Growth of carbon nanotubes on aluminium foil for supercapacitors electrodes

A new approach for the preparation of carbon nanotubes (CNTs) electrode is proposed in the present work. Multi-walled carbon nanotubes (MWCNTs) were grown by chemical vapour deposition on aluminium strips pre-plated with a nickel thin film as the catalyst. The CNTs were characterized by scanning and transmission electron microscopy, Brunauer–Emmett–Teller surface area measurement and thermogravimetric analysis. The nickel-plated aluminium foil with a layer of CNTs was further characterized for an assessment of its electrochemical behaviour as electrode for supercapacitors. The specific capacitances of the electrode, as derived from cyclic voltammetry measurement at 0.1 V s⁻¹ scan rate, was found to be 54 and 79 F g⁻¹ in aqueous and organic electrolytes, respectively, in line with the highest reported values for either activated carbon or MWCNTs electrodes. Further evidence in support of the viability of the present approach for the preparation of a CNTs electrode was obtained from electrochemical impedance spectroscopy.     

Effective electron emitters by molybdenum oxide-coated carbon nanotubes core–shell nanostructures

In this article, we showed that simple metal oxide coatings such as MoO₃ can be an effective enhancer for carbon nanotubes (CNTs) in field emission (FE) performance. For comparison, the FE properties of the pristine vertically aligned multi-walled CNTs with the metal oxide-coated CNTs were investigated. The metal oxide coating of the pristine CNTs was carried out by metal–organic chemical vapor deposition (MOCVD) method at 400 °C using Mo(CO)₆ as the precursor. The core–shell structure of the nanocomposite was studied by transmission electron microscopy (TEM). X-ray photoelectron spectroscopy (XPS) results showed that the surface of the coating material was mainly MoO₃. FE test indicated that the MoO₃-coated CNTs film exhibited an enhanced performance than the pristine CNTs with a turn-on field of 1.33 V μm⁻¹ and a field enhancement factor β estimated to be ~7000. Ultraviolet photoelectron spectroscopy (UPS) results confirmed a lower electron emission barrier height for MoO₃-coated CNTs than for the pristine CNTs. The mechanism of the enhanced FE performance is discussed based on Schottky barrier effect.     

Dispersion assessment and studies on AC percolative conductivity in polymer-derived Si–C–N/CNT ceramic nanocomposites

Nanocomposites comprise polysilazane-derived SiCN ceramic charged with carbon nanotubes (CNTs) have been prepared by dispersion of multi-walled CNTs with a diameter of 80 nm in a cross-linked polysilazane (HTT 1800, Clariant) using a simple roll-mixer method. Subsequently, the composites were warm pressed and pyrolyzed in argon atmosphere. Scanning electron microscopy (SEM) and 3D Raman imaging techniques were used as major tools to assess the dispersion of CNTs throughout the ceramic matrix. Furthermore, studies on the effect of the volume fraction of CNTs in the nanocomposites on their electrical properties have been performed. The specific bulk conductivities of the materials were analyzed by AC impedance spectroscopy, revealing percolation thresholds (ρ_c) at CNT loadings lower than 1 vol%. Maximum conductivity amounted to 7.6 × 10⁻² S/cm was observed at 5 vol% CNT. The conductivity exponent in the SiCN/CNT composites was found equal to 1.71, indicating transport in three dimensions.     

Microstructure of carbon nanotubes/PET conductive composites fibers and their properties

Poly(ethylene terephthalate) (PET) resin has been compounded with carbon nanotubes (CNTs) using a twin-screw extruder. The composites of 4 wt% CNTs in PET had a volume electrical resistance of 10³ Ω cm, which was 12 orders lower than pure PET. The volume electrical conductivity of CNTs/PET composites with different CNTs containing followed a percolation scaling law of the form σ = κ(ρ − ρ_c)^t well. Scanning electron microscopy (SEM) micrograph showed that CNTs had been well dispersed in PET matrix. Optical microscopy micrograph showed that discontinuity of conductive phase existed in some segments of composite fiber. Rheological behavior of CNTs/PET composites showed that the viscosity of CNTs/PET composites containing high nanotube loadings exhibited a large decrease with increasing shear frequency. Crystallization behavior of CNTs/PET composites was studied by differential scanning calorimetry (DSC) and the nucleating effect of CNTs in the cooling crystallization process of PET was confirmed. Composite fiber was prepared using the conductive CNTs/PET composites and pure PET resin by composite spinning process. Furthermore, cloth was woven by the composite fiber and common terylene with the ratio 1:3. The cloth had excellent anti-static electricity property and its charge surface density was only 0.25 μC/m².     

Large-scale synthesis of BN nanotubes using carbon nanotubes as template

Boron nitride nanotubes (BN-NTs) were synthesized in large scale by the reaction of NaBH₄ and NH₄Cl in the temperature range of 500-600 °C for 10-18 h, where carbon nanotubes (CNTs) were mixed together with the reactants to serve as template. Pure BN-NTs were obtained by oxidizing the product at about 800 °C in air atmosphere. The structure and morphology of the product with a surface area of 106.635 m²/g were characterized by X-ray diffraction, transmission electron microscopy, Fourier transformation infrared spectroscopy, and thermogravimetric analysis. Large scale preparation of BN-NTs could be realized by this simple and effective route.     

In situ preparation and mechanical properties of CNTs/MCMBs composites

By adding carbon nanotubes (CNTs) into medium temperature coal tar pitch, mesocarbon microbeads (MCMBs) were obtained via thermal condensation, then CNTs/MCMBs composites were in situ prepared using compression molding. The morphology, structure and mechanical properties of CNTs/MCMBs composites were characterized by optical microscope, digital camera, scanning electron microscope (SEM) and mechanical test machine. Results showed that CNTs were used as the nucleating agent and could inhibit the growth and coalescence of MCMBs. The optical textures of CNTs/MCMBs composites showed similar characteristics to the thermal condensation products from coal tar pitch with CNTs. The mass ratio of CNTs to coal tar pitch played an important role in the mechanical properties of CNTs/MCMBs composites. The density and bending strength of CNTs/MCMBs composite first increased and then decreased with the increase of the proportion of CNTs. When the proportion of CNTs was 5 wt%, the density of the composite reached the maximum (1.76 g/cm³). In addition, the bending strength of the composite reached the maximum (79.6 MPa) as adding 2 wt% CNTs into coal tar pitch.     

Bulk preparation and characterization of mesoporous carbon nanotubes by catalytic decomposition of cyclohexane on sol–gel prepared Ni–Mo–Mg oxide catalyst

Multiwalled carbon nanotubes were synthesized using Ni–Mo–Mg oxide catalyst prepared by sol–gel technique. Carbon nanotubes were formed in situ by the reduction of nickel oxide (NiO) and molybdenum oxide (MoO₃) to Ni and Mo by a gas mixture of nitrogen, hydrogen and cyclohexane at 750 °C. Scanning Electron Microscopy (SEM) was used to confirm the formation of carbon nanotubes (CNTs). The pore size distribution of carbon nanotubes (CNTs) was investigated by N₂ adsorption and desorption. It was found that the pore size fell into the mesopore range: 2 < d < 50 nm. Interpretation was also made using Raman spectroscopy, Diffuse reflectance spectroscopy, X-ray diffraction and ESR spectra. This method is found to produce a very high yield weighing over 20 times of the catalyst. Based on the experimental conditions and results obtained a possible growth mechanism of the carbon nanotubes is proposed.     

A simple method of producing single-walled carbon nanotubes from a natural precursor: Eucalyptus oil

Single-walled carbon nanotubes (SWNTs) have been synthesized by catalytic decomposition of eucalyptus oil, on a high silica-zeolite support impregnated with Fe/Co catalyst at 850 °C by the spray pyrolysis method. Catalyst with 5 wt.% (molar ratio of Co:Fe = 1:1), impregnated in zeolite was suitable for effective formation of carbon nanotubes (CNTs). As-grown CNTs were characterized by SEM, TEM and Raman spectroscopy. Raman spectroscopy reveals that as-grown CNTs are well graphitized. Raman spectroscopy also reveals that the as-prepared SWNTs have a diameter of about 0.79-1.71 nm.     

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.     

Structural modification and enhanced electron emission from multiwalled carbon nanotubes grown on Ag/Fe catalysts coated Si-substrates

Multiwalled carbon nanotubes and carbon nano-filaments were grown using Fe as the main catalyst and Ag as a co-catalyst by microwave plasma enhanced chemical vapour deposition. In this work we demonstrate the growth behaviour of carbon nanotubes (CNTs) grown on pure Fe-film and Ag–Fe films. We find that using Ag film beneath Fe film significantly abate the catalyst–substrate interactions by acting as a barrier layer as well as enhances the nucleation sites for the growth of CNTs due to the limited solubility with Fe and silicon. Scanning electron microscopy and transmission electron microscopy studies were carried out to image the microstructures of the samples. It was observed that the length of Fe catalyzed CNTs was ∼500 nm and Ag–Fe catalyzed CNTs varied from ∼600 nm to 1.7 μm. Micro Raman spectroscopy confirmed the improved crystalline nature of Ag–Fe CNTs. It was found that I_D/I_G ratio for Fe catalyzed CNTs was ∼1.08 and for Ag–Fe catalyzed CNTs was ∼0.7. The Ag–Fe catalyzed CNTs were found to be less defective as compared to Fe catalyzed CNTs. Field emission measurements using diode configuration, showed that electron emission from Ag–Fe catalyzed CNTs was much stronger as compared to Fe catalyzed CNTs. The threshold field for Ag–Fe catalyzed CNTs was (2.6 V μm⁻¹) smaller as compared to Fe catalyzed CNTs (3.8 V μm⁻¹) and thus shows better emission properties. This enhancement in electron emission mechanism as a result of introduction of Ag underlayer is attributed to the increased emitter sites and improved crystallinity.     

Enhanced electron emission from titanium coated multiwalled carbon nanotubes

Enhanced field emission properties and improved crystallinity of titanium (Ti) coated multiwalled carbon nanotubes (MWCNTs), prepared by microwave plasma enhanced chemical vapour deposition have been observed. Ti films of extremely low thicknesses (0.5 nm, 1.0 nm and 1.5 nm) were coated over carbon nanotubes (CNTs) and their field emission behaviour was investigated. The turn on field of Ti coated CNTs was found to be low (~ 0.8 V/μm) as compared to pristine CNTs (~ 1.8 V/μm). The field enhancement factor for Ti coated CNTs was quite large (~ 1.14 × 10⁴) as compared to pristine CNTs (~ 6 × 10³). This enhancement in electron emission is attributed to the passivation of defects and improved crystallinity of CNTs. Surface morphological and microstructural studies were carried out to investigate the growth of pristine and Ti coated CNTs. It was observed that Ti nanoclusters adsorb on the edges of MWCNTs and increase their crystallinity. This increase is directly correlated with the thickness of Ti film deposited. Micro Raman spectroscopy confirmed the improved crystallanity of Ti coated CNTs.     

Sol–gel route to carbon nanotube borosilicate glass composites

Dense borosilicate glass matrix composites containing up to 3 wt% of multiwalled carbon nanotubes were produced by a sol–gel process. The three different silicate precursors employed (tetramethylsilane (TMOS), methyltriethoxysilane (MTES) and methyltrimethoxysilane (MTMS)) yielded transparent xerogels which were subsequently crushed and densified by hot pressing at 800 °C. The dispersion of the carbon nanotubes was aided by using an organic–inorganic binder (3-aminopropyl triethoxysilane) which limited flocculation of the CNTs in the silica sol. After densification, the borosilicate glass composites containing up to 2 wt% CNTs showed significant improvements in hardness and compression strength, as well as thermal conductivity, whilst percolation effects lead to a dramatic increase in electrical conductivity above 1 wt%. This simple approach to disperse CNTs into a technical silicate glass matrix via the sol–gel process focusses specifically on the borosilicate system, but the procedure can be applied to produce other inorganic matrix composites containing CNTs.     

Growth of vertically aligned arrays of carbon nanotubes for high field emission

Vertically aligned multi-walled carbon nanotubes have been grown on Ni-coated silicon substrates, by using either direct current diode or triode plasma-enhanced chemical vapor deposition at low temperature (around 620 °C). Acetylene gas has been used as the carbon source while ammonia and hydrogen have been used for etching. However densely packed (∼ 10⁹ cm^− 2) CNTs were obtained when the pressure was ∼ 100 Pa. The alignment of nanotubes is a necessary, but not a sufficient condition in order to get an efficient electron emission: the growth of nanotubes should be controlled along regular arrays, in order to minimize the electrostatic interactions between them. So a three dimensional numerical simulation has been developed to calculate the local electric field in the vicinity of the tips for a finite square array of nanotubes and thus to calculate the maximum of the electron emission current density as a function of the spacing between nanotubes. Finally the triode plasma-enhanced process combined with pre-patterned catalyst films (using different lithography techniques) has been chosen in order to grow regular arrays of aligned CNTs with different pitches in the micrometer range. The comparison between the experimental and the simulation data permits to define the most efficient CNT-based electron field emitters.     

Production of empty and iron-filled multiwalled carbon nanotubes from iron–phthalocyanine polymer and their electromagnetic properties

A facile production of multiwalled carbon nanotubes (MCNTs) using iron-phthalocyanine polymer as the only carbon source with two kinds of metallic catalysts (Fe(CO)₅ and nano-iron) has been compared here. SEM, TEM and XRD were employed to figure the detailed structures of the carbon nanotubes. Consequently, catalyst played a key role in the formation of MCNTs: nano-iron resulted in iron-filled CNTs while Fe(CO)₅ led to empty CNTs. Both of these two CNTs were long and straight, with ~100 nm in diameter and several tens of micrometers in length. Moreover, dielectric and magnetic properties were carried to further study synthesized carbon nanotubes. The results showed that the empty MCNTs had better dielectric properties than iron-filled MCNTs although the iron-filled CNTs exhibited the magnetic saturation of ~3.5 emu/g and coercive force of ~594.0 Oe, which is much higher than empty MCNTs.     

A low-cost method for producing high-performance nanocomposite thin-films made from silica and CNTs on cellulose substrates

We show that thin films of silica loaded with 22 wt% of carbon nanotubes (CNTs) can be deposited on cellulose substrate via the sol–gel route by a well-controlled process. The high loadings are obtained by airbrush spraying of a diluted sol solution (which contained a much smaller concentration of CNTs) followed by drying at 200 °C. The films are nearly continuous despite the fibrous structure of the substrate. The high degree of connectivity of the stranded structure of the CNTs yields a specific electrical conductivity of 3 × 10³ Ω⁻¹ m⁻¹. In contrast, films made with high loadings of carbon black have poor electrical conductivity. Results from mechanical tensile tests of samples are also reported. This economical method of producing CNT dispersed thin films could find application in catalysis, as electrodes in fuel cells and batteries, and in sensor technologies.     

Influence of Fe nanoparticles diameters on the structure and electron emission studies of carbon nanotubes and multilayer graphene

In this paper we report the effect of Fe film thickness on the growth, structure and electron emission characteristics of carbon nanotubes (CNTs) and multilayer graphene deposited on Si substrate. It is observed that the number of graphitic shells in carbon nanostructures (CNs) varies with the thickness of the catalyst depending on the average size of nanoparticles. Further, the Fe nanoparticles do not catalyze beyond a particular size of nanoclusters leading to the formation of multilayer graphene structure, instead of carbon nanotubes (CNTs). It is observed that the crystallinity of CNs enhances upon increasing the catalyst thickness. Multilayer graphene structures show improved crystallinity in comparison to CNTs as graphitic to defect mode intensity ratio (I_D/I_G) decreases from 1.2 to 0.8. However, I_2D/I_G value for multilayer graphene is found to be 1.1 confirming the presence of at least 10 layers of graphene in these samples. CNTs with smaller diameter show better electron emission properties with enhancement factor (γ_C = 2.8 × 10³) in comparison to multilayer graphene structure (γ_C = 1.5 × 10³). The better emission characteristics in CNTs are explained due to combination of electrons from edges as well as centers in comparison to the multilayer graphene.     

Plasma treatment as a method for functionalising and improving dispersion of carbon nanotubes in epoxy resins

This study reports on the results of plasma-treated carbon nanotubes (CNTs) in the presence of oxygen and ammonia which can be scaled up for relatively large quantities of nanomaterials. The plasma treatment has been shown to change the surface chemistry and energy as well as the morphology of the carbon nanotubes. X-ray photoelectron spectroscopy analysis shows increases in oxygen and nitrogen groups on the oxygen- and ammonia-treated CNTs, respectively. Titration of the enhanced oxygen plasma-treated CNTs reveals an increased presence of carboxylic acid groups at 2.97 wt% whilst bulk density decreases from 151 kg/m³ for untreated carbon nanotubes to 76 kg/m³ after the enhanced oxygen treatment. The free surface energy has also been shown to increase from 33.70 up to 53.72 mJ/m² determined using a capillary rise technique. The plasma-treated carbon nanotubes have been mixed in epoxy and have shown an improvement in dispersion, which was quantitatively evaluated using an optical coherence tomography (OCT) technique shown to be suitable for nanocomposite characterisation. This research has demonstrated that it is possible to surface functionalise large quantities of carbon nanotubes in a single process, and that this process improves the dispersion of the carbon nanotubes in epoxy.     

Fabrication and mechanical/conductive properties of multi-walled carbon nanotube (MWNT) reinforced carbon matrix composites

Multi-walled carbon nanotube (MWNT) reinforced carbon matrix (MWNT/C) composites have been explored using mesophase pitch as carbon matrix precursor in the present work. Results show that carbon nanotubes (CNTs)can enhance the mechanical properties of carbon matrix significantly. The maximal increment of the bending strength and stiffness of the composites, compared with the carbon matrix, are 147% and 400%, respectively. Whereas the highest in-plane thermal conductivity of the composites is 86 W m^− 1 K^− 1 which much lower than that of carbon matrix (253 W m^− 1 K^− 1).At the same time the electrical resistivity of the composites is much higher than that of matrix. It is implicated that CNTs seem to play the role of thermal/electrical barrier in the composites. FSEM micrograph of the fracture surface for the composites shows that the presence of CNTs restrains the crystallite growth of carbon matrix, which is one of factors that improve mechanical properties and decrease the conductive properties of the composites. The defects and curved shape of CNTs are also the affecting factors on the conductive properties of the composites.     

Electrochemical investigation of TiO2/carbon nanotubes nanocomposite as anode materials for lithium-ion batteries

Mechanically blended composite of nanosized TiO₂ and carbon nanotubes (CNTs) was investigated as potential anode materials for Li-ion batteries. It was found that the TiO₂/CNTs nanocomposite exhibits an improved cycling stability and higher reversible capacity than CNTs. The reversible capacity of the TiO₂/CNTs composite reaches 168 mAh g^− 1 at the first cycle and remains almost constant during long-term cycling. The electrochemical results show that the TiO₂ nanoparticles in the composite not only restrain the formation of surface film, but also make a contribution to the overall reversible capacity.     

Improvement of mechanical properties in aluminum/CNTs nanocomposites by addition of mechanically activated graphite

Carbon nanotubes reinforced aluminum nanocomposite was prepared by ball milling route. CNTs were initially mixed with mechanically amorphized graphite. Specimens were analyzed by X-ray diffractometry and Raman spectroscopy. Crystallite size and dislocation density were calculated by modified Warren–Averbach method. Carbide formation was semi-quantitatively investigated via Raman spectroscopy. A band located in 950 cm⁻¹ was considered to be corresponded to Al₄C₃. Hardness of the samples was also evaluated using a Vickers micro-hardness tester. The hardness strengthening contributions were modeled to evaluate interfacial bonding between CNTs and the aluminum matrix. In specimens, including amorphized graphite, hardening was due to both work hardening and second phase strengthening otherwise, only due to work hardening. It was deducted that the amorphized graphite has a major role for mechanical properties improvement. This seems to be due to the formation of aluminum carbide at the interface which consequently increases adhesion of CNTs to aluminum.