The nanocomposites of carbon nanotube with Sb and SnSb0.5 as Li-ion battery anodes

Nanocomposites of carbon nanotubes (CNTs) with Sb and SnSb_0.5 particles were prepared by chemical reduction of SnCl₂ and SbCl₃ precursors in the presence of CNTs. SEM and TEM imaging showed that the Sb and SnSb_0.5 particles are uniformly deposited on the CNT exterior and in the CNT web. These CNT-metal composites are active anode materials for lithium ion batteries, showing improved cyclability compared to unsupported Sb and Sn-Sb particles and higher reversible specific capacities than CNTs. The reversible capacities were as high as 462 mAh/g for CNT-36 wt.% Sb and 518 mAh/g for CNT-56 wt.% SnSb_0.5. After 30 cycles, the capacity was 62.1% of the initial capacity for the former and 67.2% of the initial capacity for the later. In comparison Sb and SnSb_0.5 could only retain 17.7 and 23.5%, respectively of their initial capacities in the same number of cycles. The improvement in cyclability may be attributed to the nanoscale dimension of the metal particles and CNTs’ role as a buffer in relieving the mechanical stress induced by specific volume changes in electrochemical lithium insertion and extraction reactions.     

Hydrogen adsorption studies on single wall carbon nanotubes

Hydrogen adsorption data on as-grown and heat-treated single walled carbon nanotubes (SWNTs) obtained by a volumetric procedure using a Quantachrome Autosorb-1 equipment are presented. The amounts of hydrogen adsorbed at atmospheric pressure reach approximately 0.01 wt.% at 298 K and 1 wt.% at 77 K. The isosteric heat of adsorption has been calculated for both samples from H₂ equilibrium adsorption data at three temperatures, having initial values of 7.42 and 7.75 kJ mol⁻¹. Studies in porous structure by N₂ adsorption and density measurements in helium pycnometer are reported.     

A feasibility study of scaling-up the electrolytic production of carbon nanotubes in molten salts

The feasibility of scaling-up the electrolytic production of carbon nanotubes in molten salts has been investigated with the aid of electron microscopy (TEM and SEM). Using molten LiCl as the electrolyte and commercial graphite as both cathode and anode materials, carbon nanomaterials, including nanotubes, were prepared by constant voltage electrolysis. The cell was more than 20 times as large as that used in previous work. The nanotube concentration in the final product increased with cell voltage (including iR drop) from 1 vol.% at 4.0 V to 35 vol.% at 8.4 V. Under desired conditions, the charge and energy consumption for the cathode erosion was 0.28 Ah/g and 4.1 Wh/g, of which 60-70 wt.% were for producing nanomaterials (nanotubes: >30 vol.%). When adding 1 wt.% SnCl₂ to the electrolyte, partial and fully filled nanotubes were obtained with the nanomaterials containing up to 20 wt.% Sn. Preliminary results from applying the product as the electrode in lithium ion batteries are reported.     

Studies of electrochemical reduction of dioxygen with RRDE

The electrochemical behaviors of dioxygen (O₂) were studied by using rotate ring-disk electrode (RRDE) and other electrochemical methods at bare glassy carbon electrode (GCE) and single-walled carbon nanotubes (SWNTs)-dihexadecyl hydrogen phosphate (DHP) film modified GCE. The results showed that the electrochemical reduction of dioxygen was considered to proceed by a two-step two-electron reduction pathway at both bare GCE and SWNTs-DHP film modified GCE in 0.1 mol/L air-saturated sodium hydroxide (NaOH). Maybe because each reaction rate for two cases was different the cyclic voltammograms measurements exhibited different behaviors. The detection of ring current confirmed the presence of middle product hydrogen peroxide (H₂O₂). Furthermore, larger current and more positive reduction potential indicated that SWNTs showed a catalytic effect towards the electrochemical reduction of dioxygen.     

High growth of SWNTs and MWNTs from C2H2 decomposition over Co-Mo/MgO catalysts

A series of MgO supported catalysts having Co and Mo metals 5-40 wt.% in a ratio of 1:1 was prepared by impregnation method. Carbon nanotubes (CNTs) were grown over the catalysts by decomposition of C₂H₂ at 800 °C for 30 min. It was found that 5 and 10 wt.% Co-Mo/MgO catalysts produced single-wall nanotubes (SWNTs), whereas 20, 30 and 40 wt.% Co-Mo/MgO catalysts produced multi-wall nanotubes (MWNTs). The catalyst Mo/MgO was inactive in growing CNTs. In Co-Mo/MgO catalysts, however Mo generated a favorable environment to grow SWNTs. The growth of SWNTs was strongly dependent on the formation of small clusters of cobalt, which may generate from the decomposition of CoMoO₄ species during the nanotube growth. MWNTs were produced over comparatively larger cobalt clusters generated from Co₃O₄ phase during the nanotube growth stage. The yields of SWNTs were about 6% and 27% over 5 and 10 wt.% Co-Mo/MgO catalysts, respectively. MWNTs yield (576%) was observed over 40 wt.% Co-Mo/MgO catalyst. Carbon yield (%) highly varied with acetylene concentration.     

Physisorption of hydrogen in single-walled carbon nanotubes

The interaction of hydrogen with single-walled carbon nanotubes (SWNTs) was analysed. A SWNT sample was exposed to D₂ or H₂ at a pressure of 2 MPa for 1 h at 298 or 873 K. The desorption spectra were measured by thermal desorption spectroscopy (TDS). A main reversible desorption site was observed throughout the range 77 to 320 K. The activation energy of this peak at about 90 K was calculated assuming first-order desorption. This corresponds to physisorption on the surface of the SWNTs (19.2±1.2 kJ/mol). A desorption peak was also found for multi-walled carbon nanotubes (MWNTs), and also for graphite samples. The hydrogen desorption spectrum showed other small shoulders, but only for the SWNT sample. They are assumed to originate from hydrogen physisorbed at sites on the internal surface of the tubes and on various other forms of carbon in the sample. The nanosized metallic particles (Co:Ni) used for nanotube growth did not play any role in the physisorption of molecular hydrogen on the SWNT sample. Therefore, it is concluded that the desorption of hydrogen from nanotubes is related to the specific surface area of the sample.     

Synthesis of carbon nanostructures by arc evaporation of graphite rods with Co-Ni and YNi2 catalysts

Yields of single-walled carbon nanotubes (SWNTs) produced from electric arc evaporation of graphite electrodes with 3Co/Ni and YNi₂ catalysts differ substantially. For instance, with YNi₂ catalyst, the SWNT yield is ∼30-50 wt.% in ‘collar’ soot and ∼10-15 wt.% in ‘wall’ soot, while with 3Co/Ni catalyst, the yields are ∼15-20 wt.% and 2-3 wt.%, respectively. According to Raman spectroscopy data, the average dimension of SWNTs is ∼1.2 nm for 3Co/Ni and ∼1.4 nm for YNi₂ catalyst. Optimum conditions for synthesis also differ for catalysts compared; namely, for 3Co/Ni: current intensity is 93 A, helium pressure is 650 Torr, the electrode gap is 2.5-3 mm; for YNi₂: current intensity is 98 A, helium pressure is 500 Torr, the electrode gap is 1-2 mm.     

An effective surfactant-free isolation procedure for single-wall carbon nanotubes

An optimised isolation procedure of single-wall carbon nanotubes (SWNTs) from a SWNT soot without using any surfactant is reported. Amorphous carbon and small graphitic particles were washed away with N-methyl-2-pyrrolidone (NMP) and acetone. A large amount of graphite-coated metal particles were removed with the oxidation of the SWNT material with HNO₃ (6.5 and 4 M) and by washing the oxidised SWNT material with a mixture of methanol (MeOH) and deionised water. The isolated material was investigated with transmission electron microscopy (TEM) and Raman scattering (647.1 and 532 nm). An elemental analysis of the content of Co and Ni in the SWNT samples isolated at different steps of the isolation procedure was performed. On the basis of the TEM images and elemental analysis it was estimated that the purified material contains more than 75 wt.% of SWNTs.     

Purification of single-wall carbon nanotubes produced by arc plasma jet method

In the arc plasma jet method, a large amount of soot including single-wall carbon nanotubes (SWNTs) can be produced in a short time (1–2 g/min). However, a lot of impurities, such as amorphous carbon and catalyst metals, are included in the produced soot besides SWNT. Purification is indispensable to apply SWNTs industrially, but it was difficult until recently. Here, we report that SWNTs can be purified easily in large quantities by reflux in the hydrogen peroxide solution using catalyst of iron particle, which can activate the oxidation reaction of hydrogen peroxide solution. Higher than 90 wt.% purity of SWNTs are obtained by this technique.     

Thionine-mediated chemistry of carbon nanotubes

Thionine can be employed as a kind of useful functional molecule for the non-covalent functionalization of carbon nanotubes, as it shows a strong interaction with either SWNTs or MWNTs. Attachment of thionine molecules onto the sidewalls of carbon nanotubes would improve the solubility and lower the thermal stability of original carbon nanotubes. More importantly, it may functionalize the surface of carbon nanotubes with rich NH₂ groups and therefore open up more opportunities for the surface chemistry of carbon nanotubes. It has been proved that through the modification of small thionine molecules, other kinds of species such as cytochrome C and TiO₂ nanoparticles could be easily and selectively introduced onto the surface of carbon nanotubes. With this approach, SWNTs or MWNTs can be tailored with desired functional structures and properties.     

Electrochemical characterization of single-walled carbon nanotubes for electrochemical double layer capacitors using non-aqueous electrolyte

Single-walled carbon nanotubes (SWCNTs) were investigated by cyclic voltammetry and electrochemical impedance spectroscopy in a non-aqueous electrolyte, 1 M Et₄NBF₄ in acetonitrile, suitable for supercapacitors. Further, in situ dilatometry and in situ conductance measurements were performed on single electrodes and the results compared to an activated carbon, YP17. Both materials show capacitive behavior characteristic of high surface area electrodes for supercapacitors, with the maximum full cell gravimetric capacitance being 34 F/g for YP17 and 20 F/g for SWCNTs at 2.5 V with respect to the total active electrode mass. The electronic resistance of SWCNTs and activated carbon decreases significantly during charging, showing similarities of the two materials during electrochemical doping. The SWCNT electrode expands irreversibly during the first electrochemical potential sweep as verified by in situ dilatometry, indicative of at least partial debundling of the SWCNTs. A reversible periodic swelling and shrinking during cycling is observed for both materials, with the magnitude of expansion depending on the type of ions forming the double layer.     

A comparative study of electrochemical properties of two kinds of carbon nanotubes as anode materials for lithium ion batteries

Two kinds of carbon nanotubes (CNTs), i.e., short carbon nanotubes (CNTs-1) synthesized by co-pyrolysis method and long carbon nanotubes (CNTs-2) produced using common CVD technique were comparatively investigated as anode materials for lithium ion batteries via transmission electron microscope (TEM), high-resolution TEM and a variety of electrochemical testing techniques. The test results showed that the reversible capacities of CNTs-1 electrode were 266 and 170 mAh g⁻¹ at the current densities of 0.2 and 0.8 mA cm⁻², respectively, which were almost twice those of CNTs-2 electrode. The larger voltage hysteresis in CNTs-2 electrode was not only related to the surface functional groups on CNTs, but also to the surface resistance of CNTs, which results in greater hindrance and higher overvoltage during lithium extraction from electrode. The kinetics properties of these two CNTs electrodes were compared by AC impedance measurements. It was found that, both the surface film and charge-transfer resistances of CNTs-1 were significantly lower than those of CNTs-2; the lithium diffusion coefficient (D_Li) of both CNTs electrodes decreased as the drop of voltage, but the magnitude of the D_Li variation of CNTs-1 electrode was smaller than that of CNTs-2 electrode, indicating CNTs-1 exhibited higher electrochemical activity and more favorable kinetic properties during charge and discharge process.     

Activated carbon nanotubes-supported catalyst in fuel cells

The electrochemical property of platinum loaded on activated carbon nanotubes (Pt/ACNTs) was investigated by cyclic voltammograms (CVs) recorded in H₂SO₄ and H₂SO₄/CH₃OH aqueous solutions, respectively. Compared to 0.0046 A/cm² of Pt-loaded on pristine carbon nanotubes (Pt/CNTs) with a S_BET of 164 m²/g and 0.0042 A/cm² of conventional carbon black (Pt/C, Vulcan XC-72) with a S_BET of ∼250 m²/g, a better electrochemical activity (a high current density of 0.0070 A/cm² for weak-H₂ adsorption/desorption) of the Pt/ACNTs with high specific surface area (S_BET) of 830-960 m²/g was obtained. Furthermore, the highest current density of 0.079 A/cm² at 0.65 V in anodic sweep was observed during the methanol oxidation. On the basis of Pt size, utility ratio, and electro-active specific surface area (EAS), the Pt/ACNTs with a high Pt-loading of 50 wt.% exhibited the best electrochemical activity. The present ACNTs may be an excellent support material for electrochemical catalyst in proton exchange membrane and direct methanol fuel cells.     

Effect of surface modified porous inorganic-organic hybrid polyphosphazene nanotubes on the properties of polyethylene oxide based solid polymer electrolytes

2-(2-methyloxyethoxy)ethanol modified poly (cyclotriphosphazene-co-4,4′-sufonyldiphenol) (PZS) nanotubes were synthesized and solid composite polymer electrolytes based on the surface modified polyphosphazene nanotubes added to PEO/LiClO₄ model system were prepared. Differential Scanning Calorimetry (DSC) and Scanning Electron Microscopy (SEM) were used to investigate the characteristics of the composite polymer electrolytes (CPE). The ionic conductivity, lithium ion transference number and electrochemical stability window can be enhanced after the addition of surface modified PZS nanotubes. The electrochemical investigation shows that the solid composite polymer electrolytes incorporated with PZS nanotubes have higher ionic conductivity and lithium ion transference number than the filler SiO₂. Maximum ionic conductivity values of 4.95 × 10⁻⁵ S cm⁻¹ at ambient temperature and 1.64 × 10⁻³ S cm⁻¹ at 80 °C with 10 wt % content of surface modified PZS nanotubes were obtained and the lithium ion transference number was 0.41. The good chemical properties of the solid state composite polymer electrolytes suggested that the inorganic-organic hybrid polyphosphazene nanotubes had a promising use as fillers in solid composite polymer electrolytes and the PEO₁₀-LiClO₄-PZS nanotubes solid composite polymer electrolyte can be used as a candidate material for lithium polymer batteries.     

Covalent functionalization of single-walled carbon nanotubes by aniline electrochemical polymerization

Electrochemical polymerization of aniline in an HCl solution on a single-walled carbon nanotubes (SWNTs) film has been studied by Raman and FTIR spectroscopy. It is shown that this method leads to a covalent functionalization of SWNTs with polyaniline (PANI). A careful study in Raman scattering shows that the increase in the intensity of the band at 178 cm⁻¹ associated with radial breathing modes of SWNTs bundles suggests an additional nanotubes roping with PANI as a binding agent. A post chemical treatment with the NH₄OH solution of polymer-functionalized SWNTs involves an internal redox reaction between PANI and carbon nanotubes. As a result, the polymer chain undergoes a transition from the semi-oxidized state into a reduced one.     

Synthesis,characterization and electrochemical performances of MoO2 and carbon co-coated LiFePO4 cathode materials

The MoO₂ and carbon co-coated LiFePO₄ cathode materials were synthesized by a combined technique of solid state synthesis and the sol–gel method. Phase compositions and microstructures of the products were characterized by X-ray powder diffraction (XRD), Raman, SEM and TEM. Results indicate that MoO₂ can sufficiently coat on the LiFePO₄ surface and does not alter LiFePO₄ crystal structure, and the existence of MoO₂ increases the graphitization degree of carbon. SEM and TEM images reveal that MoO₂ presence has little impact on LiFePO₄ particle size. The electrochemical behavior of cathode materials was analyzed using galvanostatic measurement and cyclic voltammetry (CV). The results show that the existence of MoO₂ improves electrochemical performance of LiFePO₄ cathode material in specific capability and low-temperature behavior. The apparent lithium ion diffusion coefficient increases with MoO₂ content and maximizes around the MoO₂ content of x=5 wt%. It has been had further proved that the higher electronic conductivity of MoO₂ and carbon enhances the lithium ion transport to improve the electrochemical performance of LiFePO₄ cathode materials.     

Hydrogen storage on chemically activated carbons and carbon nanomaterials at high pressures

Hydrogen adsorption measurements have been carried out at different temperatures (298 K and 77 K) and high pressure on a series of chemically activated carbons with a wide range of porosities and also on other types of carbon materials, such as activated carbon fibers, carbon nanotubes and carbon nanofibers. This paper provides a useful interpretation of hydrogen adsorption data according to the porosity of the materials and to the adsorption conditions, using the fundamentals of adsorption. At 298 K, the hydrogen adsorption capacity depends on both the micropore volume and the micropore size distribution. Values of hydrogen adsorption capacities at 298 K of 1.2 wt.% and 2.7 wt.% have been obtained at 20 MPa and 50 MPa, respectively, for a chemically activated carbon. At 77 K, hydrogen adsorption depends on the surface area and the total micropore volume of the activated carbon. Hydrogen adsorption capacity of 5.6 wt.% at 4 MPa and 77 K have been reached by a chemically activated carbon. The total hydrogen storage on the best activated carbon at 298 K is 16.7 g H₂/l and 37.2 g H₂/l at 20 MPa and 50 MPa, respectively (which correspond to 3.2 wt.% and 6.8 wt.%, excluding the tank weight) and 38.8 g H₂/l at 77 K and 4 MPa (8 wt.% excluding the tank weight).     

Electrochemical insertion of lithium ions into disordered carbons derived from reduced graphite fluoride

Both covalent (obtained by direct fluorination at high temperature) and semi-ionic carbon fluorides (synthesized at room temperature) were reduced in order to obtain disordered carbons containing very small content of fluorine and different physical properties according to the reduction treatment (chemical, thermal or electrochemical). After a physical characterization (X-ray diffraction, electron spin resonance and FT-IR spectroscopies), the electrochemical behaviours of the pristine carbon fluorides and of the treated samples were investigated during the insertion of lithium using liquid carbonate-based electrolytes (LiClO₄-EC/PC, 50:50%, v/v). Both galvanostatic and voltammetric modes were performed and revealed that the voltage profiles and the capacities differed according to the starting material and the reduction treatment. Semi-ionic carbon fluoride treated in F₂ atmosphere for 2 h at 150 °C and then chemically reduced in KOH exhibits high reversible capacities (the reversible capacity is 530 mAh g⁻¹ in the second cycle); in this case, the voltage profiles show a large flat portion at potentials lower than 0.3 V which is attributed to the insertion/deinsertion of lithium ions between the small graphene sheets and/or the absorption of pseudo metallic lithium into the microporosity of the sample. Nevertheless, a part of the lithium ions are removed at potentials higher than 0.5 V versus Li⁺/Li limiting the useful capacity.     

Synthesis of titanate nanotubes and its processing by different methods

In the present studies, titanate nanotubes are synthesized using hydrolysis of commercial titania (TiO₂) nano-particle powder. The coatings of titanate nanotubes are fabricated using electro deposition method and these were subsequently processed under different conditions. These include (i) processing in atmospheric conditions, (ii) processing in vacuum, (iii) processing in Ar-gas RF-plasma, and (iv) processing in activated hydrogen (H₂) and methane (CH₄) gas mixtures using hot filament chemical vapour deposition (HF-CVD) method. It is observed that depending upon the type and processing parameters, the nanotube coatings exhibit interesting variations in the evolution and precipitation of materials phases. Typically, heating above temperatures (T_s) ∼600 °C render dehydration process leading to collapse of nanotubular structure, however, the nature of collapse is characteristically different in each case. The treatment in activated hydrogen and carbon led to the precipitation of carbon nanotubes and nanowires, while in other cases, crystallization or amorphization took place. The samples are characterized by using scanning electron microscopy (SEM), energy dispersive X-ray analysis (EDX), transmission electron microscopy (TEM), X-ray diffraction (XRD), Raman spectroscopy. The results are to be discussed in terms of reduction in thermal reaction barrier due to presence of activated particles.     

Electrochemical improvement of low-temperature petroleum cokes by chemical oxidation with H2O2 for their use as anodes in lithium ion batteries

The electrochemical performance of non-graphitized petroleum cokes has been improved by mild oxidation using hydrogen peroxide, a procedure used for the first time in these materials. For this purpose, various carbonisation temperatures and H₂O₂ treatments were tested. For low sulfur content cokes, the aqueous oxidative treatment significantly increases the capacity values above 372 mAh/g during the first cycles. In contrast, cokes with a sulfur content of ca. 5%, did not shown a real improvement. The former results have been interpreted in terms of an effective oxidation of the particles surface, which removes unorganized carbon, where lithium can be irreversibly trapped. Moreover, a stable and less resistive passivating layer grows during the first discharge of lithium, as revealed by impedance spectroscopy. Therefore, chemical procedures, as mild oxidation, open an interesting field of research for the improvement of disordered carbons as anode materials in lithium ion batteries.