High temperature annealing effects on carbon spheres and their applications as anode materials in Li-ion secondary battery

Carbon spheres (CSs) have been subjected to a high temperature annealing process at 2800 °C under an Ar atmosphere. These high temperature annealed carbon spheres (HTACSs) have been characterised by SEM, HRTEM, BET surface area, XRD, Raman, SQUID and TGA techniques. The study indicates that the original spheroidal morphology of CSs have been converted to polyhedral. The graphitic flakes possessing relatively short range order of which the original are composed of appear to have coalesced into more extended graphitic layers possessing long range order. Furthermore three dimensional interplanar graphitic ordering occurs. Charge-discharge capacity measurements have been performed on both carbon materials to access the potential of these materials in Li-ion secondary battery applications. The measurements indicate that HTACSs exhibit better performance than CSs in terms of greater reversible capacity and their longer plateau in voltage profiles.     

Surface functionalization and characterization of graphitic carbon nanofibers (GCNFs)

The preparation and characterization of herringbone graphitic carbon nanofibers (GCNFs) surface-derivatized with reactive linker molecules derived from four diamines and three triamines is reported. Surface carbon sites of as-prepared GCNFs are oxidized to carboxylic acid groups by nitric acid and covalently bound to seven different linker molecules containing pendant amino groups using carboxylate amidation chemistry. GCNF materials are characterized by TEM, IR, TGA, laser-desorption/ionization (LDI) mass spectrometry, and by elemental analysis. Approximate GCNF/(linker molecule)_x compositions are proposed consistent with acid-uptake and elemental analysis data. Direct evidence for the presence and composition of surface-bound linker molecules is provided by LDI mass spectrometry and by quantitative XPS analysis of trifluoroacetylated derivatives. The reactivity of pendant amino groups present within attached linker molecules is determined quantitatively via Fmoc analysis and synthetically by effecting nucleophilic ring-opening oligomerization of epoxy monomer.     

Raman microspectroscopy of soot and related carbonaceous materials: Spectral analysis and structural information

Experimental conditions and mathematical fitting procedures for the collection and analysis of Raman spectra of soot and related carbonaceous materials have been investigated and optimised with a Raman microscope system operated at three different laser excitation wavelengths (514, 633, and 780 nm). Several band combinations for spectral analysis have been tested, and a combination of four Lorentzian-shaped bands (G, D1, D2, D4) at about 1580, 1350, 1620, and 1200 cm⁻¹, respectively, with a Gaussian-shaped band (D3) at ∼1500 cm⁻¹ was best suited for the first-order spectra. The second-order spectra were best fitted with Lorentzian-shaped bands at about 2450, 2700, 2900, and 3100 cm⁻¹. Spectral parameters (band positions, full widths at half maximum, and intensity ratios) are reported for several types of industrial carbon black (Degussa Printex, Cabot Monarch), diesel soot (particulate matter from modern heavy duty vehicle and passenger car engine exhaust, NIST SRM1650), spark-discharge soot (Palas GfG100), and graphite. Several parameters, in particular the width of the D1 band at ∼1350 cm⁻¹, provide structural information and allow to discriminate the sample materials, but the characterisation and distinction of different types of soot is limited by the experimental reproducibility of the spectra and the statistical uncertainties of curve fitting. The results are discussed and compared with X-ray diffraction measurements and earlier Raman spectroscopic studies of comparable materials, where different measurement and fitting procedures had been applied.     

X-ray absorption near-edge structure and photoelectron spectroscopy of single-walled carbon nanotubes modified by a HBr solution

X-ray absorption near-edge structure (XANES) spectroscopy and photoelectron spectroscopy (PES) have been used to investigate single-walled carbon nanotubes (SWNTs) modified by immersion in a HBr solution at room temperature. After treatment XANES spectra of SWNTs show a new pronounced feature, which has been assigned to new bonds between the sidewall of the SWNTs and Br atoms. This investigation demonstrates the unique capabilities of the XANES spectroscopy as a tool to achieve structural and bonding information of carbon nanotubes induced by chemical processes.     

Growth of tetrahedral amorphous carbon film: Tight-binding molecular dynamics study

Molecular dynamics simulation using tight-binding potential has been performed to examine the growth and performance of tetrahedral amorphous carbon during ion deposition. The sp³ hybrid atom content, density, and compressive stress of the tetrahedral amorphous carbon film depend on the growing conditions such as substrate temperature, ion energy, ion dose, and annealing temperature. The critical temperature for sp³ transition to sp² decreases with ion energy (40, 80, and 120 eV). At low temperatures (<300 K) and low ion energies, the sp³ fraction increases up to 82%. At the annealing temperature less than 1200 K or with a few ions (<20) implanted into the film, its sp³ content and density have only slight changes while the compressive stress has a large reduction with the annealing temperature and the number of implanted ions. This large reduction in the compressive stress is due to a structural relaxation.     

Orientation of carbon nanotubes in polypropylene melt

The correlation between shear stress and the orientation of single‐walled carbon nanotubes (SWCNTs) in an SWCNT/polypropylene composite during the melt process was investigated. Highly oriented composite fibers were produced by extruding the polypropylene melt using a capillary rheometer. The experimental range of shear rates covered those of common polymer melt‐shaping processes. The effect of functionalization of the SWCNTs on orientation was also investigated. Polarized Raman spectroscopy was used to analyze the orientation of the SWCNTs. A high degree of SWCNT orientation was observed under high shear stress, and the functionalized SWCNTs induced a higher degree of orientation than did pristine SWCNTs. The existence of a critical shear stress was observed for the orientation of the SWCNTs, and their orientation was found to occur more efficiently above this critical shear stress. The crystallization temperature and heat of fusion were characterized using a differential scanning calorimeter, and both parameters were observed to increase with the incorporation of SWCNTs. © 2012 Society of Chemical Industry     

Raman spectroscopic study of the microstructure of carbon films developed from cobalt chloride‐modified polyacrylonitrile

Polyacrylonitrile (PAN) was modified with cobalt chloride at 90°C for 5 min. The carbon films prepared from original and modified PAN films were carbonized up to 1300°C. The structure of the resulting carbon film was studied using X‐ray diffraction and Raman spectroscopy. The stacking size obtained from X‐ray diffraction approaches the L_c value of the resulting carbon films as the heat treatment temperature increased. The mean average carbon basal planes in crystalline (Lc/d) also increased with increasing pyrolysis temperature. Raman spectra confirmed the progressive structural ordering as treatment temperature increased. During pyrolysis, a substantial decrease in the intensity of the band near the 1350 cm⁻¹ region was observed, indicating a decrease in the disordered structure. The crystal size (L_a) of the resulting carbon films also showed a remarkable increase with increased heat treatment temperature. The resulting carbon films developed from the modified PAN films had higher L_c and L_a than those developed from the original PAN film. It was established that cobalt catalyzes graphitization of amorphous carbon during pyrolysis. This modification not only promoted the growth of crystal size but also increased the close packing of the carbon basal planes. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 2219–2225, 1999     

Nanostructures of pyrolytic carbon from a polyacetylene thin film

Pyrolysis of a polyacetylene thin film has been performed in order to carbonize at temperatures of 500 to 1000 °C in vacuum. A trans-polyacetylene thin film was synthesized using a Ziegler-Natta catalyst. A black char below 20% in weight of the original PA film remained after pyrolysis. Structural properties and morphology of the black chars were investigated using Raman scattering spectrum, X-ray diffraction measurements, and scanning and transmission electron microscopy. Dehydrogenation and carbonization of the PA film were almost finished at a pyrolysis temperature of 800 °C. However, hollow spherical or elliptical nano-particles of tens of nanometers in size, which are composed of graphite structure, were included in the black chars obtained at all pyrolysis temperatures in this work. The formation mechanism of a graphite crystal in nanometer size from a PA crystal was discussed.     

Quantitative evaluation of sp/sp hybridization ratio in cluster-assembled carbon films by in situ near edge X-ray absorption fine structure spectroscopy

We present a near edge X-ray absorption fine structure spectroscopy characterization of nanostructured carbon films containing carbynoid species. By a careful data analysis and normalization of the spectra at the carbon K-edge we have quantitatively evaluated the extent of valence sp hybridization of the films. A sp/sp² ratio between 10% and 25% has been obtained. This result allowed the evaluation of the ratio between the sp and sp² Raman cross section at different excitation laser wavelengths.     

Screen-printed carbon electrode modified on its surface with amorphous carbon nitride thin film: Electrochemical and morphological study

The surface of a screen-printed carbon electrode (SPCE) was modified by using amorphous carbon nitride (a-CN_x) thin film deposited by reactive magnetron sputtering. Scanning electron microscopy and photoelectron spectroscopy measurements were used to characterise respectively the morphology and the chemical structure of the a-CN_x modified electrodes. The incorporation of nitrogen in the amorphous carbon network was demonstrated by X ray photoelectron spectroscopy. The a-CN_x layers were deposited on both carbon screen-printed electrode (SPCE) and silicon (Si) substrates. A comparative study showed that the nature of substrate, i.e. SPCE and Si, has a significant effect on both the surface morphology of deposited a-CN_x film and their electrochemical properties. The improvement of the electrochemical reactivity of SPCE after a-CN_x film deposition was highlighted both by comparing the shapes of voltammograms and calculating the apparent heterogeneous electron transfer rate constant.     

Raman spectroscopic study of conformational changes in the amorphous phase of poly(lactic acid) during deformation

The conformational distribution change of amorphous poly(lactic acid) (PLA) induced by deformation has been studied using Raman spectroscopy. Spectroscopic features associated with the rotational isomeric states (ttt, ttg′, tg′t, tg′g′) have been established experimentally and supported by normal coordinate analysis. Deformation induced a significant increase in the most favorable tg′t conformation. Based on the relative intensities of Raman-active skeletal modes, a quantitative method has been developed that can be used to elucidate structural changes in a variety of deformed polymer samples. For biaxially oriented PLA films, the overall tg′t conformation increased from the 76% in undeformed sample to a value as high as 92%. The change in conformational distribution in the amorphous phase follows a different trend (76-88%) as compared to the increase in sample crystallinity (0-43%). A large change in amorphous chain conformation occurred at relatively low draw ratios. In contrast, the large change in the degree of crystallinity occurred at higher draw ratios.     

An in situ Raman study of dimethyl carbonate synthesis from carbon dioxide and methanol over zirconia

In situ Raman spectroscopy has been used to investigate the mechanism of dimethyl carbonate (DMC) synthesis via the reaction of methanol with carbon dioxide over zirconia. Methanol adsorption leads to the appearance of adsorbed methoxide groups, whereas CO₂ adsorption leads to the formation of carbonate species. Monomethyl carbonate species, (CH₃O)COO(Zr)₂, are formed by the reaction of methoxide and monodentate carbonate species and DMC is formed via the further reaction of monomethyl carbonate species with methanol. This sequence is supported by evidence that DMC decomposition on zirconia proceeds via the reverse of the proposed mechanism.     

Raman spectroscopic study of effect of steam and carbon dioxide activation on microstructure of polyacrylonitrile‐based activated carbon fabrics

This work presents the different effects of steam and carbon dioxide activation on the microstructure of an oxidized polyacrylonitrile (PAN) fabric. An investigation was conducted on a series of carbonized fabrics and two series of activated carbon fabrics. The fabrics were activated by steam and carbon dioxide using heat‐treatment temperatures of 900–1100°C. Steam and carbon dioxide developed the microstructure initially present in the PAN‐based activated carbon fabrics, but with different effects. These fabrics in the form of fabric and powder were examined by X‐ray diffraction and Raman spectrometry. This study indicated that carbon dioxide only reacted with the crystalline edges or the irregular carbon on the fiber surface and that the inside structure of the fibers was not greatly affected. When the fabrics were activated using steam, water molecules reacted not only on the fiber surface but also with the carbon at the crystal edge and/or the nonregular carbon in the fibers, which led to communicating pore structures on the surface and in the inner portions of the fiber. This activation also promoted the denitrogenation reactions. Because of these structures and reactions, the activated carbon fabrics, which were activated by steam, had the highest stacking height for carbon layer planes (L_c), the highest number of layer planes (L_c/d₀₀₂), the highest oxygen content, the largest crystal size (L_a), and the highest density over the other samples. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 1090–1099, 2001     

A practical route to the production of carbon nanocages

Carbon-coated iron nanoparticles with diameters ranging from 5 to 50 nm and a few layers of graphitic shells have been synthesized in a mass scale by laser-induction complex heating evaporation. Through the studies on the dissolution behavior of the inner iron cores under the treatments of HCl and HNO₃ acids at different conditions, a practical route with the combined treatments of HNO₃ and HCl acids has been optimized to produce carbon nanocages. The nanocages thus obtained have some channels and are full of defects in the shells, as characterized by high-resolution transmission electron microscopy and Raman spectroscopy. Similar treatments should also be applicable to some other carbon-coated metal nanoparticles, e.g., Ni-C and Co-C, for the same purpose.     

Two-dimensional Raman spectroscopic study on the structural changes of a poly(3-chlorothiophene) film during the heating process

Two-dimensional Raman spectroscopy has been applied to provide the information on charge carriers and thermal stability of a doped poly(3-chlorothiophene) (PCTh) film. The strong spectral intensity at 1420 cm⁻¹ shows that positive polarons are the major charge carriers in doped PCTh. On the other hand, peaks in the 2D contour maps separate the overlapped bands around 1386 cm⁻¹, confirming the existence of positive bipolarons in PCTh. The positive asynchronous cross peak located at 1420/1386 cm⁻¹ further indicates that bipolarons have a higher thermal stability compared with polarons in the doped PCTh. The increase of the spectral intensity at 1454 cm⁻¹ and the decrease of the spectral intensity at 1420 cm⁻¹ indicate that during the heating process, a structural change occurs in the PCTh film.     

Preparation and characterisation of novel “sea-cucumber”-like structures containing carbon and boron

Spray-pyrolysis of a ferrocene-xylene-triethylborane mixture at 900 °C results in a novel “sea-cucumber”-like structure containing carbon and boron. SEM studies show that these structures are hollow with diameter between 100 and 500 nm and lengths varying from 30 to 40 μm. HRTEM and EELS studies reveal that the hollow structures are partly filled with iron. They are formed by a more graphitic internal core, which hardly contains any B. This core is coated by a more disordered B-containing C material. The amount of B in this coating is around 3 at.%. In addition, at this pyrolysis temperature, the growth of open-ended tubular nanostructures (30-40 nm diameter; 100-200 nm length) on the surface of the sea-cucumber-like structure is observed. These tubular nanostructures are not very graphitic and exhibit a similar composition to the coating of the sea-cucumber-like structure (around 3 at.% of B). The study of material produced at different pyrolysis temperatures show that the growth of these tubular nanostructures and the boron content are temperature dependent. Finally, preliminary results corresponding to oxidation resistance studies are presented.