Preparation and electrochemical characterizations of MnO2-dispersed carbon aerogel as supercapacitor electrode material

The nano-sized amorphous α-MnO₂-dispersed carbon aerogels (CAs) were prepared by liquid phase co-precipitation technique. Different MnO₂ contents and heating temperatures were taken to prepare the composites. The composites prepared were used to make electrodes of electrochemical supercapacitors. Electrochemical properties of the electrodes were studied by cyclic voltammetry and galvanostatic charge–discharge. The specific capacitances of the MnO₂-dispersed CAs and the nano-MnO₂ ingredient in the composite are up to 219 F g^?1 and 401 F g^?1 at 5 mA.cm^?2, 1.6 times and 5.0 times greater than that of neat CA and MnO₂, respectively.     

Vanadium pentoxide nanobelts: One pot synthesis and its lithium storage behavior

In this paper, we report a synthesis, characterization and electrochemical properties of V₂O₅ nanobelts. V₂O₅ nanobelts have been prepared via hydrothermal treatment of commercial V₂O₅ in acidic (HCl/H₂SO₄) medium at relatively low temperature (160 °C). The hydrothermally derived products have been characterized by powder X‐ray diffraction (XRD), Fourier transform infrared spectroscopy (FT‐IR), Raman spectroscopy, X‐ray photo electron spectroscopy (XPS), UV‐Vis spectroscopy, Scanning/Transmission electron microscopy (SEM/TEM). XRD pattern of V₂O₅ nanobelts show an orthorhombic phase. From the FTIR spectrum, the peak observed at 1018 cm⁻¹ is characteristic of the stretching vibration mode of the terminal vanadyl, V = O. The UV‐Vis absorption spectrum of V₂O₅ nanobelts show maximum absorbance at 430 nm, which was blue‐shifted compared to that of bulk V₂O₅. TEM micrographs reveal that the products consist of nanobelts of 40‐200 nm in thickness and several tens of micrometers in length. The electrochemical analysis shows an initial discharge capacity of 360 mAh g⁻¹ and its almost stabilized capacity is reached to 250 mAh g⁻¹ after 55 cycles. A probable reaction mechanism for the formation of orthorhombic V₂O₅ nanobelts is proposed.     

Development of porous silicon matrix and characteristics of porous silicon/tin oxide structures

Porous silicon (PSi) was formed at different current densities in the range of 5-60 mA/cm² by electrochemical anodized etching in HF for different durations in the range of 10-30 min. Above this PSi structure, SnO₂ films were deposited by the spin coating technique. The PSi has been characterized by X-ray diffraction studies. Peaks pertaining to PSi along with those corresponding to SnO₂ are observed. Atomic force microscopic studies indicate that very fine needle like silicon nanostructures are observed which is the result of the best PSi structure formed at 30 mA/cm². For the SnO₂ covered PSi structures, larger grains are observed with uniform coverage. The PSi samples prepared at current densities above and below 30 mA/cm² show PL spectra with asymmetric and overlapped peaks. The PL profile of thin SnO₂ film coated on PSi shows a peak at 633 nm and a small hump at about 660 nm.     

Well‐defined Sb2S3 nanostructures: citric acid‐assisted synthesis,electrochemical hydrogen storage properties

Well‐defined (three‐dimensional) 3‐D dandelion‐like Sb₂S₃ nanostructures consisted of numerous nanorods have been achieved via a facile citric acid‐assisted solvothermal process. The as‐prepared products were characterized by X‐ray diffraction (XRD), field‐emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM) and high‐resolution TEM (HRTEM), respectively. The influence factors of the formation of the hierarchical Sb₂S₃ nanostructures are discussed in details based on FESEM characterizations. By simply controlling the quantity of citric acid, the nucleation and growth process can be readily tuned, which brings the different morphologies and nanostructures of the final products. On the basis of a series of contrastive experiments, the aggregation‐based process and anisotropic growth mechanism are reasonably proposed to understand the formation mechanism of Sb₂S₃ hierarchical architectures with distinctive morphologies including nanorods, and dandelion‐like nanostructures. Charge‐discharge curves of the obtained Sb₂S₃ nanostructures were measured to investigate their electrochemical hydrogen storage behaviors. It revealed that the morphology played a key role on the hydrogen storage capacity of Sb₂S₃ nanostructure. The dandelion‐like Sb₂S₃ nanostructures exhibited higher hydrogen storage capacity (108 mAh g⁻¹) than that of Sb₂S₃ nanorods (95 mAh g⁻¹) at room temperature.     

Amorphous tin–iron oxide thin films with 3D reticular porous morphology for lithium‐ion batteries

Porous reticular tin–iron oxide composite have been prepared by electrostatic spray deposition method for lithium‐ion batteries. The structure of depsitied electrodes are investigated by X‐ray Diffraction (XRD), which shows that the film is amorphous. Electrochemical characterization by galvanostatic charge‐discharge tests demonstrate that the conversion reactions in these electrodes enable initial discharge capacities of about 1551 mAh/g for tin–iron oxide thin film electrode, and the reversible capacity stayed in the range of 769–601 mAh/g during the successive 30 cycles. The high porosity of the 3D reticular structure can provide more reaction sites on the electrode surface and accommodate volume variation of Sn particles during Li alloying–dealloying. Such a composite film are expected to be applied as attractive anodes for lithium‐ion batteries.     

A preparation of carbon fibers using a block copolymer surfactant template and its application to anode of lithium ion batteries

Hard carbon nanofiber (HCNF) bundles were prepared using reverse hexagonal micelle (H₂) phase formed by a template of an amphiphilic block copolymer surfactant and their anode performance in lithium ion batteries was analyzed. Prepared HCNF showed a higher discharge capacity at voltage region above 0.8 V (vs. Li/Li+) than that of control carbon. Rate capability was also examined in order to demonstrate merit of the fibrous morphology of CNF, with current values corresponding to 0.1, 0.2, 0.5, 1 and 2 C rate. Prepared HCNF electrode exhibited higher rate capability than control carbon, which was attributed to morphological difference.     

Electrochemical performance of B and M phases VO2 nanoflowers

VO₂ exists in four phases, among which, the M/R phase VO₂ is well known for its reversible metal‐semiconductor phase transition at about 68 °C, and VO₂ (B) is a promising candidate cathode material to be applied in aqueous lithium‐ion battery owing to its proper electrode potential and layered structure. In this study, VO₂ (B) nanoflowers was synthesized via one‐step hydrothermal process and then successfully transformed into the VO₂ (M) by heat treatment. Electrochemical behaviors of the two samples were evaluated by cycling discharge and cyclic voltammetry (CV). The results showed that flower‐like VO₂ (B) had the first discharge capacity of 180.33 mAhg‐1, an outstanding value of 52.8% for the capacity retention after 50 cycles. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Effect of temperature on dielectric properties of SnO2/Sb2O3 mixed thin films

Thin films of various thicknesses in the MIM structure have been prepared from the powder of SnO₂/Sb₂O₃ mixed sample by the thermal evaporation technique in a vacuum of 10⁻⁵ Torr. Dielectric properties of SnO₂/Sb₂O₃ mixed thin films have been studied with temperature starting from LNT to RT and above RT and frequency ranging from 100 Hz to 16 kHz. The activation energy for the migration of charge carriers in SnO₂/Sb₂O₃ mixed thin films has been calculated and it is found to be 0.23 eV. The results thus obtained on dielectric properties of SnO₂/Sb₂O₃ mixed thin films are presented and discussed.     

WO3-based electrochromic system with hybrid organic–inorganic gel electrolytes

Thin metal oxide films for a WO₃-based symmetric electrochromic system with a nickel oxide layer as the counter electrode have been prepared by spray pyrolysis on SnO₂:F coated soda-lime float glass, at a temperature of 670–720 °C and using metal acetylacetonates as precursors. The films have been characterized for composition and morphology by scanning electron microscopy equipped with an X-ray energy dispersive analyzer (SEM/EDAX), X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD). Electrochromic properties have been examined in the electrochemical cells of a smart window arrangement using lithium ion doped sol–gel derived organic–inorganic hybrid materials as electrolytes. Hybrids with room-temperature ionic conductivities of 10^?4–10^?3 Ω^?1 cm^?1 have been synthesized from tetraethyl orthosilicate (TEOS) with an addition of 35 mass % of organic compounds. Coloration-bleaching of WO₃ films with lithium ions from hybrid electrolytes has resulted in the desired modulating the properties in the visible and near infrared spectrum range. An XPS analysis has shown the presence of a lower oxidized tungsten oxide phase (WO_2.92) in the WO₃ film.     

Synthesis by precipitation method and investigation of SnO2 nanoparticles

In this paper the synthesis of SnO₂ nanoparticles with average particle size up to about 70 nm using SnCl₂2H₂O and NH₄OH in 1‐botanol solution by the precipitation method is reported and the inhibition of sodium dodecyl sulphate (SDS) on the SnO₂ particle growth is investigated by soaking SnO₂precursor in the SDS solution for 24 h. The as‐prepared SnO₂and SDS modified‐SnO₂ powders, then, were calcined at different temperatures and the X‐ray powder diffraction (XRD) and Fourier transform infrared spectroscopy (FT‐IR) were used to characterize the output samples. The XRD results reveal that the structure of tin‐dioxide is tetragonal rutile and the as‐prepared SnO₂ nanoparticles grow with increasing the annealing temperature, while the SDS treatment prevents the particle growth under the same condition. Furthermore, the FT‐IR results indicate the formation of tin‐hydroxyl group which are then converted into tin‐dioxide with heat treatment. Further characterization of the samples by the transmission electron microscopy (TEM) and the photoluminescence (PL) spectroscopy was carried out. The room temperature PL spectra of SnO₂exhibits broad and strong peak attributed to the surface defects such as oxygen vacancies and intensity of which decreases with the increase in particle size. (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Stoichiometry and point defects in lithium niobate crystals

Investigations of the OH⁻ ion incorporation into LiNbO₃ crystals and the comparison of calculated and measured densities show that undoped congruent lithium niobate crystals contain Li⁺ and O^{− −} ion vavancies O and Li⁺. If really present, stacking faults are of inferior importance. The good agreement of the absorption edges of stoichiometric and of 2.7 mol% MgO containing congruent lithium niobate crystals is explained by the occupance of all oxygen sites within these crystals.     

Preparation of lithium carbonate hollow spheres by spray pyrolysis

Lithium carbonate (Li₂CO₃) hollow spheres were prepared by spray pyrolysis of lithium bicarbonate (LiHCO₃) in this research. The products were characterized by X‐ray diffraction (XRD), scanning electron microscope (SEM), crystal size distribution (CSD) analysis and BET surface area measurement. The XRD figure of the product is nearly the same as the standard pattern, indicating the product achieved by spray pyrolysis has pure Li₂CO₃ crystalline phase. The SEM images show the self‐assembly hollow spheres are composed of about 200 nm primary particles. While the CSD analysis shows the macro‐volume mean crystal size ranges 4‐9 μm depending on the experimental conditions. The BET surface area of the product reaches 7.24 m²/g, which is much higher than the best value reported in the literature. The product prepared in this work has great potential application prospect in the lithium‐battery industry. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Effects of synthesis conditions on the yields and properties of HZSM‐5

In the SiO₂‐Al₂O₃‐TPAOH‐NH₄OH system through a two‐step procedure, the effects of synthesis parameters on the yields and properties of HZSM‐5 were studied. As the feeding n(SiO₂)/n(Al₂O₃) ratio increased, the yields of synthesized samples were between 11% and 14% while the crystallinity tended to decrease at the ratio > 300. At the ratio of 150, the yield was 13.7% and the ratio of actual yield to theoretical yield was 93%. The sample shaped ellipse‐like particles of 3 × 10⁻⁶ m. At the n(NH₃)/n(SiO₂) ratio of 1.5, the yield was 13.1% and the sample showed regular ellipse‐like particles of 2 × 10⁻⁶ m. Too high dosage of NH₄OH lowered the yield and the crystallinity. The addition of seed crystal favored the HZSM‐5 synthesis in high crystallinity. At the addition amount of 4%, the yield reached 13.9% and the sample shaped in spherical particles of 0.5 × 10⁻⁶ m. Synthesized HZSM‐5 with a surface area of 455 m²·g⁻¹ and intrinsic acidity showed highly catalytic activity toward the methanol conversion to olefins reaction.     

Effect of Electric Field on Dielectric Properties of SnO2 Sb2O3 and their Mixed Thin Films

Thin films of various thicknesses in the MIM structure have been prepared from the the powders of SnO₂, Sb₂O₃ and (SnO₂ + Sb₂O₃) of high purity by the thermal evaporation technique in a vacuum of 10⁻⁵ Torr. Dielectric properties of SnO₂, Sb₂O₃, and their mixed thin films have been studied with ac and dc electric fields and frequency. Capacitance and loss tangent are almost independent on dc voltage upto 1.0 V for SnO₂, 10.0 V for Sb₂O₃ and 2.5 V for mixed films. These capacitors become unstable at 1.0 V for SnO₂ films and 2.5 V for mixed films. For higher film thicknesses the decay in these films starts at higher voltages. Capacitance and loss tangent increases with applied ac voltage in SnO₂, Sb₂O₃, and their mixed films. A comparison of the capacitance values of SnO₂, Sb₂O₃, and their mixed films showed that the capacitance values are less in Sb₂O₃ as compared to SnO₂ films. In mixed films the capacitance is greater than the constituent films. These studies have shown that Sb₂O₃ films are found to be more stable compared to SnO₂ and their mixed films for ac and dc voltages. The results thus obtained on SnO₂, Sb₂O₃, and their films are presented and discussed.     

Crystal growth of FeCO3 in mixed monoethylene glycol and water solvent

The transportation of natural gas in long subsea pipelines is a challenge when it comes to hydrate prevention, corrosion and mineral scaling. When monoethylene glycol (MEG) is injected into carbon steel pipelines to prevent formation of gas hydrates, the solubility of the corrosion products is altered. Understanding the kinetics of FeCO₃ precipitation may make it possible to avoid deposition in the gas liquid separation process and improve solids removal in MEG recovery units. In this work, the growth kinetics of iron carbonate (siderite) has been studied in seeded batch experiments in MEG‐water solutions with 0 and 40 wt% MEG at 50 and 70 °C. Precautions were taken to keep anaerobic conditions and avoid oxidation of ferrous ions. The growth rate (G) was measured as function of supersaturation (S) and fitted to the equation: G = k_r(S‐1)^g. The growth order (g) was approximately 2 independent of the MEG concentration at the two temperatures. The growth rate constant (k_r) was in the range of 6 × 10⁻¹¹ to 1 × 10⁻¹⁰ m/s. Temperature increase from 50 to 70°C had no measurable effect on the growth rate while in the presence of 40 wt% MEG the growth rate constant decreased.     

Identification of crystal symmetry in Kramers and non‐Kramers ions by optical absorption: Divalent copper and nickel ions in diamagnetic lattices

The optical absorption spectra of Ni(II) doped hexaimidazole zinc(II) dichloride tetrahydrate (HZDT) and Cu(II) doped magnesium potassium phosphate hexahydrate (MPPH) have been studied at room temperature. Ni(II)/HZDT spectrum consists of three strong and one weak band. The calculated value of Dq is 1051 cm^‐1 and the interelectron repulsion parameters B and C are 854 and 3626 cm^‐1 respectively. The correlation of optical work with EPR has yielded the spin‐orbit interaction parameters λ and ξ as –225 and –450 cm^‐1 respectively. The symmetry around the Ni(II) ion is distorted octahedral, as suggested by EPR results. The estimated percentage covalency of the nickel‐nitrogen bond is around 30%. The optical absorption studies of Cu(II)/MPPH show three bands, which are identified as ²B_1g → ²A_1g, ²B_1g → ²B_2g and ²B_1g → ²E_g transitions. The octahedral field parameter Dq and the tetragonal field parameters have been evaluated from the observed adsorption bands. (© 2004 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Ageing effect on dielectric properties of SnO2, Sb2O3, and their mixed thin films

Thin films of various thicknesses in the form of MIM structures have been prepared from the powders of high purity of SnO₂, Sb₂O₃, and their mixed powders separately by the thermal evaporation technique in a vacuum of 10⁻⁵ Torr. The dielectric properties of these oxide thin films have been studied with ageing time and also with frequency at room temperature. The results obtained have shown that the capacitance and loss tangent of the structures initially fall off rapidly and thereafter they attain a constant value even after ageing the capacitors for about 20 days. The rapid fall of capacitance and loss tangent may be due to the rapid decrease in the density of defects due to ageing time. The results thus obtained on SnO₂, Sb₂O₃, and their mixed thin film capacitors are presented and discussed.     

Influence of Host Lattice in Interstital Dopant Sites: EPR Studies on Cu (II) Doped Sarcosine Cadmium Bromide Single Crystals

EPR study of Cu(II) doped in sarcosine cadmium bromide single crystals are carried out at room temperature. The impurity ions occupy the interstitial position in this crystal lattice. Crystalline field around the Cu(II) ion in this low symmetry crystal is rhombic. The transitions arise from a single paramagnetic site with g_xx = 2.1082, g_yy = 2.0005, g_zz = 2.2071, and A_xx = ‐64 x 10^‐4 cm^‐1, A_yy = ‐23 x 10^‐4 cm^‐1, A_zz =‐185 x 10^‐4 cm^‐1. The ground state is an admixture of dx2‐y2 and dz2 states. The observed molecular orbital coefficient value a2 = 0.85 reveals a moderate covalency of the s bonding and b2 = 0.967 indicates the weak pi bonding. A strong interaction between Cu(II) and nitrogen ligands is found to exist.     

Optical absorption of Fe3+ Ion in LiF crystals

The absorption spectrum of LiF—Fe³⁺ single crystals was investigated at liquid nitrogen temperature. Six new absorption bands, unobserved earlier in other works, were found, which were located at 11 200, 16 000, 22 700, 27300, 30 500, and 41 900 cm⁻¹. The spectrum was interpreted in the cubic cristalline field approximation with D_q = 1397 cm⁻¹, B = 657 cm⁻¹, C = 3226 cm⁻¹. Above mentioned bands were assigned to the transitions from a ground state ⁶A_1g to the levels ⁴T_1g(G), ⁴T_2g(G), ⁴A_1g(G) (⁴E_g), ⁴E_g(D), ²T_1g(F), and ⁴T_1g(F), respectively.     

Conductivity stabilization by metal and oxide additives in ceramics on the basis of VO2 and glass V2O5–P2O5

Conductivity behavior during the temperature cycling through the phase transition temperature of VO₂ (T_t = 68 °C) was investigated in glass-ceramics based on VO₂ and vanadium phosphate glass (VPG) for compositions without and with Cu and SnO₂ additives. Copper and SnO₂ additives stabilize the conductivity of glass-ceramics at temperature cycling. For ceramics (wt%) (80 − y)VO₂–5Cu–15VPG–ySnO₂ the best stabilizing effect takes place when SnO₂ content is in the interval 35 wt% < y < 50 wt%. Ceramics with such SnO₂ content keeps a stable value of the conductivity change (∼10²) in the vicinity of VO₂ phase transition temperature and shows the conductivity decrease no more than of 2.5 times after 3000 thermal cycles. The reasons of conductivity stabilizing in VO₂-based glass-ceramics with additives of Cu and SnO₂ are being discussed. The analysis resting on the percolation theory has shown the increase of conductivity stability in VO₂-based glass-ceramics when the VO₂ volume fraction and the average size of VO₂ crystallites decrease and the ceramics surface tension increases.