broad range of applications. However, the lack of suitable large-scale manufacturing techniques, which we define as being of the order 10000 tonnes per annum, continues to inhibit their widespread use. Of the three established synthesis methods for CNTs: (i) chemical vapour deposition (CVD), (ii) laser ablation, and (iii) arc discharge, CVD techniques show the greatest promise for economically viable, large-scale synthesis. In particular, the fluidised bed CVD (FBCVD) technique, where the CVD reaction occurs within a fluidised bed of catalyst particles, has the potential to produce high quality CNTs, inexpensively, in large quantities. In this work we report on the development of a catalytic chemical vapour deposition process, using batch fluidised bed reactors, for the synthesis of straight and spiral carbon nanotubes at pilot scale (up to 1 kg/hr). We believe this to be the first report of the synthesis of spiral carbon nanotubes using fluidised bed CCVD. Iron, nickel and cobalt transition metal catalysts supported on non-porous alumina substrates were fluidised in a mixture of nitrogen, hydrogen and ethylene at temperatures between 550 and 800 degrees C for between 15 and 90 minutes. Nanotube yield was inferred from thermogravimetric analysis and the quality and size of the CNTs from transmission electron microscopy. Conflicting information in the literature about the influence of synthesis parameters on CNT properties suggests that further investigation is necessary to understand the synthesis process at a fundamental level, i.e., independent of reactor design and operation.     

CNTs添加对MmMn0.4Co0.7Al0.3Ni3.4贮氢合金负极性能的影响

对商用MmMn0.4Co0.7Al0.3Ni3.4贮氢合金中添加多壁碳纳米管(CNTs)、Ni的电化学性能进行了研究.结果表明,CNTs的加入可以提高电极的放电容量和初始活化性能,合金中添加CNTs、CNTs+Ni的电极完全活化只需11个循环,其最大放电容量分别为255、271mAh/g.而添加Ni的电极则需24个循环才达到最大容量(245mAh/g);合金中添加CNTs、CNTs+Ni的电极具有更高的放电平台和更好的高倍率放电性能(HRD),在1000 mAh/g放电电流下,添加CNTs、CNTs+Ni、Ni以及未添加电极的HRD值依次为80.5%、83.9%、66.9%和62.4%,线性极化和电化学阻抗测试表明,CNTs的加入可有效减少欧姆电阻、提高电极表面的电荷迁移速率,更有利于在大电流下进行放电.     

锂空气电池用碳纳米管/钴锰氧化物复合电极材料的制备及电化学性能

采用沉淀法合成了不同钴锰含量的碳纳米管(CNTs)/钴锰氧化物纳米复合材料. 利用XRD、SEM、TEM、BET和FT-IR等方法对材料进行了表征, 考察了不同复合材料对锂空气电池放电及充电过程的影响, 同时对循环性能进行了研究. 结果表明: 钴锰比例为4:0与0:4时, 产物为CNTs/Co₃O₄与CNTs/Mn₃O₄, 钴锰比例为3:1、2:2、1:3时, 产物为CNTs/(Co, Mn)(Co, Mn)₂O₄。产物具有良好的分散性能, 氧化物负载在碳管表面, 其中CNTs/Mn₃O₄的分散性能最好。随着锰含量的增加, 电池的放电性能提高, CNTs/Mn₃O₄的放电电压达到2.92 V。随着钴含量的增加, 电池的充电性能提高, 充电电压最低为3.80 V。钴锰比为3:1时的产物充放电过电势(△V)仅为1.05 V, 5次循环后依然保持着良好的放电性能。     

Electrochemical reduction of nitrobenzene at carbon nanotube electrode

The electrochemical behaviors of nitrobenzene at a pyrolytic graphite electrode modified with carbon nanotubes (CNTs) were studied using cyclic voltammetry and constant-potential electrolysis technique, and the CNT-modified electrode was characterized with Fourier transform infrared spectroscopy (FTIR), high resolution transmission electron microscopy (HRTEM) and scanning electron microscopy (SEM) measurements. A CNT-modified packed-bed flow reactor was also constructed for electrocatalytic reduction of nitrobenzene. The results showed that CNTs exhibited high activity for nitrobenzene reduction to aniline and the electrochemical reduction of nitrobenzene at CNT-modified electrode followed the pathway of nitrobenzene-->phenylhydroxylamine-->aniline. CNTs had been functionalized with profuse carboxylic group and other oxygen-containing groups, became open with some lacuna on the wall, and were distributed symmetrically on the electrode with forming a three-dimensional layer, resulting in the high catalytic-activity for nitrobenzene reduction to aniline. The removal of nitrobenzene was over 95% with electrolysis for 50 min at -1.20 V in pH 5 solution using the CNT-modified packed-bed flow reactor, and no other product was obtained except aniline. The removal of nitrobenzene was over 95% with electrolysis for 80 min at -1.20 V in pH 7 solution and was 87% with electrolysis for 120 min in pH 9 solution. A little phenylhydroxylamine besides aniline was obtained during the initial electrolysis stage, and then all reduced to aniline. The average current efficiency at pH 5, 7 and 9 was 46, 51 and 63%, respectively. The electrolysis products were mineralized easily through aerobiotic biodegradation.     

Influence of the solution temperature on carbon nanotube formation by arc discharge method

Carbon nanotubes (CNTs) represent an important group of nanomaterials with attractive geometrical, electrical and chemical properties and are synthesised using a variety of techniques. In this study, CNTs are fabricated by arc discharge in liquid with a fully automatic setup, while this system is equipped with a heat exchange system. This fully automatic setup enables the controlling of gap between the two electrodes and temperature of the media. Furthermore, this system can cool down the solution that is heated due to arc and keep the temperature of solution constant during the arc discharge. The temperature of the solution affects the synthesising and structuring of CNTs. In this study, CNTs are fabricated between two graphite electrodes, which are submerged in LiCl (0.25?N) and with a voltage of 25?V, while Ni and Mo are used as catalysts. For comparative study, CNTs are synthesised under different thermal conditions, below zero, at environment temperature and at high temperature (up to 80°C), and the results are analysed, compared and discussed. The scanning electron microscopy, transmission electron microscopy and Raman spectroscopy are employed to study the morphology of these carbon nanostructures. The general impact of the solution temperature upon nanoproduct structures will be discussed.     

Synthesis of fuel oil and carbon nanotubes in an autoclave using plastic waste as precursor

In this study, the synthesis of fuel oil and carbon nanotubes (CNTs) using waste plastic in a batch pyrolysis reactor of 750?mL capacity was carried out. Density, calorific values and FTIR spectroscopy confirmed the formation of fuel oil. The calorific value of oil was higher than the energy needed for pyrolysis process. The same reactor was used as an autoclave for the synthesis of CNTs. SEM and TEM results showed that carbon nanotubes of 40–60?nm diameters were grown on Ni/Mo/MgO catalyst. CNT yield was around 3.2?g of CNTs per 6?g of PP. The purity of CNTs was investigated by thermogravimetric analysis (TGA). The present study proposes a feasible process to convert plastic waste into furnace oil by rapid pyrolysis and synthesis of CNTs.     

Carbon fiber/epoxy composite property enhancement through incorporation of carbon nanotubes at the fiber–matrix interphase – Part I: The development of carbon nanotube coated carbon fibers and the evaluation of their adhesion

A new method to realize the uniform coating of carbon nanotubes (CNTs) to carbon fibers (CFs) has been developed, which enables the scalable fabrication of CNT containing CF/epoxy composites. In this method, CNTs are treated by cationic polymers, then, the CNTs are coated to CFs by immersion into a CNT/water suspension. Good dispersion is achieved by repulsive force between positively charged CNTs and uniform coating of the CNTs is achieved by attractive forces between positively charged CNTs and negatively charged CFs. It is found that the use of specific cationic polymers including polyethyleneimine (PEI) results in stable CNT/water suspensions, and uniform coating of the CNTs. Single fiber fragmentation tests of the CF/epoxy composites were conducted to evaluate the strength of interface and interphase under shear loading. The results show that the combination of epoxy resin sizing and PEI treated CNT coating to CFs results in high interfacial shear strength.     

Voltage effects on the production of nanocarbons by a unique arc-discharge set-up in solution

Well graphitised nanocarbons including onion-like fullerenes and single- and multi-walled carbon nanotubes (CNTs) were synthesised in high yield by automatic arc-discharge method in solution. This technique is considered a low-cost method since it does not require any expensive equipment. Herein, an arc discharge full automatic set-up was used for fabrication of CNTs which enables controlling of the gap between the two electrodes and the voltage as well. Carbon nanostructures under a controlled amount of voltage (from 10 to 30 V) were synthesised where Ni : Mo as a catalyst and LiCl 0.25 M as a solution were used. Subsequently, a modified acid treatment method was applied as purification stage of the products. The production rate of CNTs was as high as 7.7 mg min^?1 while the voltage was set at 30 V. Scanning electron microscopy and transmission electron microscopy as well as Raman spectroscopy were employed to study the morphology of these carbon nanostructures. The results indicated that CNTs synthesised at a voltage of 30 V had the best quality and elongated straight structures. The mechanism of the voltage conditions for preparing nanocarbons as well as their characterisation are discussed.     

碳纳米管有机离子盐合成和有规组装

采用两步法合成了一类新型可组装的碳纳米管有机离子盐。研究了有机修饰剂添加量、反应时间、温度对产物的影响,得到反应的优选条件为：DC5700/氧化碳纳米管质量比0.75/60℃/2h。红外、拉曼光谱研究证实了接枝物与碳纳米管之间为化学接枝。电子显微镜观察表明碳纳米管有机离子盐具有典型的有机-无机＂壳核＂结构,并且通过控制反应条件能实现碳纳米管有机离子盐的有规组装阵列。     

锂离子电池碳纳米管负极材料储锂性能研究

将碳纳米管用于锂离子电池负极材料,用循环伏安及充放电实验研究了电极的性能.结果表明,碳纳米管用作锂离子电池负极,具有较高的储锂容量,首次放电容量达560mAh/g,但首次不可逆容量损失也大,高达430mAh/g.经过第1次充放电的容量损失后,随后各次的容量损失很小,碳纳米管的循环性能趋于稳定.     

Electrical and thermal property enhancement of fiber-reinforced polymer laminate composites through controlled implementation of multi-walled carbon nanotubes

Aligned carbon nanotubes (CNTs) are implemented into alumina-fiber reinforced laminates, and enhanced mass-specific thermal and electrical conductivities are observed. Electrical conductivity enhancement is useful for electrostatic discharge and sensing applications, and is used here for both electromagnetic interference (EMI) shielding and deicing. CNTs were grown directly on individual fibers in woven cloth plies, and maintained their alignment during the polymer (epoxy) infiltration used to create laminates. Using multiple complementary methods, non-isotropic electrical and thermal conductivities of these hybrid composites were thoroughly characterized as a function of CNT volume/mass fraction. DC and AC electrical conductivity measurements demonstrate high electrical conductivity of >100 S/m (at 3% volume fraction, ∼1.5% weight fraction, of CNTs) that can be used for multifunctional applications such as de-icing and electromagnetic shielding. The thermal conductivity enhancement (∼1 W/m K) suggests that carbon-fiber based laminates can significantly benefit from aligned CNTs. Application of such new nano-engineered, multi-scale, multi-functional CNT composites can be extended to system health monitoring with electrical or thermal resistance change induced by damage, fire-resistant structures among other multifunctional attributes.     

Vacuum gauges with emitters based on carbon nanotubes

New vacuum gauges with emitters based on carbon nanotubes (CNTs) are described. The relation between the field emission from CNTs and the residual pressure in the vacuum chamber is considered. The operation of the proposed pressure sensor obeys the electric discharge theory based on the Paschen law, whereby the pressure is determined by measuring the discharge current as a function of the concentration of a gas (air) ionized as a result of the collisions with electrons emitted from CNTs.     

Field emission study of carbon nanotubes forest and array grown on Si using Fe as catalyst deposited by electro-chemical method

Vertically aligned carbon nanotubes are synthesized by Low Pressure Chemical Vapor Deposition (LPCVD) on Si substrate coated with Fe as a catalyst at a pressure of 20 Torr and at a growth temperature of 600 degrees C. The catalyst film is prepared by electro-chemical method which is very unique and a low cost method. Three precursor gases Acetylene (C2H2), Ammonia (NH3) and Hydrogen (H2) at the flow rate of 20 sccm, 100 sccm and 100 sccm respectively are allowed to flow through the Low Pressure Chemical Vapor Deposition reactor for 10 minutes. Scanning Electron Microscope (SEM) images show that synthesized CNTs are vertically aligned and uniformly distributed with a high density. Raman analysis shows G-band at 1574 cm(-1) and D-band at 1370 cm(-1). The G-band is higher than D-band, which indicates that CNTs are highly graphitized. The field emission measurement reveals good field emission properties of as-grown vertically aligned carbon nanotubes with turn-on field of 1.91 V/microm at the current density 10 mA/cm2. The field enhancement factor is calculated to be 7.82 x 10(3) for as-grown carbon nanotubes.     

不同压力下碳纳米管的电弧法合成及其表征(英文)

采用电弧放电法在氦气/乙炔混合气氛中,在不同压力下合成了碳纳米管.运用场发射扫描电镜、场发射透射电镜、X-射线衍射仪和拉曼光谱对碳纳米管的形貌进行了表征.采用可见发射光谱对碳纳米管的形成过程进行了原位诊断研究.场发射扫描电镜结果表明,在氦气/乙炔气氛中合成的碳纳米管的长度大于50微米,许多碳颗粒沉积在碳纳米管壁上.场发射透射电镜结果表明,在0.100MPa下合成的碳纳米管的壁厚明显大于0.035MPa下合成的碳纳米管的壁厚.可见发射光谱诊断结果表明,CH和C2物种可能作为碳纳米管形成的前驱体,其中,以H原子作为无定形炭的刻蚀物种.阳极消耗速率和产物在阴极的沉积速率随着反应器中压力的增加而增加.因此,可以通过加强阳极和乙炔的蒸发速率及CH和C2物种的沉积速率而增加碳纳米管的形成速率.