Li-intercalation electrochemical/electrochromic properties of vanadium pentoxide films by sol electrophoretic deposition

Thin films of orthorhombic V₂O₅ have been prepared by sol electrophoretic deposition (EPD) followed by post-treatment at 500 °C. Their electrochemical and optical performances have been investigated for possible applications in electrochemical/electrochromic devices. Li⁺-intercalation properties of the films have been explored in two voltage ranges: 0.4 to −1.1 V and 0.4 to −1.6 V versus Ag/Ag⁺, respectively. High capacities of over 300 mAh/g are acquired in the wider voltage range at a current density of 50 μA/cm² and moderate capacities of 140 and 110 mAh/g are obtained in the narrower voltage range at a current density of 25 and 50 μA/cm², respectively. Electrochemical measurements have shown that the films demonstrate good cyclability in both voltage ranges. X-ray diffraction, scanning electron microscopy and optical spectra have been used to examine the changes in crystallinity, microstructure, morphology and transmittance of the films during cycling. Films cycled to a deeper voltage of −1.6 V versus Ag/Ag⁺ deliver higher capacity with appreciable morphological change, while films cycled in the narrower voltage range show moderate capacity and maintain the morphology, optical responses and crystalline structure. Voltage range can be optimized in between to acquire both high capacity and stability in structure, electrochemical and optical properties. High Li⁺-intercalation capacity and good cyclic stability are attributed to the porous structure of V₂O₅ films prepared by EPD.     

Porous NiO/Ag composite film for electrochemical capacitor application

A highly porous NiO/Ag composite film is prepared by the combination of chemical bath deposition and silver mirror reaction. The as-prepared NiO/Ag composite film has an interconnecting reticular morphology made up of NiO flakes with highly dispersed Ag nanoparticles of about 6 nm. The pseudocapacitive behavior of the NiO/Ag composite film is investigated by cyclic voltammograms (CV) and galvanostatic charge–discharge tests in 1 M KOH. The NiO/Ag composite film exhibits weaker polarization, higher specific capacitance and better cycling performance as compared to the unmodified porous NiO film. The specific capacitance of the porous NiO/Ag composite film is 330 F g⁻¹ at 2 A g⁻¹ and 281 F g⁻¹ at 40 A g⁻¹, respectively, much higher than that of the unmodified porous NiO film (261 F g⁻¹ at 2 A g⁻¹ and 191 F g⁻¹ at 40 A g⁻¹). The enhancement of pseudocapacitive properties is due to highly dispersed Ag nanoparticles in the composite film, which improves the electric conductivity of the film electrode.     

Morphological and electrochemical properties of LiV3O8 cathode powders prepared by spray pyrolysis

Lithium trivanadate (LiV₃O₈) powders are prepared by spray pyrolysis. The precursor powders of LiV₃O₈ obtained by spray pyrolysis have spherical and rod-like morphologies. The LiV₃O₈ powders post-treated at 300 °C and 400 °C also have spherical and rod-like morphologies. However, the LiV₃O₈ cathode powders post-treated at 500 °C consist of only rod-like crystals. The crystalline structure of the precursor powders that were directly prepared by spray pyrolysis comprised of LiV₃O₈ layers along with a small amount of β-Li_0.33V₂O₅ impurity. The peak due to β-Li_0.33V₂O₅ persisted in the XRD spectrum even after post-treatment at 300 °C. On the other hand, crystalline structures of the powders post-treated at 400 °C and 500 °C comprised pure LiV₃O₈ layers. The initial discharge capacities of the LiV₃O₈ cathode powders decrease from 344 mAh g⁻¹ to 261 mAh g⁻¹ when the post-treatment temperatures increase from 300 °C to 500 °C. The discharge capacities of the LiV₃O₈ cathode powders obtained after post-treatment at 400 °C and 500 °C are approximately 255 mAh g⁻¹ and 236 mAh g⁻¹, respectively, after 40 cycles.     

Ion-sensing properties of 1D vanadium pentoxide nanostructures

ABSTRACT: The application of one-dimensional (1D) V2O5.nH2O nanostructures as pH sensing material was evaluated. 1D V2O5.nH2O nanostructures were obtained by a hydrothermal method with systematic control of morphology forming different nanostructures: nano-ribbons, nano-wires and nano-rods. Deposited onto Au-covered substrates, 1D V2O5.nH2O nanostructures were employed as gate material in pH sensors based on separative extended gate FET as an alternative to FET isolation from the chemical environment. 1D V2O5.nH2O nanostructures showed pH sensitivity around the expected theoretical value. Due to high pH sensing properties, flexibility and low cost, further applications of 1D V2O5.nH2O nanostructures comprise enzyme-FET-based biosensors using immobilized enzymes.     

Hydrated Mn(IV) oxide-exfoliated graphite composites for electrochemical capacitor

Commercially available low cost exfoliated graphite (EG, nominal diameter 130 μm) was used as a conductive substrate for electrochemical capacitor of hydrated Mn(IV) oxide, MnO₂·nH₂O. The MnO₂·nH₂O-EG composites were prepared by addition of EG to potassium permanganate solution, followed by 1 h stirring and then slow addition of manganese(II) acetate solution. By this procedure submicrometer or smaller sized MnO₂·nH₂O particles having mesopores of 6-12 nm in diameter were formed on the graphite sheets of EG. Although EG alone showed only about 2 F g⁻¹, the composites showed good rectangular cyclic voltammograms at 2-20 mV s⁻¹ in 1 mol L⁻¹ Na₂SO₄. The capacitance per net amount of MnO₂ increased proportionally with EG content, that is, utilization ratio of MnO₂ increased with EG content. The composites of MnO₂·nH₂O and smaller diameter of EG (nominal diameter 45 μm) or artificial graphite powder (average diameter 3.7 μm) showed fairly good performance at 2 mV s⁻¹, but with increasing potential scan rate the rectangular shape was distorted and capacitance decreased drastically. The results implies that sheet-like structure is more effective than small particles as conductive materials, when the formation procedure of composite is the same. Large sized EG may be a promising conductive material for electrochemical capacitors.     

Enhanced surface hydrophobisation for improved performance of carbon aerogel electrochemical capacitor

A more efficient surfactant vinyltrimethoxysilane (vtmos) than previously reported one, sodium oleate (OAS), has been employed to enhance surface hydrophobisation of carbon aerogel for electric double layer capacitor (EDLC) application. In comparison with attachment of hydrophobic moiety of OAS species to carbon surface grafting of vinyltrimethoxysilane functional group enhances more efficiently the hydrophobisation of carbon material and the affinity toward propylene carbonate (PC) solvent, and accordingly improves more considerably the wettability of carbon in PC-based electrolyte solution. The enhanced wettability facilitates more rapid electrolyte ions transport within micropores of the vtmos modified carbon aerogel, resulting in lower internal resistance and energy loss than OAS modified carbon capacitor, and also favors more surface area for EDL formation, resulting in higher specific capacitance and energy for vtmos modified carbon aerogel electrochemical capacitor. In addition, vtmos modified carbon material has shown comparable charge-discharge cycling stability to that obtained by the original carbon.     

Diameter dependent optical and field emission properties of vanadium pentoxide nanobelts

Vanadium Pentoxide is considered as an intriguing material for several advanced technological applications such as supercapacitors, Lithium-ion batteries, photo-catalysis and optical waveguide. In this work, we have presented a facile and non-toxic method for the synthesis of Vanadium Pentoxide nanobelts. Considering the aforesaid motivations, we tuned the size of Vanadium Pentoxide nanobelts by simply varying the synthesis temperature. The XRD results confirm that the obtained phase is Vanadium Pentoxide with no impurities found within the experimental limitations. The analysis by Scanning Electron Microscopy (SEM) depicts that the diameter of nanobelts decreased from 52.7nm to 44.7nm with the increase in synthesis temperature within range 180^oC-220 °C respectively. The UV–Vis-Spectrum shows that bandgap of nanobelts increased in the range 2.25eV-3eV with the increase in synthesis temperature within range 180^oC-220 °C. For field emission measurements, the variation in field enhancement factor and turn-on voltage is also observed. These results indicate that by just varying a simple parameter one can tune the band gap and electronic properties of Vanadium Pentoxide nanobelts. These studies show that Vanadium Pentoxide nanobelts can be promising candidate for optoelectronic device.     

Synthesis of TiO2 microspheres by ultrasonic spray pyrolysis and photocatalytic activity evaluation

This work presents and discusses TiO₂ microspheres synthesized by ultrasonic spray pyrolysis. A simple setup allowed for the continuous production of TiO₂ nanocrystals. During the process, the particles experienced a short residence time (ca. 40 s) at the set temperature (700 °C), promoting phase stability and limited particle coarsening. As a result, porous anatase TiO₂ microspheres with crystallite size ～8 nm and specific surface area ～27 m² g^-1 were produced as soft spherical agglomerates of ～0.6 μm. Samples were analyzed using X-ray diffraction, BET specific surface area, SEM, TEM, XPS, and UV/Vis diffuse reflectance spectra, as well as in their photocatalytic activities. Photoactivity was evaluated through the degradation of the model contaminant acetaminophen under UV irradiation, and the results confirmed the superior performance of the synthesized TiO₂ microspheres, exceeding the commercial standard TiO₂ P25 by ca. 60% in terms of reactivity.     

Nano-composite of polypyrrole/modified mesoporous carbon for electrochemical capacitor application

Nano-thin polypyrrole (PPy) layers were coated on chemically modified ordered mesoporous carbon (m-CMK-3) by an in situ chemical polymerization. Structural and morphological characterizations of m-CMK-3/PPy composites were carried out using field emission scanning electron microscopy. Pseudo-capacitive behavior of the deposited PPy layers on m-CMK-3 was investigated by cyclic voltammetry, galvanostatic charge-discharge and electrochemical impedance spectroscopy. As results of this study, the thin layer of PPy in the composite electrode was effective to obtain fully reversible and very fast Faradaic reaction. A maximum discharge capacity of 427 F g⁻¹ or 487 F g⁻¹ after correcting for weight percent of PPy phase at the current density of 5 mA cm⁻², could be achieved in a half-cell setup configuration for the m-CMK-3/PPy composites electrode, suggesting its potential application in electrode material for electrochemical capacitors.     

Synthesis of NiO-YSZ composite particles for an electrode of solid oxide fuel cells by spray pyrolysis

NiO-YSZ (YSZ: Y₂O₃-stabilized ZrO₂) composite particles for a Ni-YSZ cermet anode in solid oxide fuel cells (SOFCs) were synthesized via spray pyrolysis (SP). The formation mechanism of the composite particles by this process was analyzed. The internal microstructure of the particles synthesized during SP processing was observed at each heating temperature of 200, 300, 400 and 1000 °C, and then the formation mechanism of the composite structure was discussed. As a result, it was found that NiO-YSZ composite particles were formed through the following steps. Firstly, during the evaporation stage up to 200 °C, a filled particle with Ni(CH₃COO)₂ and YSZ fine grains were formed from the atomized droplet containing Ni ion and dispersed YSZ sol by volume precipitation. Secondly, during the continuous thermolysis stage up to 400 °C, YSZ grains were formed and moved to the surface of the composite particle by the outgas and the oxidation of Ni(CH₃COO)₂. Finally, the NiO-YSZ composite particle that has NiO grains uniformly covered with fine YSZ grains was formed after the final sintering stage up to 1000 °C.     

Facile synthesis and electrochemical capacitance of composites of polypyrrole/multi-walled carbon nanotubes

Composites of polypyrrole (PPy) and multi-walled carbon nanotubes (MWCNTs) were synthesized by a facile method involving one-step electrochemical deposition from a thin-layer of ionic liquid solution attached on a glassy carbon electrode. The morphology of the composites was characterized by field emission scanning electron microscopy, and the capacitance properties were investigated by cyclic voltammetry (CV). The charge-discharge behavior of the composites prepared in this work was examined by chronopotentiometry at a constant current density for multi-cycle scans. The results show that the PPy/MWCNT composites have a porous 3D nanostructure, with high specific capacitance (SC) of 890 F/g (for the mass of the PPy in the composites) calculated from CV at 2 mV/s in 1.0 M KCl. The stability of the composites in 1.0 M KCl electrolyte was also examined by multi-cycle CV and only 9% decrease of SC value was observed for the 1000 cycles.     

Porous silicon pillar and bilayer structure as a nucleation center for the formation of aligned vanadium pentoxide nanorods

Porous silicon single layer (PSM), bilayer (PSB) and pillar (PSP) structures have been evaluated as nucleation centers for vanadium pentoxide (V₂O₅) crystals. Deposition of vanadium precursor over different substrates (drop casting technique), followed by annealing treatment under Ar-H₂ (5% H₂) atmosphere, induced crystallization of vanadium oxide. With respect to c-Si/SiO₂ substrate, V₂O₅ nanorods with relatively large aspect ratio were formed over and within PSP structures. On the other hand, pores in PSM and PSB were found to be filled with relatively smaller crystals. Additionally, PSB provided a nucleation substrate capable to align the nanocrystals in a preferential orientation, while V₂O₅ crystals grown on PSP were found to be randomly aligned around the nanoporous pillar microstructure. Nanorods and nanocrystals were identified as V₂O₅ by temperature-controlled XRD measurements and evidence of their crystalline nature was observed via transmission electron microscopy. A careful analysis of electronic microscopy images allows the identification of the facets composing the ends of the crystals and its corresponding surface free energy has been evaluated employing the Wulff theorem. Such high surface area composite structures have potential applications as cathode material in Lithium-ion batteries.     

Firing characteristics of size-controlled silver-glass composite powders prepared by spray pyrolysis

Size-controlled spherical silver-glass composite powders were directly prepared by using spray pyrolysis. The mean sizes of the composite powders changed from 0.34 to 0.78 μm when the concentration of the spray solution was changed from 0.05 to 2 M. The firing characteristics of composite powders formed from the spray solutions with a glass content equal to 3 wt.% of the silver component were affected by the mean sizes of the powders. Silver-conducting films formed from large-sized composite powders had a denser structure than those formed from small-sized composite powders. Further, silver-conducting films formed from composite powders with a mean size of 0.78 μm had specific resistances of 3 and 2 μΩ cm at firing temperatures of 450 and 500 °C. However, silver-conducting films formed from composite powders with a mean size of 0.34 μm had specific resistances of 8.2 and 6.9 μΩ cm at firing temperatures of 450 and 500 °C.     

Characterization of luminescent SrAl2O4 films doped with terbium and europium ions deposited by ultrasonic spray pyrolysis technique

SrAl₂O₄, SrAl₂O₄:Tb³⁺ and SrAl₂O₄:Eu³⁺:Eu²⁺ films were synthesized by means of the ultrasonic spray pyrolysis technique. These samples, characterized by X-Ray Diffraction, showed the monoclinic phase of the strontium aluminate. Images of the surface morphology of these films were obtained by SEM and the chemical composition was measured by EDS and XPS. The photoluminescence and cathodoluminescence characteristics of the films were studied as a function of the terbium and europium concentrations. The optimal PL emission intensities were reached at 8?at% for terbium doped films and 6?at% for europium doped samples. The CL emission spectra for europium doped films showed the typical bands of Eu³⁺ ions and also a broadband centered at 525?nm which is attributed to Eu²⁺ ions. XPS measurements confirm the presence of Eu³⁺ and Eu²⁺ in europium doped SrAl₂O₄ films, without having been subjected to a reducing atmosphere. Chromatic diagrams exhibited green color for SrAl₂O₄:Tb³⁺ films, red and yellow colors for SrAl₂O₄:Eu³⁺:Eu²⁺ films. The PL decay curves were also obtained: the averaged decay time was 2.7?ms for SrAl₂O₄:Tb³⁺ films and 1.9?ms for SrAl₂O₄:Eu³⁺ films. Similar results were obtained by the stretched exponential model.     

Synthesis of spherical LiMn2O4 microparticles by a combination of spray pyrolysis and drying method

Lithium manganese oxide (LiMn₂O₄) has been synthesized by a spray pyrolysis method from the precursor solution; LiNO₃ and Mn(NO₃)₂·6H₂O were stoichiometrically dissolved into distilled water. The synthesized LiMn₂O₄ particles exhibited a pure cubic spinel structure in the X-ray diffraction (XRD) patterns, however they were spherical hollow spheres for various concentrations of precursor solution. Thus, the as-prepared LiMn₂O₄ particles were then ground in a mortar and dispersed into distilled water. To make a well dispersed slurry solution, a dispersion agent was also added into the slurry solution. The LiMn₂O₄ microparticles with a spherical nanostructure were finally prepared by a spray drying method from the slurry solution. The tap density of the LiMn₂O₄ microparticle prepared by a combination of spray pyrolysis and drying method was larger than that by a conventional spray pyrolysis method.The as-prepared samples were sintered at 750 °C for 1 h in air and used as cathode active materials for lithium batteries. Test experiments in the electrochemical cell Li|1 M LiClO₄ in EC:DEC = 1:1|LiMn₂O₄ demonstrate that the sample prepared by the present method is a promising cathode active material for 4 V lithium-ion batteries at high-charge-discharge and elevated temperature operation. The LiMn₂O₄ compounds by the combination of spray pyrolysis and drying method are superior to that by the conventional spray pyrolysis method in terms of electrochemical characteristics and tap density.     

Characterization of silver and silver/nickel composite particles prepared by spray pyrolysis

Pure silver and silver/nickel composite particles were prepared by spray pyrolysis of aqueous solutions of AgNO₃, and mixed salts of AgNO₃ and Ni(NO₃)₂·6H₂O, respectively. In the case of pure silver, reduction to metallic silver and subsequent sintering to highly spherical and dense particles took place immediately and almost simultaneously once favorable conditions for the former were imposed, irrespective of the nature of the carrier gas. For the composite particles, the high rates of reduction and sintering of the silver were still maintained, while crystallization of the silver, and the reduction and sintering of the nickel were considerably retarded, compared to the spray pyrolysis of each pure salt. Once the counterpart salt was added, the size of the composite particles increased compared to that of each pure metallic particles, but it was little affected by the furnace set temperature, the residence time and the molar ratio of the two precursor salts. Within single particles, an increase in either the temperature or the residence time caused segregation—silver in the shells and nickel in the cores—and improved the particles' surface smoothness and sphericity accordingly.     

Synthesis of ceria nanoparticles by flame electrospray pyrolysis

A flame electrospray pyrolysis is presented for synthesizing CeO₂ nanoparticles with a dense morphology, high crystallinity and nanometer size. Hydrated cerium nitrate precursor dissolved in an ethanol/diethylene glycol butyl ether mixture was injected into a CH₄/air premixed flame using an electrospray method. The number size distributions of the as-prepared particles were trimodal. It is suggested that the particles for the fine mode were formed by a Rayleigh disintegration of the charged precursor droplets during the droplet evaporation. The particles for the coarse and middle modes are surmised to come from primary and secondary droplets, respectively, which were formed simultaneously during the atomization processes. The CeO₂ nanoparticles for the coarse mode were nonspherical and composed of few crystallites. The nanoparticles for the fine and middle modes were nearly spherical and nonagglomerated. The as-prepared CeO₂ nanoparticles showed highly crystallinity.     

Design of carbon fiber reinforced boron nitride matrix composites by vacuum-assisted polyborazylene transfer molding and pyrolysis

In the present study, the vacuum-assisted polyborazylene transfer molding (VAPTM) followed by pyrolysis at 1450 °C under nitrogen was successfully applied to prepare C/BN composites with a relative density of 94.7%, and an open porosity of 5.1 vol%. Rheology measurements combined with TG experiments and measurement of the weight gain of the composites after each polymer impregnation pyrolysis (PIP) cycles allowed fixing elaboration parameters (10 PIP cycles using two types of polyborazylene) to generate C/BN composites as high temperature vacuum compatible materials which demonstrate potentialities for vacuum technology and space applications. Scanning electron micrographs of composites demonstrated that the BN matrix appropriately filled the space between the fibers with a low fiber-matrix bonding which affects the compressive modulus. The thermal diffusivity and electrical conductivity of the BN matrix have been measured and showed that carbon fibers have poor effects on the intrinsic properties of BN.     

Synthesis of nanocrystalline TaC powders via single-step high temperature spray pyrolysis from solution precursors

Nanocrystalline powders for high temperature ceramics (HTC) and ultrahigh temperature ceramics (UHTC) are important materials for aerospace and other important industrial applications. In this study, a low cost, single-step synthesis method for nanocrystalline HTC and UHTC powders is reported, which is based on high temperature spray pyrolysis (HTSP) process. The synthesis starts with solution of oxide and carbon precursors dissolved in common organic solvents, which are broken into fine droplets (e.g., via nebulizer). The droplets then go through processes of solvent removal, thermolysis, and rapid in situ carbothermal reduction (CTR), all in one single pass in a tube furnace operated at high temperature. The synthesis method was demonstrated successfully using the example of tantalum carbide (TaC) from precursors of tantalum chloride (TaCl₅) and phenolic resin in a single-step HTSP process with maximum temperature of 1650 °C in one pass that finished within minutes, yielding agglomerated nanocrystalline TaC UHTC powders.     

Test of vanadium pentoxide as anode for the electrooxidation of toluene: A theoretical approach of the electrode process

Vanadium pentoxide (V₂O₅) films were prepared by electrochemical and thermal decomposition of vanadyl sulphate on titanium dioxide covered titanium plates and glassy carbon discs. The prepared material by thermal decomposition showed high surface area and good physical stability; while the electrodeposited films, although being homogeneous, showed poor adhesion. The V₂O₅ electrodes were chemically and electrochemically stable in aqueous (1 M H₂SO₄ + 1 M NaOH, pH 3) and organic (0.1 M But₄NPF₆ + CH₃CN) solutions. In both cases, a well defined electrochemical response was observed. At the experimental conditions, the prepared materials were not active for the electrooxidation of toluene. The theoretical modeling suggests that the lack of activity is due to the weak interaction between toluene and the V₂O₅ surface.