Revealing the role of calcium ion intercalation of hydrated vanadium oxides for aqueous zinc-ion batteries

Exploring suitable high-capacity V_(2)O_(5)-based cathode materials is essential for the rapid advancement of aqueous zinc ion batteries(ZIBs).However,the typical problem of slow Zn^(2+)diffusion kinetics has severely limited the feasibility of such materials.In this work,unique hydrated vanadates(CaVO,BaVO)were obtained by intercalation of Ca^(2+)or Ba^(2+)into hydrated vanadium pentoxide.In the CaVO//Zn and BaVO//Zn batteries systems,the former delivered up to a 489.8 mAh g^(-1)discharge specific capacity at 0.1 A g^(-1).Moreover,the remarkable energy density of 370.07 Wh kg^(-1)and favorable cycling stability yard outperform BaVO,pure V_(2)O_(5),and many reported cathodes of similar ionic intercalation compounds.In addition,pseudocapacitance analysis,galvanostatic intermittent titration(GITT)tests,and Trasatti analysis revealed the high capacitance contribution and Zn^(2+)diffusion coefficient of CaVO,while an in-depth investigation based on EIS elucidated the reasons for the better electrochemical performance of CaVO.Notably,ex-situ XRD,XPS,and TEM tests further demonstrated the Zn^(2+)insertion/extraction and Zn-storage mechanism that occurred during the cycle in the CaVO//Zn battery system.This work provides new insights into the intercalation of similar divalent cations in vanadium oxides and offers new solutions for designing cathodes for high-capacity aqueous ZIBs.

Synergism of preintercalated manganese ions and lattice water in vanadium oxide cathodes for high-capacity and long-life Zn-ion batteries

Aqueous Zn-ion batteries(AZIBs)are recognized as a promising energy storage system with intrinsic safety and low cost,but its applications still rely on the design of high-capacity and stable-cycling cathode materials.In this work,we present an intercalation mechanism-based cathode materials for AZIB,i.e.the vanadium oxide with pre-intercalated manganese ions and lattice water(noted as MVOH).The synergistic effect between Mn^(2+)and lattice H_(2)O not only expands the interlayer spacing,but also significantly enhances the structural stability.Systematic in-situ and ex-situ characterizations clarify the Zn^(2+)/H^(+)co–(de)intercalation mechanism of MVOH in aqueous electrolyte.The demonstrated remarkable structure stability,excellent kinetic behaviors and ion-storage mechanism together enable the MVOH to demonstrate satisfactory specific capacity of 450 mA h g^(−1)at 0.2 A g^(−1),excellent rate performance of 288.8 mA h g^(−1)at 10 A g^(−1)and long cycle life over 20,000 cycles at 5 A g^(−1).This work provides a practical cathode material,and contributes to the understanding of the ion-intercalation mechanism and structural evolution of the vanadium-based cathode for AZIBs.

Vanadium oxide nanospheres encapsulated in N-doped carbon nanofibers with morphology and defect dual-engineering toward advanced aqueous zinc-ion batteries

Vanadium-based electrodes are regarded as attractive cathode materials in aqueous zinc ion batteries(ZIBs)caused by their high capacity and unique layered structure.However,it is extremely challenging to acquire high electrochemical performance owing to the limited electronic conductivity,sluggish ion kinetics,and severe volume expansion during the insertion/extraction process of Zn^(2+).Herein,a series of V_(2)O_(3)nanospheres embedded N-doped carbon nanofiber structures with various V_(2)O_(3)spherical morphologies(solid,core-shell,hollow)have been designed for the first time by an electrospinning technique followed thermal treatments.The N-doped carbon nanofibers not only improve the electrical conductivity and the structural stability,but also provides encapsulating shells to prevent the vanadium dissolution and aggregation of V_(2)O_(3)particles.Furthermore,the varied morphological structures of V_(2)O_(3)with abundant oxygen vacancies can alleviate the volume change and increase the Zn^(2+)pathway.Besides,the phase transition between V_(2)O_(3)and Zn_XV_(2)O_(5-m)·n H_(2)O in the cycling was also certified.As a result,the as-obtained composite delivers excellent long-term cycle stability and enhanced rate performance for coin cells,which is also confirmed through density functional theory(DFT)calculations.Even assembled into flexible ZIBs,the sample still exhibits superior electrochemical performance,which may afford new design concept for flexible cathode materials of ZIBs.

Removal of tungsten and vanadium from molybdate solutions using ion exchange resin

The removal of tungsten(W)and vanadium(V)from molybdate solutions was studied using the poly hydroxyl chelating resin D403in batch and column experiments.The batch experiments indicated that tungsten and vanadium could be preferentially adsorbed by the D403resin for4h in molybdate solution at a pH of approximately9.25.Separation factors,αVMo andαWMo,wereabove45and18,respectively,when the molar ratios of Mo/V and Mo/W in the solution exceeded40.Elution tests illustrated that vanadium and tungsten could be easily eluted from the resin with1mol/L sodium hydroxide solution in only1h.To further explore the sorption mechanism of the resin,the experimental equilibrium isotherm data of the three metals fitted well with the Freundlich model.The column experiments confirmed the adaptability of the D403resin in the production of sodium molybdate with a removal rate of tungsten surpassing90%and that of vanadium of99.4%.

Infrared transition properties of vanadium dioxide thin films across semiconductor-metal transition

Vanadium dioxide thin films were fabricated through annealing vanadium oxide thin films deposited by dual ion beam sputtering. X-ray diffraction （XRD）, atom force microscopy （AFM）, and Fourier transform infrared spectrum （FTIR） were employed to measure the crystalline structure, surface morphology, and infrared optical transmittance. The phase transition properties were characterized by transmittance. The results show that the annealed vanadium oxide thin film is composed of monoclinic VO2, with preferred orientation of （011）. The maximum of transmittance change is beyond 65% as the temperature increases from 20 to 80 C. The reversible changes in optical transmittance against temperature were observed. The change rate of transmittance at short wavelength is higher than that at long wavelength at the same temperature across semiconductor-metal phase transition. This phenomenon was discussed using diffraction effect.

Concentration and separation of vanadium from alkaline media by strong alkaline anion-exchange resin 717

With strong alkaline anion-exchange resin 717 as the sorbent and NaOH solution as the eluent, a study on the sorption from alkaline solution and elution of vanadium（V）, silicon（iv）, and aluminium（III） was carried out. Different parameters affecting the sorption and elution process, including temperature, pH values as well as the ratio of resin to solution, were investigated. The results show that sorption degree of vanadium（V） increases with a decrease ofpH values, and V（V） ions are easier sorbed than Si（IV） and AI（III） ions under the same conditions. The sorption degree ofV（V）, Si（IV）, and AI（III） at pH 9.14 for 15 man are 90.6%, 33.5%, and 21.6%, respectively. Si（IV）, AI（III）, and V（V） ions sorbed on 717 resin were eluted by use of 2 mol·L^-1 NaOH solution; the desorption degree ofV（V）, Si（IV）, and AI（III） for 5 min are 81.7 %, 99.1%, and 99.3%, respectively.

Water molecules and oxygen-vacancy modulation of vanadium pentoxide with fast kinetics toward ultrahigh power density and durable flexible all-solid-state zinc ion battery

Aqueous zinc ion battery(ZIB)with many virtues such as high safety,cost-effective,and good environmental compatibility is a large-scale energy storage technology with great application potential.Nevertheless,its application is severely hindered by the slow diffusion of zinc ions in desirable cathode materials.Herein,a technique of water-incorporation coupled with oxygen-vacancy modulation is exploited to improve the zinc ions diffusion kinetics in vanadium pentoxide(V_(2)O_5)cathode for ZIB.The incorporated water molecules replace lattice oxygen in V_(2)O_5,and function as pillars to expand interlayer distance.So the structural stability can be enhanced,and the zinc ions diffusion kinetics might also be promoted during the repeated intercalation/deintercalation.Meanwhile,the lattice water molecules can effectively enhance conductivity due to the electronic density modulation effect.Consequently,the modulated V_(2)O_5(H-V_(2)O_5)cathode behaves with superior rate capacity and stable durability,achieving 234 mA h g^(-1)over 9000 cycles even at 20 A g^(-1).Furthermore,a flexible all-solid-state(ASS)ZIB has been constructed,exhibiting an admirable energy density of 196.6 Wh kg^(-1)and impressive power density of 20.4 kW kg^(-1)as well as excellent long-term lifespan.Importantly,the assembled flexible ASS ZIB would be able to work in a large temperature span(from-20 to 70℃).Additionally,we also uncover the energy storage mechanism of the H-V_(2)O_5 electrode,offering a novel approach for creating high-kinetics cathodes for multivalent ion storage.

Kinetics and Mechanism of Iridium(Ⅲ)-Catalyzed Oxidation of Ethanol Amine by Cerium(Ⅳ) in Sulfuric Acid Media

In this study, the kinetics and mechanism of the iridium（ Ⅲ ） -catalyzed oxidation of ethanol amine（EAN） by cerium（Ⅳ） in a sulfuric acid medium was investigated using titrimetric technique of redox in a temperature range of 298--313 K. It was found that the reaction is of first order with respect to Ce（ Ⅳ ） and It（ Ⅲ ）, and a positive fractional order with respect to EAN. It was also found that the pseudo-first-order （ [EAN ] 〉〉 [ Ce （ Ⅳ） ] ） rate constant koba decreases with the increase of [ H^＋ ] and [ HSO^-4 ]. Under the protection of nitrogen gas, the reaction system can initiate the polymerization of acrylonitrile, indicating the generation of free radicals. On the basis of the experimental results, a suitable mechanism was proposed. From the dependence of koba on the concentration of hydrogen sulfate, Ce（SO4）2 was found to be the kinetically active species. The rate constants of the rote-determining step together with the activation parameters were evaluated.

Kinetic modeling of adsorption of vanadium and iron from acid solution through ion exchange resins

This study assessed the adsorption process and the reaction kinetics involved in the selective recovery of vanadium from an acid solution containing iron as an impurity.Four commercial resins were studied:Lewatit^(®)MonoPlus TP 209 XL,Lewatit^(®) TP 207,Dowex^(TM)M4195(chelating resin)and Lewatit^(®) MonoPlus S 200 H(strong cationic exchange resin).To investigate the effect of time on the adsorption process,batch experiments were carried out using the following initial conditions:pH 2.0,298 K,and a proportion of 1 g of resin to 50 mL of solution.The variation of pH over time was analyzed.Chelating resin released less H+ions as the adsorption occurred,resulting in a lower drop of pH when compared to S 200 H resin.Ion adsorption by the resins was also evaluated through FT-IR and SEM−EDS before and after the experiments.Among the evaluated kinetic models(pseudo-first order,pseudo-second order,Elovich and intraparticle diffusion models),the pseudo-second order model best fits the experimental data of the adsorption of vanadium and iron by all of the four resins.M4195 resin showed the highest recovery of vanadium and the lowest adsorption of iron.Kinetic data,which are fundamental to industrial processes applications,are provided.

Effect of iron transformation on Acidithiobacillus ferrooxidans bio-leaching of clay vanadium residue

The acid bio-leaching process of vanadium extraction from clay vanadium water-leached residue was studied and the effect of the performance of iron transformation was investigated.Acidithiobacillus ferrooxidans affects the dissolution of vanadium through the catalytic effect on Fe^3+/Fe^2+couple and material exchange.The passivation of iron settling correlates with ferrous ion content in bio-leaching solution.In medium containing A.ferrooxidans and Fe(Ⅲ),the increment in Fe(Ⅱ)concentration leads to the formation of jarosite,generating a decline in vanadium extraction efficiency.Analysis of cyclic voltammetry shows that Fe(Ⅱ)ion is apt to be oxidized and translated into precipitate by A.ferrooxidans,which strongly adsorbed to the surface of the residue.Fe(Ⅲ)ion promotes the vanadium extraction due to its oxidizing activity.Admixing A.ferrooxidans to Fe(Ⅲ)medium elevates the reduction of low valence state vanadium and facilitates the exchange of substance between minerals and solution.This motivates 3.8%and 21.8%increments in recovery ratio and leaching rate of vanadium compared to the Fe(Ⅲ)exclusive use,respectively.Moreover,Fe(Ⅱ)ion impacts vanadium extraction slightly in sterile medium but negatively influences vanadium leaching in the presence of bacteria.

Water quality,natural chemical weathering and ecological risk assessment of the contaminated area of vanadium ore in Yinhua River,China:Evidence from major ions and trace elements

There are abundant vanadium ores in the Cambrian strata in southern Shaanxi,China.Many years of mining activities and surface leaching have polluted the surface water to a certain extent,but the researches on the water quality characteristics and pollution degree are relatively weak.This contribution was organized to investigate the surface water quality by general parameters,including TDS,Eh,pH,DO,TOC,COD,and EC,in the vanadium ore belt(Yinhua River basin).Major ions were determined to detect the water type and natural chemical weathering,while trace elements were used to illustrate their geochemical characteristics and ecological risk assessment of heavy metals.The study found that the surface water was weakly alkaline and mainly dominated from normal to pool grade.The particle size with1000–10,000 nm of suspended particles was the main carrier of organic matter.The concentration of HCO_(3)^(-)and SO_(4)^(2-)in the anions and Ca^(2+)and Mg^(2+)ions in the cations were relatively high,and the water type was Ca-Mg-HCO_(3)-SO_(4) type.Rock weathering had a great influence on surface water,and the weathering products were mainly silicate and carbonate.Compared with the Type river,the contents of V elements showed an obvious positive anomaly,which may be affected by mining activities of vanadium ore and the annual leaching of the tailings pond.As and Cd in the surface water was polluted seriously.The integrated pollution index suggested that the surface water pollution was serious,and the main stream was more serious with the increasing tailings ponds.

Radiation synthesis and characteristics of PTFE-g-PSSA ion exchange membrane applied in vanadium redox battery

Radiation-induced grafting of styrene onto polytetrafluoroethylene (PTFE) membranes was studied by a simultaneous irradiation technique.Grafting was carded out usingγ-radiation from a ^(60)Co source at room temperature. Effects of absorbed dose,atmosphere,dose rate,and the concentration of initial monomer on the degree of grafting (DOG) were investigated and the most appropriate grafting condition was obtained.Subsequently,sulphonation of the grafted PTFE membrane (PTFE-g-PS) was carried out and a series of ion exchange membranes (PTFE-g-PSSA) was prepared.Further characterizations of FTIR,TGA,and SEM testified that grafting and sulphonation of the membranes were successfully processed;moreover,grafting of styrene not only occurred in the surface of PTFE membrane,but also in the micropores of the membrane.Ion exchange capacity (IEC) and conductivity were found increase with the grafting yield.The results suggest that at a low dose,such as 17 kGy,the ion exchange membrane (IEM) which will be suitable for vanadium redox battery (VRB) use can be obtained.

Removal of vanadium from ammonium molybdate solution by ion exchange

The separation techniques of vanadium and molybdenum were summarized, and a new method of removal V(Ⅴ) from Mo(Ⅵ) by adsorption with chelate resin was presented. Nine kinds of chelate resins were used to investigate the adsorbent capability of V(Ⅴ) in ammonium molybdate solution with static method. The test results show that DDAS, CUW and CW-2 resins can easily adsorb V(Ⅴ) in ammonium molybdate solution, but hardly adsorb Mo(Ⅵ). The dynamic experimental results show more than 99.5% of V(Ⅴ) can be adsorbed, and the adsorption rate of Mo(Ⅵ) is less than 0.27% at 294-296 K for 60 min at pH 7.42-8.02. The mass ratio of V to Mo decreases to l/5 0000 in the effluent from 1/255 in the initial solution. The loaded resin can be desorbed by 5% NH3·H2O solution, and the vanadium desorption rate can reach 99.6%. The max concentration of vanadium in desorbed solution can reach 20 g/L, while the concentration of molybdenum is less than 0.8 g/L.

Vanadium Nitride Nanoparticles as Anode Material for Lithium Ion Hybrid Capacitor Applications

A high production efficiency synthesis method was used to produce a stacked vanadium nitride nanoparticle structure with an inexpensive raw material as an anode material and high surface area polystyrene was used the cathode material for lithium ion hybrid capacitors. The Li-HCs cell displayed an excellent specific capacitance of 64.2 F·g^-1 at a current density of 0.25 A·g^-1 and a wide potential window of 0.01 to 3.5 V. Furthermore, the device exhibited a high energy density of 109.3 W·h·kg^-1 at a power density of 512.3 W·kg^-1 and retained an energy density of 69.2 W·h·kg^-1 at a high power density of 3 498.9 W· kg^-1 at 2 A·g^-1. Due to the short synthesis time and simple raw materials, this method is suitable for industrial production.

SPES/PVDF Binary Membrane as an Alternative Proton Exchange Membrane in Vanadium Redox Flow Battery Application

SPES/PVDF blends were employed to prepare the ion exchange membranes for vanadium redox flow battery(VRB) application for the first time. The addition of the highly crystalline and hydrophobic PVDF effectively limited the swelling behavior of SPES. The vanadium ion permeability of SPES/PVDF membranes was one order of magnitude lower than that of Nafion 117 membrane and pristine SPES membrane. Single cells with SPES/PVDF composite membranes showed significantly lower capacity loss, higher coulombic efficiency and higher energy efficiency than that with Nafion117 and pristine SPES membranes. The blend membrane with 40 wt% of PVDF(denoted as S_(0.6) P_(0.4)) showed energy efficiency of 83.2% at 30 mA?cm^(-2), which was superior to that of the Nafion117 and SPES membranes. In the self-discharge test, S_(0.6) P_(0.4) membrane showed twice longer duration in open circuit decay than that with Nafion 117 membrane. With all the good properties and low cost, the SPES/PVDF membranes are expected to have excellent commercial prospects as ion exchange membranes for VRB system.

Reconstructing proton channels via Zr-MOFs realizes highly ion-selective and proton-conductive SPEEK-based hybrid membrane for vanadium flow battery

There is an urgent need to break through the trade-off between proton conductivity and ion selectivity of proton exchange membrane(PEM)in vanadium flow battery(VFB).Proton channels in PEM are the key to controlling the ion sieving and proton conductivity in VFB.Herein,two types of proton channels are reconstructed in the hybrid membrane via introducing modified Zr-MOFs(IM-UIO-66-AS)into SPEEK matrix.Internal proton channels in IM-UIO-66-AS and interfacial proton channels between grafted imidazole groups on Zr-MOFs and SPEEK greatly improve the conductivity of the IM-UIO-66-AS/SPEEK hybrid membrane.More importantly,both reconstructed proton channels block the vanadium-ion permeation to realize enhanced ion selectivity according to the size sieving and Donnan exclusion effects,respectively.Moreover,the hybrid membrane exhibits good mechanical property and dimensional stability.Benefiting from such rational design,a VFB loading with the optimized membrane exhibits enhanced voltage efficiency of 79.9%and outstanding energy efficiency of 79.6%at 200 m A cm^(-2),and keeps a notable cycle stability for 300 cycles in the long-term cycling test.Therefore,this study provides inspiration for preparing next-generation PEMs with high ion selectivity and proton conductivity for VFB application.

Influence of solvent on ion conductivity of polybenzimidazole proton exchange membranes for vanadium redox flow batteries

Polybenzimidazole(PBI)is a kind of proton transport membrane material,and its ion conductivity is a key factor affecting its application in vanadium redox flow batteries(VRFBs).The casting solvent of PBI has a significant influence on the acid doping level of PBI membranes which is closely related to ionic conductivity.In this paper,3,3′-diaminobenzidine(DABz)and 4,4′-Dicarboxydiphenylether(DCDPE)were used as raw materials by solution condensation to prepare the PBI with ether bond groups.The chemical structure of PBI was determined by1H NMR and FT-IR,and the prepared PBI had good solubility which can be dissolved in a variety of solvents.The PBI proton exchange membranes were prepared by solution coating with 5 different solvents of N,N-dimethylformamide(DMF),N,N-dimethylacetamide(DMAc),dimethyl sulfoxide(DMSO),1-methyl-2-pyrrolidone(NMP),methane sulfonic acid(MSA).The effects of different solvents on the ion conductivity and physicochemical properties were discussed in detail.The results showed that the PBI membrane prepared by using MSA as solvent(the PBI+MSA membrane)exhibits high water uptake,acid doping level and low vanadium ion permeability.The VRFB assembled with the PBI+MSA membrane exhibited higher coulombic efficiency(CE)99.87%and voltage efficiency(VE)84.50%than that of the commercial Nafion115 membrane at100 m A·cm-2,and after 480 cycles,the EE value can still be maintained at 83.73%.The self-discharge time of a single battery was recorded to be as long as 1000 h.All experimental data indicated that MSA is the best solvent for casting PBI membrane.

Preparation of Vanadium Dioxide Films for Protection from High-energy Laser Hits

Vanadium dioxide(VO 2)thin films are used for protection from high-energy laser hits due to their semiconductor-to-metal phase transition experienced during heating at temperature of approximately 68 ℃,which followed by a abrupt change of optical behavior, namely from transparent semiconductor state below 68 ℃ to highly reflective metallic state beyond 68 ℃.The preparation and properties of the films are described as well as the primary principle of the device for protection from high energy laser hits. An ion-beam-sputtering system is used to deposit VO 2 thin films.The technique is reactive ion beam sputtering of vanadium at temperature of 200 ℃ on Si, Ge and Si 3N 4 substrates in a well controlled atmosphere of argon with a partial pressure of O 2, followed by a post annealing at 400-550 ℃ with argon gas.The optical transmittance changes from 60% to 4% are obtained within the temperature range from 50 ℃ to 70 ℃. X-ray diffraction (XRD) shows that the films are of single-phase VO 2.

钒(Ⅳ)-硫胺素荧光光度法的研究与应用

利用钒(Ⅳ)作为氧化剂将硫胺素氧化成硫胺荧,建立了一种测量痕量硫胺素的荧光分光光度法,并将该方法应用于药物中硫胺素的测定.该方法测定硫胺素的线性范围为0.8～240.0μg/L;检出限为0.45μg/L;对于40.0μg/L的硫胺素测定10次,其相对标准偏差为1.5%.

由电导率测定VO^(2+)在Nafion 1135阳离子交换膜中扩散系数

研究通过电导率测定钒离子VO2+在Nafion 1135离子交换膜中的扩散系数的方法。采用交流阻抗技术测定含不同浓度VO2+的0.1 mol/L硫酸电解质溶液在有无膜时的阻抗值,采用有膜时的阻抗减去无膜时阻抗值得到了不同条件下的膜阻抗。结果表明:阻抗大小与电极距离成正比,有膜与无膜时分别测定的阻抗与电极距离的关系曲线近似呈平行线,与电解液组成无关;膜阻抗随着溶液中VO2+浓度的增加而增加。根据基于Nernst-Planck扩散对流方程的二元离子在交换膜中扩散系数与电导率的关系方程计算了钒离子VO2+在Nafion 1135离子交换膜中的扩散系数为4.5×10-12m2/s。