Electrodeposition of mesoporous V2O5 with enhanced lithium-ion intercalation property

Mesoporous vanadium oxide (V₂O₅) thin films were deposited electrochemically onto indium tin oxide-coated glass substrates from an aqueous solution of vanadyl sulfate using CTAB (hexadecyltrimethylammonium bromide) as a templating agent. For comparison, a control sample was electrodeposited without CTAB templating. Transmission electron microscopy and small angle X-ray diffraction indicated the presence of mesoporosity with a well-ordered lamellar phase in the electrodeposited films. The crystallinity of the V₂O₅ thin films was confirmed by X-ray diffraction. Cyclicvoltammetry and chronoamperometry were used to measure electrochemical properties of synthesized films. The mesoporous films prepared with CTAB templating had a much higher capacity and lithium-ion diffusion rate than the non-porous electrode prepared without CTAB templating.     

High‐performance Flexible Complementary Electrochromic Device Based on Plasma Modified WO3 Nano Hybrids and V2O5 Nanofilm with Low Operation Voltages

Tungsten trioxide‐poly(3,4‐ethylenedioxythiophene) (WO₃‐PEDOT) and tungsten trioxide‐polyfuran (WO₃‐PFu) were prepared by rf rotating plasma polymerization. Electrochromic hybrid thin films were fabricated onto flexible polyethylene terephthalate (PET)/ indium tin oxide (ITO) film using electron beam evaporation method. In order to deeply characterize all films, scanning electron microscopy‐energy dispersive X‐ray spectroscopy (SEM‐EDS) and electrochemical impedance spectroscopy (EIS) techniques were used. The counter electrode effect on plasma modified WO₃ nano hybrids‐based electrochromic devices (ECDs) was evaluated. By incorporating flexible vanadium pentoxide (V₂O₅) film as counter electrode, complementary ECDs were constructed through combining the hybrid flexible films (WO₃‐PEDOT, WO₃‐PFu) as working electrodes, which exhibit highly efficient electrochromic performance with low voltage operation. Especially, WO₃‐PEDOT/V₂O₅‐based ECD owns a high optical modulation of 61.5 % at 750 nm driven by −1.0 V (coloration) and +1 V (bleaching) with fast response times (coloration time: 13.58 s, bleaching time: 8.07 s) and a high coloration efficiency of 527 cm² C⁻¹. This study can supply useful and efficient avenue for designing flexible complementary electrochromic device for energy‐saving flexible electronics.     

Synthesis of self-assembled nanorod vanadium oxide bundles by sonochemical treatment

Self-assembled nanorod of vanadium oxide bundles were synthesized by treating bulk V₂O₅ with high intensity sonochemical technique. The synthesized materials were characterized by X-ray diffraction (XRD), scanning electron microscope (SEM), transmission electron microscope (TEM) and temperature-programmed reduction (TPR) in H₂. Catalytic behaviour of the materials over anaerobic n-butane oxidation was studied through temperature-programmed reaction (TPRn). Catalytic evaluation of the sonochemical treated V₂O₅ products was also studied on microreactor. XRD patterns of all the vanadium samples were perfectly indexed to V₂O₅. The morphologies of the nanorod vanadium oxides as shown in SEM and TEM depended on the duration of the ultrasound irradiation. Prolonging the ultrasound irradiation duration resulted in materials with uniform, well defined shapes and surface structures and smaller size of nanorod vanadium oxide bundles. H₂-TPR profiles showed that larger amount of oxygen species were removed from the nanorod V₂O₅ compared to the bulk. Furthermore, the nanorod vanadium oxide bundles, which were produced after 90, 120 and 180 min of sonochemical treatment, showed an additional reduction peak at lower temperature (850 K), suggesting the presence of some highly active oxygen species. TPRn in n-butane/He over these materials showed that the nanorod V₂O₅ with highly active oxygen species showed markedly higher activity than the bulk material, which was further proven by catalytic oxidation of n-butane.     

High-efficiency ozone generation via electrochemical oxidation of water using Ti anode coated with Ni–Sb–SnO<Subscript>2</Subscript>

Ozone (O₃) has been generated on Ni–Sb–SnO₂/Ti electrode as anode immersed in acidic media at 25 °C by electrochemical process. The anode was electrochemically characterized by cyclic voltammetry and morphologically characterized by scanning electron microscopy (SEM) and X-ray diffraction. The concentration of dissolved ozone was determined by a UV/Vis spectrophotometer. The type of electrode with different times coating on the titanium mesh and different acid type and various concentrations (C _acid) were used, and the stability of the electrode was investigated under the experimental conditions by SEM images. Results shows that higher efficiency (53.7%) for O₃ generation by electrochemical oxidation of water were obtained in HClO₄ (1 M) and an applied potential of 2.4 V vs. Ag/AgCl in 150 ml volume undivided electrochemical cell.     

Thin films of vanadium oxide grown on vanadium metal: oxidation conditions to produce V2O5 films for Li‐intercalation applications and characterisation by XPS,AFM, RBS/NRA

Thin films of vanadium oxide were grown on vanadium metal surfaces (i) in air at ambient conditions, (ii) in 5 mM H₂SO₄ (aq), pH 3, (iii) by thermal oxidation at low oxygen pressure (10^?5 mbar) at temperatures between 350 and 550 °C and (iv) at near‐atmospheric oxygen pressure (750 mbar) at 500 °C. The oxide films were investigated by atomic force microscopy (AFM), X‐ray photoelectron spectroscopy (XPS), X‐Ray diffraction (XRD) and Rutherford backscattering spectrometry (RBS) and nuclear reaction analysis (NRA). The lithium intercalation properties were studied by cyclic voltammetry (CV). The results show that the oxide films formed in air at room temperature (RT), in acidic aqueous solution, and at low oxygen pressure at elevated temperatures are composed of V₂O₃. In air and in aqueous solution at RT, the oxide films are ultra‐thin and hydroxylated. At 500 °C, nearly atmospheric oxygen pressure is required to form crystalline V₂O₅ films. The oxide films grown at pO₂ = 750 mbar for 5 min are about 260‐nm thick, and consist of a 115‐nm outer layer of crystalline V₂O₅. The inner oxide is mainly composed of VO₂. For all high temperature oxidations, the oxygen diffusion from the oxide film into the metal matrix was considerable. The oxygen saturation of the metal at 450 °C was found, by XPS, to be 27 at.% at the oxide/metal interface. The well‐crystallized V₂O₅ film, formed by oxidation for 5 min at 500 °C and 750 mbar O₂, was shown to have good lithium intercalation properties and is a promising candidate as electrode material in lithium batteries. Copyright © 2005 John Wiley & Sons, Ltd.     

UV-Visible and IR Spectroelectrochemical Properties of V2O5 Crystalline Films Charged/Discharged in Extended Potential Range

Electrochemical properties of amorphous and crystalline V₂O₅ films, dip-coated from V-oxoisopropoxide sols and thermally treated at various temperatures (100, 150, 200 and 300°C), have been studied in extended potential range, i.e. from 1.4 to –1.6 V vs. Ag/AgCl in 1M LiClO₄/propylen carbonate (PC) electrolyte. The formation of various lithiated (-, -, - and -Li _x V₂O₅) phases was correlated with the values of insertion coefficient x obtained from cyclic voltammograms (CV) of crystalline V₂O₅ films (300°C). Reversible charging was observed when films were cycled up to –1.0 V vs. Ag/AgCl, while the extension of the potential to –1.3 V vs. Ag/AgCl change the CV of films irreversibly. Charging of crystalline V₂O₅ films was followed by the help of in-situ UV-visible spectroscopy, that revealed the intensity variations of the polaron absorption above 600 nm and the presence of the absorbing V³⁺ species between 550 and 650 nm. Ex-situ IR spectra of the crystalline films charged/discharged at –1.6V/1.4V vs. Ag/AgCl confirmed the amorphisation of the films' structure.     

Characterization of thin metastable vanadium oxide films by Raman spectroscopy

Thin films are potentiodynamically generated on vanadium in Ba²⁺/acetate electrolyte systems at high voltages. The influence of the anodic potential up to 400 V on the composition and structure of the about 500 nm thin anodic conversion films are investigated. Raman spectroscopy indicates that different film types depend on the electrochemical process parameters. The relationship between the Raman laser excitation power and the amorphous or microcrystalline film structure is also discussed. Beside metastable disordered structures the films contain crystalline phases of V₂O₅, V₄O₉ and barium vanadate, respectively.     

Preparation and characterization of silver and indium vanadate co-doped TiO2 thin films as visible-light-activated photocatalyst

Novel visible-light-activated photocatalytic Ag/InVO₄-TiO₂ thin films were developed in this paper through a sol-gel method from the TiO₂ sol containing Ag and InVO₄. The photocatalytic activities of Ag/InVO₄-TiO₂ thin films were investigated based on the oxidation decomposition of methyl orange in aqueous solution. The Ag/InVO₄-TiO₂ thin films were characterized by X-Ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), X-ray photoelectron spectroscopy (XPS) and UV-vis absorption spectroscopy (UV-vis). The results revealed that the Ag/InVO₄-TiO₂ thin films extended the light absorption spectrum toward the visible region; the Ag and InVO₄ co-doped thin films significantly enhanced the methyl orange photodegradation under visible light irradiation. It has been confirmed that the Ag/InVO₄-TiO₂ thin films could be excited by visible light (E < 3.2 eV). The significant enhancement in the Ag/InVO₄-TiO₂ photo activity under visible light irradiation can be ascribed to the simultaneous effects of doped noble metal Ag by acting as electron traps and InVO₄ as narrow band gap sensitizer.     

W18O49 nanorods decorated with Ag/AgCl nanoparticles as highly-sensitive gas-sensing material and visible-light-driven photocatalyst

A novel gas-sensing material and photocatalyst was successfully obtained by decorating Ag/AgCl nanoparticles on the W₁₈O₄₉ nanorods through a clean photochemical route. The as-prepared samples were characterized using combined techniques of X-ray diffractometry, electron microscopy, energy dispersive X-ray spectrometry, and X-ray photoelectron spectroscopy. Gas-sensing measurements indicate that the Ag/AgCl/W₁₈O₄₉ NRs sensors exhibit superior reducing gas-sensing properties to those of bare W₁₈O₄₉ NRs, and they are highly selective and sensitive to NH₃, acetone, and H₂S with short response and recovery times. The Ag/AgCl/W₁₈O₄₉ NRs photocatlysts also possess higher photocatalytic performance than bare W₁₈O₄₉ NRs for degradation of methyl orange under simulated sunlight irradiation. Possible mechanisms concerning the enhancement of gas-sensing and photocatalytic activities of the Ag/AgCl/W₁₈O₄₉ NRs composite were proposed.     

Plasma Modified V2O5/PEDOT Hybrid Based Flexible Electrochromic Devices

Vanadium oxide/poly (3,4‐ ethylenedioxythiophene)(V₂O₅‐PEDOT) hybrid materials were prepared in a rotating quartz plasma reactor via capacitively coupled radio frequency (RF 13.56 MHz) plasma. Thin films of V₂O₅‐PEDOT hybrid and V₂O₅ were obtained by electron beam evaporation technique onto flexible PET substrate for electrochromic devices (ECDs) applications. As a counter electrode, both RF magnetron sputtered MoO₃ onto ITO coated PET and only ITO coated PET electrodes were used. Characterizations of the films were carried out via using scanning electron microscopy‐energy dispersive X‐ray spectroscopy (SEM‐EDX) and X‐ray diffraction (XRD). Hybrid ECDs results showed that synergistic effect depending on improved stability between V₂O₅ and PEDOT. As a result, we developed all solid complementary electrochromic devices including V₂O₅, V₂O₅‐PEDOT and MoO₃ films. The electrochromic device characteristics such as electrochromic contrast, coloration efficiency, switching time were calculated from optical and electrochemical measurements. The highest coloration efficiency and optical contrast were obtained as 53 cm²/C and 17 % for V₂O₅‐PEDOT/MoO₃‐based ECD.     

XPS study of the Li intercalation process in sol–gel‐produced V2O5 thin film: influence of substrate and film synthesis modification

We report on the process of lithium intercalation in V₂O₅ thin films deposited onto standard ITO‐coated glass substrates. The films were deposited via a well‐established sol–gel route, and the samples were examined as working electrodes in a range of potentials versus lithium reference electrode. This paper follows up issues arising from parallel spectroscopic characterizations of the films by X‐ray photoelectron spectroscopy (XPS). Specifically, the XPS examination showed that not all of the Li‐ion charge inserted was accounted for by the V(5) to V(4) reduction, but the stoichiometric balance could be maintained only by considering additional oxygens arising from the intercalation procedure, leading to Li₂O formation. In this work, we have examined the possibility that the source of oxygen is the ITO substrate. To this purpose, films of V₂O₅ deposited on silicon substrates have been prepared using the sol–gel process and examined by XPS after electrochemical intercalation/de‐intercalation cycles. We show that in this case a perfect balance between electrochemical charge, inserted Li and reduced vanadium is obtained. A further indication of ITO‐substrate effects was obtained from examination, by the same methods, of some unconventional V₂O₅ films that had been co‐precipitated with a siloxane, designed to provide a template structure. The results obtained from this material imply that a barrier layer is formed at the ITO interface and, therefore, the formation of Li₂O is avoided. The results are discussed in terms of the possible degradation of conventional V₂O₅ on ITO as a result of electrochemically induced interface reactions. Copyright © 2005 John Wiley & Sons, Ltd.     

Characterization of transition metal nitride formation in rapid thermal processing (RTP)

The potential of RTP for the preparation of transition metal nitrides by reaction of metal thin films in molecular nitrogen was investigated. The films and the nitridation process were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), energy dispersive x-ray analysis (EDX) in a scanning electron microscope (SEM) and secondary neutral mass spectrometry (SNMS). The chemical states of vanadium at the utmost surface, detected by XPS, are related to V₂O₅ before RTP and to vanadium nitride, oxide and oxynitride after RTP. The deposition of a 3 nm Si top layer prevents V from oxidation and its selective removal before RTP enhances the proportion of nitride determined by XPS after RTP. From comparative experiments in a conventional tube furnace the advantages of RTP became obvious. With short process times of the RTP technique the integral amount of residual oxygen is kept low and oxide formation is largely avoided. The nitrogen content and the different polycrystalline phases formed by varying process time and temperature provide information about reactivity and the nitridation process. The nitrogen to vanadium ratio was determined by EDX and SNMS, revealing that the N content reaches saturation after only 5 seconds at 1100?°C.     

Characterization of thin metastable vanadium oxide films by Raman spectroscopy

Thin films are potentiodynamically generated on vanadium in Ba²⁺/acetate electrolyte systems at high voltages. The influence of the anodic potential up to 400 V on the composition and structure of the about 500 nm thin anodic conversion films are investigated. Raman spectroscopy indicates that different film types depend on the electrochemical process parameters. The relationship between the Raman laser excitation power and the amorphous or microcrystalline film structure is also discussed. Beside metastable disordered structures the films contain crystalline phases of V₂O₅, V₄O₉ and barium vanadate, respectively. Received: 15 July 1997 / Revised: 16 February 1998 / Accepted: 21 February 1998     

Fe_2O_3-Modified Hydrogen Storage Alloys as Electrocatalyst for Borohydride Oxidation

The effects of hot alkaline treatment and Fe₂O₃ modification of hydrogen storage alloy on the electrocatalytic activity for oxidation of borohydride have been investigated using linear sweep voltammetry. The performance of borohydride electrochemical oxidation was significantly influenced by the hot alkaline treatment and Fe₂O₃ modification of the hydrogen storage alloy. The results showed that the current density of the Fe₂O₃‐modified hot alkaline‐treated hydrogen storage alloy electrode containing 5 wt% Fe₂O₃ reached 125 mA·cm^?2 in 0.10 mol·L^?1 NaBH₄ and 2 mol·L^?1 NaOH solution at ?0.55 V vs. saturated Ag/AgCl, KCl electrode.     

掺杂钒和硅对TiO2薄膜超亲水性的影响

0引言 TiO2薄膜是众多氧化物半导体薄膜中研究最为广泛的一种材料．其表面的超亲水性和表面自清洁效应开辟了光催化薄膜功能材料的新的研究领域，已成为众多研究者研究的对象。但是如果薄膜仅由TiO2组成，当光照停止，水在TiO2薄膜表面的润湿角逐渐升高．并恢复原始状态。TiO2的禁带较宽，普通光线如太阳光等都不能将其激发．限制了其实际应用。因此如何使TiO2材料的光谱响应范围由紫外光反扩展到可见．光区一日如何更长时间地保持薄膜良好的亲水性是目前研究的重点。     

X-ray and Raman study of spray pyrolysed vanadium oxide thin films

Vanadium oxide thin films were prepared by spray pyrolysis using solutions of vanadium chloride (VCl₃) with different concentrations on glass substrates heated at 200 and 250 °C. The influence of substrate temperature (T_s) and solution concentration (molarity) on structural and vibrational properties is discussed by using X-ray diffraction and Raman spectroscopy. The results revealed that at 0.05 M and T_s = 200 °C, V₄O₉ thin films are obtained. At 250 °C, V₂O₅ phases with preferential orientation are observed and the films become polycrystalline when the molarity increases.     

Preparation and properties of VO2 thin films by a novel sol–gel process

Vanadium dioxide (VO₂) thin films were fabricated using a simple and novel sol–gel process in which V₂O₅ was used as the vanadium source; oxalic acid was used as the reducing agent; and polyvinyl alcohol was used as the film former to control the viscosity of the VO₂ precursor solution and bond vanadium ions. The microstructure and surface morphology of VO₂ films were studied by X-ray diffraction and scanning electron microscopy, respectively. The results showed that using polyvinyl alcohol forms porous nanostructure of VO₂ films with a uniform grain size of ~25 nm. The measured optical reflectance shows well-defined phase transition as observed by an increase of reflectance upon heating above the transition temperature from ~11 to ~30 % at 1,100 nm. Upon cooling, the expected hysteresis is observed.     

Poly(3,4-ethylenedioxythiophene)V2O5 hybrids for lithium batteries

A series of hybrid electrode materials, poly(3,4-ethylenedioxythiophene)/V₂O₅, has been synthesized using an oxidative insertion and polymerization reaction. FTIR, X-ray diffraction and transmission electron microscopy studies have shown that the incorporation of polymer between V₂O₅ slabs leads to an enhanced bidimensionality. The electrochemical lithium capacity has been increased up to ∼330 mAh/g at the second discharge in the range of 2.0–4.4 V vs. Li. This improvement of electrochemical performance compared to pristine V₂O₅ is attributed to the higher electric conductivity and enhanced bidimensionality.     

Improvement in stability of LiMn2O4 thin-film electrodes by oxygen-plasma irradiation to precursor gel

LiMn₂O₄ thin-film electrodes were prepared by the sol?Cgel method combined with oxygen-plasma irradiation. Oxygen plasma with a power of 10 or 90?W was irradiated to the precursor thin film prepared from lithium acetate, manganese acetate tetrahydrate and polyvinylpyrrolidone on a Pt plate, and then it was fired at 723 or 973?K. X-ray diffraction and Raman measurements indicated that oxygen-plasma irradiation was effective to increase the crystallinity of the resulting LiMn₂O₄. Atomic force microscope observation showed that the particle size of LiMn₂O₄ in the resulting thin-film electrode was decreased and homogeneous distribution of LiMn₂O₄ particles was achieved. Oxidation of the electrolyte at higher potentials was suppressed and capacity retention at 328?K was dramatically improved for the LiMn₂O₄ thin-film electrode obtained at 973?K. The improved electrochemical stability is ascribed to the elimination of organic materials from precursor by oxygen-plasma irradiation.     

V2O5 xerogel-poly(ethylene oxide) hybrid material: Synthesis, characterization, and electrochemical properties

In this work, we report the synthesis, characterization, and electrochemical properties of vanadium pentoxide xerogel-poly(ethylene oxide) (PEO) hybrid materials obtained by varying the average molecular weight of the organic component as well as the components’ ratios. The materials were characterized by X-ray diffraction, ultraviolet/visible and infrared spectroscopies, thermogravimetric analysis, scanning electron microscopy, electron paramagnetic resonance, and cyclic voltammetry. Despite the presence of broad and low intensity peaks, the X-ray diffractograms indicate that the lamellar structure of the vanadium pentoxide xerogel is preserved, with increase in the interplanar spacing, giving evidence of a low-crystalline structure. We found that the electrochemical behaviour of the hybrid materials is quite similar to that found for the V₂O₅ xerogel alone, and we verified that PEO leads to stabilization and reproducibility of the Li⁺ electrochemical insertion/de-insertion into the V₂O₅ xerogel structure, which makes these materials potential components of lithium ion batteries.