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.     

PB/ITO-PET柔性电致变色薄膜制备及性能研究

柔性电致变色器件具有体积小、重量轻、可弯曲等优点,在可穿戴设备、曲面显示器、节能及自适应伪装等领域具有潜在应用前景。本工作以铁氰化钾、氯化钾、无水氯化铁为原料,采用电沉积方法在ITO-PET柔性基底上沉积普鲁士蓝(PB)制得PB/ITO-PET电致变色薄膜,并利用扫描电子显微镜、紫外光谱仪、电化学工作站对PB/ITO-PET电致变色薄膜微观结构和电化学性能进行分析表征。结果表明,电沉积时间为200 s时得到的PB/ITO-PET电致变色薄膜在700 nm波长处光吸收率达到0.755,且PB/ITO-PET电致变色薄膜可在较低电压(0.6 V/-0.3 V)下实现着色和褪色。其光调制范围为68%,着色/褪色响应时间分别为9 s/8 s,着色效率为108 cm2/C。PB/ITO-PET电致变色薄膜经1000次着色-褪色循环后光调制范围为68%,着色效率为100.3 cm2/C。PB/ITO-PET电致变色薄膜500次弯曲,着色效率为105.5 cm2/C,并经1000次着色-褪色循环后着色效率为91 cm2/C,光调制范围为65%。利用ITO-PET为离子存储层(对电极)、凝胶电解质和PB/ITO-PET为工作电极组装得到柔性电致变色器件,其光调制范围为53%,着色/褪色响应时间分别为13 s/18 s。     

石煤钒矿硫酸浸出制备五氧化二钒试验研究

石煤钒矿中的钒以铝氧化钒和氧化钒水合物赋存于矿石云母和黏土矿物中,并以低价态产出。将石煤钒矿破碎磨粉至粒度小于0.15 mm,在添加剂（含氧化剂和络合剂的无机盐混合物）和硫酸的协同作用下,在加热和搅拌条件下,用硫酸直接浸出石煤钒矿中的钒,矿粉中钒的浸出回收率可达76%以上。浸出液经调pH、氧化、分离富集、精钒制备等工序,可以制备出产品质量优于YB/T 5304-2011《五氧化二钒》98级标准的五氧化二钒产品。     

石煤钒矿提取五氧化二钒工艺研究与工业实践

将黑色岩系(石煤)钒矿粉碎后与复合添加剂混合,经转窑氧化焙烧、水淬浸取与湿法球磨分级、双重搅拌动态浸取与交换、饱和树脂清洗与解吸、解吸液除杂与沉钒、粗钒脱水与脱氨等工序,生产出高品质五氧化二钒。通过对上述各工序影响钒浸出率的因素进行综合试验与工业实践,总结出从黑色岩系(石煤)钒矿中提取五氧化二钒的新工艺。该工艺实现了石煤钒矿中钒的焙烧转化浸出率在80%以上,矿粉中钒的综合回收率大于70%,产品质量优于YB/T 5304-2006《五氧化二钒》98级的要求。     

Oxidative dehydrogenation of ethyl alcohol over vanadium pentoxide supported on magnesia

The catalytic dehydrogenation of ethyl alcohol on vanadium pentoxide supported on magnesia was studied in a flow system. The catalysts were characterised by DTA, X-ray, surface area and electrical conductivity measurements. The results revealed that the yield of acetaldehyde is strongly affected by the nature of compounds formed as a result of the interaction between MgO and V₂O₅. The Mg₃V₂O₈ formed at a calcination temperature of 550°C is the most active and selective catalyst. The activity of this spinel was correlated with the creation holes and the position of the Fermi potential. On the other hand, the catalyst calcined at 650°C was accompanied by the formation of an MgV₂O₆ spinel, which exhibited low activity and low selectivity.     

Quantum chemical SINDO1 study of vanadium pentoxide

An improved set of parameters for vanadium in the semiempirical quantum chemical SCF MO method SINDO1 is presented. It is shown that both the geometries and heats of formation of a number of vanadium-containing compounds calculated by this method are in good agreement with available experimental data. Model clusters of increasing size are used for the study of geometric and energetic properties of vanadium pentoxide. Both hydrogen atom and proton adsorption on the (010) surface of vanadium pentoxide and a subsequent formation of different oxygen vacancies have been investigated. Based on these computational results the reactivities of V₂O₅-surface oxygen atoms for adsorption are discussed.     

Synthesis of nanosized vanadium pentoxide/carbon composites by spray pyrolysis for electrochemical capacitor application

Nanostructured vanadium pentoxide/carbon (V₂O₅/carbon) composite powders with enhanced specific capacitance were synthesized by the spray pyrolysis technique. Electrochemical properties were examined by the cyclic voltammetry technique. Following analysis of powders sprayed at different temperatures, composite powders obtained at an optimum temperature of 450 °C yielded a maximum specific capacitance of 295 F g⁻¹ in 2 M KCl electrolyte at a 5-mV s⁻¹ scan rate. The weight percentage of carbon-related species was 2.7 wt% in this V₂O₅/carbon composite, as detected by thermogravimetric analysis (TGA) and confirmed by transmission electron microscope energy dispersive spectroscopy (TEM-EDS) analysis. Following initial X-ray diffraction (XRD) characterization, scanning electron microscope (SEM), TEM and high-resolution TEM (HRTEM) imaging revealed a specific morphology of spherical shell agglomerates of V₂O₅ nanorods and nanoribbons, with each shell comprising a network of these one- and two-dimensional nanoparticles in an amorphous carbon matrix. The V₂O₅ network was not fully dense, and the majority of the nanorod sizes were in the range of 50-150 nm, with additional long nanoribbons extending from the outsides of the spherical shells. The specific surface area was 18 m² g⁻¹ for the composite powders, and the pore size distribution revealed that the majority of pores had diameters in the range of 40-50 Å, which was relatively larger than the pore diameters obtained at 500 °C and would be beneficial for electrochemical performance. The enhancement of the specific capacitance in V₂O₅/carbon composites was attributed to the distribution of amorphous carbon throughout the V₂O₅ and the particular open nanostructure.     

用天然碱浸法从废钒催化剂中回收五氧化二钒的试验

用地下天然碱对硫酸生产废钒催化剂进行直接浸取,得到ρ（Ｐ２Ｏ５＿为１５～１６ｋｇ／ｍ＾３的含钒溶液;用高子交换法对浸出液进行净化处理,然后沉钒、脱氮,得到ｗ（Ｖ２Ｏ３）９９．５的产品,钒收率达到８５％。     

Mechanism of anodic oxidation of molybdenum in nearly-neutral electrolytes studied by electrochemical impedance spectroscopy and X-ray photoelectron spectroscopy

Anodic oxidation of molybdenum in weakly acidic, nearly neutral and weakly alkaline electrolytes was studied by voltammetric and electrochemical impedance spectroscopic measurements in a wide potential and pH range. Current vs. potential curves were found to exhibit two pseudo-Tafel regions suggesting two parallel pathways of the dissolution process. Electrochemical impedance spectra indicated the presence of at least two reaction intermediates. X-ray photoelectron spectroscopic (XPS) results pointed to the formation of an oxide containing Mo(IV), Mo(V) and Mo(VI), the exact ratio between different valence states depending on potential and pH of the solution. A physico-chemical model of the processes is proposed and a set of kinetic equations for the steady-state current vs. potential curve and the impedance response are derived. The model is found to reproduce quantitatively the current vs. potential curves and impedance spectra at a range of potentials and pH and to agree qualitatively with the XPS results. Subject to further improvement, the model could serve as a starting point for the optimization of the electrochemical fabrication of functional molybdenum oxide coatings.     

Corrosion behavior of electrodeposited Wo3 thin films

In this study, nanostructured tungsten trioxide (WO₃) thin films were deposited on Indium tin oxide (ITO)-coated glass substrate using electrochemical deposition (ECD). After deposition, the films were annealed at 450 °C for 2 h in an air atmosphere. X-ray diffraction (XRD) analysis confirmed that the prepared WO₃ thin films have crystalline phases. According to the absorption measurements, the optical bandgap of the WO₃ film was calculated as Eg 2.80 eV. Based on the scanning electron microscopy (SEM) images, the surface morphology of the thin films was influenced by deposition conditions. Raman spectroscopy analysis was also used to further examine the structure and chemical compositions of the thin films. The nature of the nanostructured WO₃ thin films was studied with Electrochemical Impedance Spectroscopy (EIS) and Tafel. Nyquist, open circuit potential and Bode analysis were used to evaluate structural changing and corrosion behavior of the prepared WO₃ thin films. With the help of these measurements and analyzes, the parameters such as solution resistance (Rs), polarization resistance (Rpo), a constant phase element (CPE) and a CPE exponent (n) were calculated as 43.43 Ω cm², 2.67 × 10⁶ Ω cm², 18.45 × 10⁻⁶ Ω⁻¹ s cm⁻², 0.958, respectively. Also, the corrosion features of the WO₃ thin films were investigated with the help of tafel measurements and the corrosion potential and current values were calculated as −0.583 V and 5.09 × 10⁻¹⁵ A, respectively. It is thought that the prepared thin film might have the potential to be used industrially with these features.     

Fe doping effect of vanadium oxide films for enhanced switching electrochromic performances

In the present study, Fe-doped V₂O₅ films showing impressive electrochromic (EC) performance were developed using the sol-gel spin-coating method. To confirm the optimized Fe-doping effect on the V₂O₅ films for the EC performance, we adjusted the Fe atomic percentages to 0.0, 0.5, 1.0, and 1.5?at%, respectively. With the effect of Fe doping on the V₂O₅ films, the obtained films resulted in the formation of the oxygen vacancies. As the result, when the optimum Fe atomic percentage was 1.0?at%, the enhanced switching speeds (3.7?s for the bleaching speed and 2.0?s for the coloration speed) and enhanced coloration efficiency value (47.3?cm²/C) compared to the other films were implemented. This can be attributed to the improved electrical conductivity and Li⁺ diffusion coefficient that led to efficient generation of the EC reaction activity and narrowing the optical bandgap at the coloration state to increase transmittance modulation. Therefore, this unique film can be a promising EC material to improve the performance for the EC devices.     

Fast electrochromic response and high coloration efficiency of Al-doped WO3 thin films for smart window applications

Herein, vertically aligned Al:WO₃ nanoplate arrays were directly grown on ITO glass by a facile electrodeposition method and annealed in an argon atmosphere at 450 °C for 2h. Besides, this study reports the influence of Al doping on the electrochromic properties of WO₃ film in detail. Electrochromic properties such as cyclic voltammetry, chronoamperometry and optical transmittance were analyzed by protonic insertion/extraction in the 1 M LiClO₄/propylene carbonate as an electrolyte. The noticeable reversible color changing from transparent to the blue can be realized under the potential bias of ±1.0 V. XRD studies show that the produces films have highly crystalline structure. The EDS results clearly confirm the incorporation of Al element into the WO₃ network. From the optical absorption measurement, direct band gap energies are calculated as 3.62 and 3.34 eV for the WO₃ and the Al:WO₃, respectively. Compared to the as-prepared WO₃, the Al:WO₃ film exhibits outstanding electrochromic performance, including wide optical modulation (55.9%), high coloration efficiency (148.1 cm²C^-1), quick reaction kinetics (1.23 s and 1.01 s for colored and bleaching times, respectively), good rate capability and cycle durability at a wavelength of 632.8 nm. EIS measurements based on a charge-transfer resistance reveal that the dramatic improvement in the electrochemically active surface is achieved in the Al:WO₃ film. The increase of active surface facilitates transport kinetics for electron and ion intercalation/deintercalation within the porous metal oxide to enhance coloration efficiency. Comparatively energy levels of the WO₃ and the Al:WO₃ electrochromic films are also represented. From the Mott-Schottky studies, it is estimated that the donor concentration of the films is of the order of 10²⁰ cm⁻³. Taken together, these results not only provide important insight into a promising electrode for electrochromic displays applications, but also offer an economic and effective strategy for manufacturing of other doped metal oxide films.     

掺钒二氧化钛的可见光催化性能研究

制备高活性可见光响应型掺钒TiO2光催化剂,以荧光灯为光源,光催化降解亚甲基蓝为模型反应,对可见光下TiO2的催化活性进行评价。研究了掺钒TiO2制备方法、掺钒量及氧化剂对光催化氧化的影响。结果表明,溶胶-凝胶法制备的TiO2催化活性较高,且工序简单,钒离子掺杂均匀;掺钒能使TiO2具有可见光响应,最佳掺钒量为1%;外加氧化剂H2O2能提高掺钒TiO2催化活性。     

Electrochemical behaviour of passive films on molybdenum-containing austenitic stainless steels in aqueous solutions

Passivation and its breakdown reactions have been studied on Mo-containing stainless steel specimens using different electrochemical techniques. Mo-containing stainless steel specimens were polarized in both naturally aerated NaCl and Na₂SO₄ solutions of different concentrations at 25 ± 0.2 °C between −1000 and 1500 mV versus saturated calomel electrode (SCE). The results of potentiodynamic polarization showed that i_corr and i_c increases with increasing either Cl⁻ or SO₄²⁻ concentration indicating the decrease in passivity of the formed film. EIS measurements under open circuit conditions confirmed that the passivity of the film decrease with increase in either Cl⁻ or SO₄²⁻ concentration.     

Electrochemical corrosion performance in 3.5% NaCl of the electrodeposited nanocrystalline Ni films with and without dispersions of Cr nanoparticles

Nanocrystalline (nc) Ni films with and without dispersions of Cr nanoparticles were electrodeposited from a nickel sulfate bath. The grain size of the nc-Ni films was reduced with increasing in the co-deposition content of Cr nanoparticles. Potentiodynamic polarization tests showed that increasing in the co-deposition content resulted in an enlarged passive region of the nc-Ni in 3.5% NaCl through reducing the corrosion potential and increasing the breakdown potential. Scanning electron microscopy (SEM) observation indicated that the polarized pure nc-Ni film exhibited numerous large and deep pits. However, they became smaller and shallower when 4.5 wt.% Cr nanoparticles were co-deposited, and almost disappeared when 10.9 wt.% Cr were co-deposited. X-ray photoelectron spectroscopy (XPS) analysis showed that the different electrochemical corrosion performance was associated with the ability of the Cr nanoparticles co-deposited nc-Ni film to form a continuous Cr-oxide passive film.     

Commercial polymer films as calibration standards for EIS measurements

The current protocol regarding calibration and troubleshooting of potentiostats used to conduct electrochemical impedance spectroscopy (EIS) measurements on coated metals involves dummy cells made of simple electrical components. This concept has two major limitations: first, the instrument is used at an impedance range it has not been calibrated for—the instrument is calibrated for impedances in the order of ohms, but corrosion protective coatings usually have impedance values in the range of GΩ cm² or higher; second, commercial coating systems do rarely behave like ideal equivalent circuits of electronic components. In view of these limitations, we propose the use of thin polymer films such as PVF or poly ethylene terephthalate (PET) as new calibration standards for EIS measurements. These films are well defined in thickness and composition and give a highly reproducible response when subjected to EIS measurements. In addition, they closely mimic commercial coating systems with regard to target impedance range and electrical characteristics.     

Design and fabrication of MoSe2/WO3 thin films for the construction of electrochromic devices on indium tin oxide based glass and flexible substrates

Electrochromic devices (ECDs) have the ability to block the heat generated by sunlight, making them ideal for use in smart windows. Herein, we report the fabrication of ECDs using MoSe₂/WO₃ (MSW) as the electrochromic material, for smart windows applications. A solvothermal method was used for the synthesis of MoSe₂, while WO₃ was synthesized using a sol-gel approach. Subsequently, MoSe₂/WO₃ (MSW) hybrids with different wt% of MoSe₂ (0.05 wt%, 0.2 wt%, 0.5 wt%) were synthesized using an ultra-sonication approach. The physicochemical features of these MSW hybrids herein termed as MSW 0.05, MSW 0.2 and MSW 0.5, were investigated using X-ray diffraction (XRD), X-ray photon electron spectroscopic (XPS), scanning electron microscope (SEM), and EDS techniques and compared with pristine MoSe₂ and WO₃. The ECDs synthesized using MSW 0.05 showed increased coloration efficiency (62 cm^2 C-1) with an applied potential range of 0 to −1.5 V. Subsequently, the ECDs based on indium tin oxide (ITO) and MSW 0.05 demonstrated excellent electrochromic performance and stability for 10,000 cycles. The enhanced electrochromic performance of the MSW-based ECDs may be attributed to the conductive nature as well as the synergistic effects between MoSe₂ and WO₃ when compared to the WO₃-based ECDs. The synthesized MSW also showed promise as an electrochromic material in flexible ECDs for smart windows applications.     

The influence of vanadium pentoxide on the structure and dielectric properties of poly(vinyl alcohol)

Polymers containing metal oxides of nanoscale dimensions have attracted attention because of their unique properties and new findings concerning technological applications. Polymers containing vanadium pentoxide (V₂O₅) have attracted our interest in respect of their potential applications in memory and switching devices. Poly(vinyl alcohol) (PVA) containing different concentrations of V₂O₅ ranging from 0 to 0.5 wt% were prepared. The synthesized PVA/V₂O₅ composites were cast as self‐standing flexible films. The composites were characterized using X‐ray diffraction (XRD) and Fourier transform infrared (FTIR) spectroscopy. An attempt was made to study the relaxation characteristics of PVA/V₂O₅ samples. The permittivity and dielectric loss were determined as a function of V₂O₅ concentration. The results show that the optimum concentration is 0.3 wt%. The electrical conductivity and dielectric modulus in the temperature range 303–433 K at various frequencies (10–100 kHz) for the optimum concentration were investigated. XRD and FTIR results show that the addition of V₂O₅ reduces the crystallinity of PVA due to the interaction of vanadium ions with the OH groups of PVA. The application of the dielectric modulus formulism gives a simple method for evaluating the activation energy of the dielectric relaxation. The frequency dependence of the electrical conductivity follows the Jonscher universal dynamic law. The conductivity in the direct regime is described by the small polaron model. The electrical conductivity and dielectric properties show that Hunt's model is well adapted to PVA/V₂O₅ films. Copyright © 2010 Society of Chemical Industry     

Redox behavior and optical response of nanostructured poly(3,4-ethylenedioxythiophene) films grown in a camphorsulfonic acid based micellar solution

Poly(3,4-ethylenedioxythiophene) (PEDOT) films have been electropolymerized from an aqueous micellar solution comprising camphorsulfonic acid (CSA), lithium trifluoromethanesulfonate (LiCF₃SO₃) and EDOT. The inclusion of the dopants CS⁻ and CF₃SO₃⁻ in the polymer structure and an unusually high doping level of 0.54 have been ascertained by the X-ray photoelectron spectroscopy. Transmission electron microscopy and atomic force microscopy studies show that the micellar effect of CSA leads to a morphology wherein polymer particles link together to form elongated shapes and also endows the film with a surface roughness of 25-30 nm. These nanostructures permit a facile intercalation-deintercalation of anions in the film during redox cycling. Electrochemical impedance spectroscopy show that the charge transfer phenomenon at the PEDOT-electrolyte interface is dominant in the high frequency region and diffusion controlled ionic movement prevails in the low frequency regime. The use of these films as potential cathodes in electrochromic windows is rationalized not only on the basis of their high scalability and ease of processing but also due to their large coloration efficiency (123 cm² C⁻¹) and transmission modulation (50%) at a photopic wavelength of 550 nm. But further improvement in color-bleach kinetics and reproducibility of redox behavior is desirable to broaden their spectrum of utility.     

The effect of nanoscale vanadium pentoxide on the electrical and mechanical properties of poly(vinyl alcohol)

Poly(vinyl alcohol) (PVA) loaded with vanadium pentoxide (V₂O₅) nanoparticles was successfully prepared at room temperature and ambient pressure. Transmission electron microscopy was used to characterize the final product. It was found that V₂O₅ nanoparticles were well dispersed and uniform in shape and that the diameter of the particles was confined to within 8 nm. Addition of small amounts (0.2–1 wt%) of nanoparticulate V₂O₅ to PVA increased the electrical conductivity as well as the modulus of elasticity. The deformation behaviour after preparing the nanocomposites, irrespective of V₂O₅ concentration, is similar to that of the unfilled elastomer, implying that the mechanism of large deformation is mainly governed by the matrix. Copyright © 2007 Society of Chemical Industry