Manganese is a major impurity in acidic vanadium-bearing leaching solutions,but its effects on vanadium precipitation via hydrolysis and acidic ammonium salts remain unclear.In this study,vanadium-bearing leachates wi...Manganese is a major impurity in acidic vanadium-bearing leaching solutions,but its effects on vanadium precipitation via hydrolysis and acidic ammonium salts remain unclear.In this study,vanadium-bearing leachates with varying manganese concentrations(VL-cMn)were prepared through calcium,a calcium-manganese composite,and manganese-based roasting of vanadium slag(VS)to investigate the influence of manganese on vanadium precipitation behavior during hydrolysis precipitation(HP)and ammonium salt precipitation(AP),as well as the microscopic characteristics and purity of the resulting V_(2)O_(5) products.The results showed that increasing the pH mitigated the negative effects of Mn on the V precipitation rate during HP.However,as the manganese concentration increased from 5.69 to 15.38 g/L,the V precipitation rate gradually declined at higher temperatures and longer reaction times.The precipitates exhibited increased microstructural density,which might had contributed to the formation of Mn-bearing phases.Additionally,the average grain size of V_(2)O_(5) was reduced and the particles were increasingly agglomerated,leading to a 2.55%decrease in product purity.For AP,as manganese concentration increased,raising the pH counteracted the negative impact of Mn on the V precipitation rate and reduced the required amount of ammonium sulfate.Moreover,Mn was unevenly adsorbed on the surface of the precipitates.Although V_(2)O_(5) grains gradually shrank and became denser,there was no significant effect on the final product purity,which remained above 99.3%.In conclusion,roasting with added manganese salts influenced the hydrolysis of vanadium but had no significant effect on acidic ammonium salt precipitation.展开更多
Vanadium redox flow batteries(VRFBs)are a means of large-scale energy storage due to their excellent scalability,safety,long cycling life,and decoupled power and energy capacities.However,the slow redox kinetics of va...Vanadium redox flow batteries(VRFBs)are a means of large-scale energy storage due to their excellent scalability,safety,long cycling life,and decoupled power and energy capacities.However,the slow redox kinetics of vanadium species on conventional carbon electrodes remains a major limitation to their performance.We investigated the deposition of carbon black,carbon nanotubes,and electrochemically exfoliated graphene(Exf-Gr)onto thermally-activated carbon paper(ACP)by spray coating to increase the electrode electrocatalytic activity.The modified electrodes were characterized using scanning electron microscopy,X-ray diffraction,Raman spectroscopy,X-ray photoelectron microscopy,and surface area analysis,while their electrochemical properties were evaluated by cyclic voltammetry,electrochemical impedance spectroscopy,and singlecell VRFB testing.Among the modified electrodes,Exf-Gr/ACP had the best performance,achieving a 2.9-fold reduction in charge transfer resistance compared to pristine ACP and delivering 2.5 times the discharge capacity in single-cell tests.This improvement is attributed to Exf-Gr’s high surface area,favorable catalytic activity,and excellent dispersion on the ACP substrate.Surface modification with electrochemically exfoliated graphene is a highly effective strategy for improving the electrode performance in VRFB systems,with significant implications for large-scale energy storage.展开更多
The current vanadium extraction process from sodium roasted vanadium slag poses risks such as ammonia pollution.This study proposes a novel calcium-based vanadium extraction and hydrolysis precipitation process,achiev...The current vanadium extraction process from sodium roasted vanadium slag poses risks such as ammonia pollution.This study proposes a novel calcium-based vanadium extraction and hydrolysis precipitation process,achieving clean and efficient vanadium recovery.The introduction of Ca O facilitates the targeted reconstruction and conversion of vanadium and calcium in the solution,forming acidsoluble calcium vanadate intermediates.Under optimal conditions,n(Ca)/n(V)ratio of 1.75,extraction temperature of 90℃,and extraction time of 90 min,the vanadium extraction ratio reached 99.83%.This process also separates vanadium from sodium and silicon,enabling one-step purification of the vanadium solution.Subsequent sulfuric acid leaching,conducted at p H of 4.0,90℃,and 60 min,achieved a vanadium leaching ratio of 99.72%,further separating vanadium from calcium and other impurities.Finally,the purified vanadium solution underwent hydrolysis precipitation at p H of 2.1 and 95℃for60 min,achieving a precipitation ratio of 98.69%.The calcined product yielded V_(2)O_(5) with a purity of 98.60%.Compared to the conventional sodium roasting—water leaching along with ammonium salt precipitation process,this innovative method eliminates ammonia-nitrogen wastewater emissions.This study provides a foundation for the development of new vanadium extraction technologies from vanadium slag.展开更多
Vanadium is a strategic metal in many countries,and it is mainly extracted from vanadium slag produced in titanomagnetite metallurgy.The traditional sodium roasting process for vanadium extraction poses environmental ...Vanadium is a strategic metal in many countries,and it is mainly extracted from vanadium slag produced in titanomagnetite metallurgy.The traditional sodium roasting process for vanadium extraction poses environmental threats,and a green calcification pro-cess has been proposed.However,the vanadium extraction rate in the calcification process is much lower than in the sodium roasting pro-cess,which is related to vanadium solid solubility in Fe_(2)TiO_(5).Previous studies about vanadium behavior in Fe_(2)TiO_(5) were conducted in air,with a vanadium oxidation state of V5+.Vanadium with lower oxidation states has been detected in the tailings in the calcification process.The present paper studied the effects of vanadium oxidation states on the solid solubility in Fe_(2)TiO_(5) through solid-state reaction,X-ray diffraction characterization,transmission electron microscopy characterization,X-ray photoelectron spectroscopy analysis,and solid solu-tion modeling.The relative interaction values between vanadium oxides and Fe_(2)TiO_(5) are obtained as|L_(V_(2)O_(3))|>|L_(V_(2)O_(4))|>|L_(V_(2)O_(5)),indicating that vanadium with lower valence is preferable to be solid dissolved in Fe_(2)TiO_(5).The results imply that insufficiently oxidized vanadium increases the vanadium content in the Fe_(2)TiO_(5) phase during vanadium slag’s calcification roasting.Besides,experimental conditions op-timization shows that higher experimental temperature,vanadium introduction as V2O3,and a high-purity argon atmosphere would lead to higher vanadium solubility in Fe_(2)TiO_(5),and high temperature is beneficial for the release of vanadium from vanadium-containing Fe_(2)TiO_(5) when dissociated in air.展开更多
China is the world’s largest producer of vanadium products,whose major vanadium resource is vanadium slag obtained by smelting vanadium−titanium magnetite ores.The vanadium extraction techniques from vanadium slag ha...China is the world’s largest producer of vanadium products,whose major vanadium resource is vanadium slag obtained by smelting vanadium−titanium magnetite ores.The vanadium extraction techniques from vanadium slag have progressed stepwise toward greenization during the past 30 years in China.This review has systematically summarized these developments and classified the developments into three stages.The early stage is the efficient vanadium extraction techniques such as the sodium roasting−water leaching technique.The developed stage is the clean vanadium extraction techniques including the calcification roasting−acid leaching technique and sub-molten salt technique.The advanced stage is the green vanadium extraction techniques,for example the magnesiation roasting−acid leaching technique.The mechanisms,advantages and disadvantages of industrially applied and literature reported vanadium extraction techniques in each development stage are elaborated from multiple perspectives.Finally,future development directions are pointed out,aiming to inspire green extraction technique of vanadium worldwide.展开更多
Specialized vanadium(V)-iron(Fe)-based alloy additives utilized in the production of V-containing steels were investigated.Vanadium slag from the Panzhihua region of China was utilized as a raw material to optimize pr...Specialized vanadium(V)-iron(Fe)-based alloy additives utilized in the production of V-containing steels were investigated.Vanadium slag from the Panzhihua region of China was utilized as a raw material to optimize process parameters for the preparation of V-Fe-based alloy via silicon thermal reduction.Experiments were conducted to investigate the effects of reduction temperature,holding time,and slag composition on alloy-slag separation,alloy microstructure,and the oxide content of residual slag,with an emphasis on the recovery of valuable metal elements.The results indicated that the optimal process conditions for silicon thermal reduction were achieved at reduction temperature of 1823 K,holding time of 240 min,and slag composition of 45 wt.%SiO_(2),40 wt.%CaO,and 15 wt.%Al_(2)O_(3).The resulting V-Fe-based alloy predominantly consisted of Fe-based phases such as Fe,titanium(Ti),silicon(Si)and manganese(Mn),with Si,V,as well as chromium(Cr)concentrated in the intercrystalline phase of the Fe-based alloy.The recoveries of Fe,Mn,Cr,V,and Ti under the optimal conditions were 96.30%,91.96%,86.53%,80.29%,and 74.82%,respectively.The key components of the V-Fe-based alloy obtained were 41.96 wt.%Si,27.55 wt.%Fe,12.13 wt.%Mn,5.53 wt.%V,4.86 wt.%Cr,and 3.74 wt.%Ti,thereby enabling the comprehensive recovery of the valuable metal from vanadium slag.展开更多
The ammonium salt precipitation method is frequently utilized for extracting vanadium from the leaching solution obtained through sodium roasting of vanadium slag.However,Na^(+)and NH_(4)^(+)ions in the vanadium preci...The ammonium salt precipitation method is frequently utilized for extracting vanadium from the leaching solution obtained through sodium roasting of vanadium slag.However,Na^(+)and NH_(4)^(+)ions in the vanadium precipitation solution can not be effectively separated,leading to a large amount of ammonia-nitrogen wastewater which is difficult to treat.In this study,the manganese salt pretreatment process is used to extract vanadium from a sodium roasting leaching solution,enabling the separation of vanadium and sodium.The vanadium extraction product of manganese salt is dissolved in acid to obtain vanadium-containing leaching solution,then vanadium is extracted by hydrolysis and vanadium precipitation,and V_(2)O_(5)is obtained after impurity removal and calcination.The results show that the rate of vanadium extraction by manganese salt is 98.23%.The vanadium extraction product by manganese salt is Mn_(2)V_(2)O_(7),and its sodium content is only 0.167%.Additionally,the acid solubility of vanadium extraction products by manganese salt is 99.52%,and the vanadium precipitation rate of manganese vanadate solution is 92.34%.After the removal of manganese and calcination process,the purity of V_(2)O_(5)product reached 97.73%,with a mere 0.64%loss of vanadium.The Mn_(2)^(+)and NH_(4)^(+)ions in the solution after vanadium precipitation are separated by precipitation method,which reduces the generation of ammonia-nitrogen wastewater.This is conducive to the green and sustainable development of the vanadium industry.展开更多
All-vanadium flow batteries(VFBs)are one of the most promising large-scale energy storage technologies.Conducting an operando quantitative analysis of the polarizations in VFBs under different conditions is essential ...All-vanadium flow batteries(VFBs)are one of the most promising large-scale energy storage technologies.Conducting an operando quantitative analysis of the polarizations in VFBs under different conditions is essential for developing high power density batteries.Here,we employ an operando decoupling method to quantitatively analyze the polarizations in each electrochemical and chemical reaction of VFBs under different catalytic conditions.Results show that the reduction reaction of V^(3+)presents the largest activation polarization,while the reduction reaction of VO_(2)^(+)primarily contributes to concentration polarizations due to the formation of the intermediate product V_(2)O_(3)^(3+).Additionally,it is found that the widely used electrode catalytic methods,incorporating oxygen functional groups and electrodepositing Bi,not only enhance the reaction kinetics but also exacerbate concentration polarizations simultaneously,especially during the discharge process.Specifically,in the battery with the high oxygen-containing electrodes,the negative side still accounts for the majority of activation loss(75.3%)at 200 mA cm^(-2),but it comes down to 36,9% after catalyzing the negative reactions with bismuth.This work provides an effective way to probe the limiting steps in flow batteries under various working conditions and offers insights for effectively enhancing battery performance for future developments.展开更多
The addition of vanadium substantially enhances the strength of the high-nitrogen austenitic stainless steel(HNASS),while maintaining excellent ductility and pitting corrosion resistance.The effects of vanadium microa...The addition of vanadium substantially enhances the strength of the high-nitrogen austenitic stainless steel(HNASS),while maintaining excellent ductility and pitting corrosion resistance.The effects of vanadium microalloying on the microstructure,mechanical properties,and pitting resistance of HNASS were systematically analyzed with a focus on the role of VN during the pitting process.The results suggest that vanadium promoted the precipitation of VN,contributing to grain boundary pinning and grain refinement.As vanadium content increased,the number of precipitates rose,and the average grain size decreased.At lower vanadium content(0-0.2 wt.%),the strength of the material was significantly reinforced with increasing vanadium content,while maintaining excellent ductility and pitting resistance.However,when the vanadium content reached 0.3-0.4 wt.%,precipitates demonstrated a substantially increased number and coarsened,accompanied by the formation of numerous dislocations around the precipitates.This brought about further strength reinforcement but a marked decline in ductility and pitting resistance.Additionally,pitting corrosion was initiated at the matrix-VN interface.Compared to the matrix,VN exhibited higher reactivity and preferentially reacted with Cl−ions,provoking dissolution.However,NH4+generated during the dissolution of VN facilitated repassivation of the material,suppressing further pitting propagation.展开更多
The Jahn-Teller effect of Mn^(3+)brings drastic structural changes to MnO_(2)-based materials and accelerates the destruction and deactivation of the internal structure of the materials,thus leading to severe capacity...The Jahn-Teller effect of Mn^(3+)brings drastic structural changes to MnO_(2)-based materials and accelerates the destruction and deactivation of the internal structure of the materials,thus leading to severe capacity fading and phase change of MnO_(2)-based materials in aqueous zinc ion batteries(AZIBs).Here,this study doped high valent vanadium ions into MnO_(2)(VMO-x)to inhibit manganese's Jahn-Teller effect.Through a series of characterizations,such as X-ray diffraction(XRD),Raman spectroscopy,and scanning electron microscopy(SEM),it was discovered that the introduction of vanadium ions effectively increased the interlayer spacing of MnO_(2),facilitating the transport of ions into the interlayer.Additionally,Fourier transform infrared spectroscopy(FTIR)and X-ray photoelectron spectroscopy(XPS)demonstrated vanadium doped could effectively adjust the electronic structure,decreasing the average oxidation state of manganese,thereby inhibiting the Jahn-Teller effect and significantly enhancing the stability of the VMO-x cathode.The theoretical calculation showed that introducing vanadium ions enhanced the interaction between the main material and Zn^(2+),optimized its electron transport capacity,and led to better electrical conductivity and reaction kinetics of the VMO-5.Benefiting from this,the VMO-5 cathode exhibited an outstanding capacity of 283 mAh/g and maintained a capacity retention rate of 79%after 2000 cycles,demonstrating excellent electrochemical performance.Furthermore,the mechanism of H^(+)/Zn^(2+)co-intercalation/deintercalation was demonstrated through mechanism analysis.Finally,the test results of the pouch cell demonstrated the excellent flexibility and safety exhibited by the VMO-5 make it have great potential in flexible devices.This work presented a novel approach to doping high valence metal ions into manganese-based electrodes for AZIBs.展开更多
The large-scale exploitation of vanadium(Ⅴ) bearing minerals has led to a massive accumulation of Ⅴ tailings, of which Ⅴ pollution poses severe ecological risks. Although the mechanisms of Ⅴ stress to the microbia...The large-scale exploitation of vanadium(Ⅴ) bearing minerals has led to a massive accumulation of Ⅴ tailings, of which Ⅴ pollution poses severe ecological risks. Although the mechanisms of Ⅴ stress to the microbial community have been reported, the influential pathways in a multi-medium-containing system, for example, the soil-tailings-groundwater system,are unknown. The dynamic redox conditions and substance exchange within the system exhibited complex Ⅴ stress on the local microbial communities. In this study, the influence pathways of Ⅴ stress to the microbial community in the soil-tailings-groundwater system were first investigated. High Ⅴ contents were observed in groundwater(139.2 ± 0.15 μg/L) and soil(98.0–323.8 ± 0.02 mg/kg), respectively. Distinct microbial composition was observed for soil and groundwater, where soil showed the highest level of diversity and richness. Firmicutes, Proteobacteria, Actinobacteria, and Acidobacteria were dominant in soil and groundwater with a sum relative abundance of around 80 %. Based on redundancy analysis and structural equation models, Ⅴ was one of the vital driving factors affecting microbial communities. Groundwater microbial communities were influenced by Ⅴ via Cr, dissolved oxygen, and total nitrogen, while Fe, Mn, and total phosphorus were the key mediators for Ⅴ to affect soil microbial communities. Ⅴ affected the microbial community via metabolic pathways related to carbonaceous matter, which was involved in the establishment of survival strategies for metal stress. This study provides novel insights into the influence pathways of Ⅴ on the microorganisms in tailings reservoir for pollution bioremediation.展开更多
A simplified CaO-V_(2)O_(5)-MnO_(2) system was established to qualitatively and quantitatively investigate the transformation behavior of vanadates.The results demonstrated dynamic transformations between calcium vana...A simplified CaO-V_(2)O_(5)-MnO_(2) system was established to qualitatively and quantitatively investigate the transformation behavior of vanadates.The results demonstrated dynamic transformations between calcium vanadate and manganese vanadate as n(CaO)/n(V_(2)O_(5))/n(MnO_(2))ratios and roasting temperatures varied.When MnO_(2) was incrementally added with n(CaO)/n(V_(2)O_(5))of 2,some Ca_(2)V_(2)O_(7) converted to Mn_(2)V_(2)O_(7).The mass of vanadium as calcium vanadate consistently exceeded that as manganese vanadate.Conversely,when CaO was gradually added with n(MnO_(2))/n(V_(2)O_(5))of 2,Mn_(2)V_(2)O_(7) tended to transform into Ca_(2)V_(2)O_(7) and Ca3V2O8.The affinity of vanadium for calcium was higher compared that of vanadium for manganese.The specific type of calcium vanadate formed depended on both n(CaO)/n(V_(2)O_(5))/n(MnO_(2))values and roasting temperatures,while manganese vanadate remained predominantly as Mn_(2)V_(2)O_(7).The influence of roasting temperature on the conversion between calcium vanadate and manganese vanadate was minimal.At n(CaO)/n(V_(2)O_(5))/n(MnO_(2))of 2/1/2 and temperatures ranging from 650 to 850°C,the mass ratio of vanadium present as calcium vanadate to manganese vanadate stabilized at approximately 2.展开更多
A series of innovative green metallurgical processes using novel reaction media including the NaOH/KOH sub-molten salt media and the NaOH-NaNO3 binary molten salt medium, for the extraction of vanadium and chromium fr...A series of innovative green metallurgical processes using novel reaction media including the NaOH/KOH sub-molten salt media and the NaOH-NaNO3 binary molten salt medium, for the extraction of vanadium and chromium from the vanadium slag have been developed. In comparison with the traditional sodium salt roasting technology, which operates at 850 ℃, the operation temperatures of these new processes drop to 200-400 ℃. Further, the extraction rates of vanadium and chromium utilizing the new approaches could reach 95% and 90%, respectively, significantly higher than those in the traditional roasting process, which are 75% and approximate zero, respectively. Besides, no hazardous gases and toxic tailings are discharged during the extraction process. Compared with the conventional roasting method, these new technologies show obvious advantages in terms of energy, environments, and the mineral resource utilization efficiency, providing an attractive alternative for the green technology upgrade of the vanadium production industries.展开更多
A novel process of vanadium extraction from vanadium slag in its molten state was conducted at the laboratory scale by oxidation with pure oxygen in the presence of CaO. The effect of mass ratio of CaO to V2O5 on the ...A novel process of vanadium extraction from vanadium slag in its molten state was conducted at the laboratory scale by oxidation with pure oxygen in the presence of CaO. The effect of mass ratio of CaO to V2O5 on the recovery of vanadium was studied. The sintered samples were leached by H2SO4 solution and characterized by XRD, XPS, SEM and EDS techniques. Compared with the roasting process, the energy saving effect of the proposed process was also discussed. The results showed that vanadium-rich phases were formed and vanadium mainly existed in the forms of CaV2O5 and Ca2V2O7. The formation mechanism of calcium vanadates in the molten vanadium bearing slag was explained. The XRD and XPS results implied that there was a limit to the oxidation reaction of V(IV) to V(V) under the high temperatures even though oxygen-supply was sufficient. An increase in the CaO content led to an increase in the formation of Ca2V2O7. About 90%of the vanadium recovery was obtained under optimal experiment conditions (mass ratio of CaO to V2O5 of 0.6, particle size 120 to 150μm, leaching temperature 90 °C, leaching time 2 h, H2SO4 concentration 20%, liquid to solid ratio 5:1 mL/g, stirring speed 500 r/min). The energy of 1.85×106 kJ could be saved in every 1000 kg of vanadium bearing slag using the proposed process from the theoretical calculation results. Recovery of vanadium from the molten vanadium bearing slag and utilisation of its heat energy are important not only for saving metal resources, but also for energy saving and emission reduction.展开更多
The oxidation process of low-grade vanadium slag in the presence of Na2CO3 was investigated by XRD,SEM/EDS and TG-DSC techniques.The results show that the vanadium slag is oxidized in a temperature range from 273 to 7...The oxidation process of low-grade vanadium slag in the presence of Na2CO3 was investigated by XRD,SEM/EDS and TG-DSC techniques.The results show that the vanadium slag is oxidized in a temperature range from 273 to 700 °C.Olivine phases and spinel phases are completely decomposed at 500 and 600 °C,respectively.Most of water-soluble sodium vanadates are formed between 500 and 600 °C.When roasting temperature reaches above 700 °C,the vanadium-rich phases of sodium vanadates can be obviously observed.However,at temperature above 800 °C,the samples are sintered.Most of the vanadium is enwrapped by glassy phase compounds which lead to the decrease of the leaching rate of vanadium.At the same time,the effect of roasting temperature on extraction of vanadium and characterization of leach residues were discussed.展开更多
The reduction behaviors of FeO·V2O3 and FeO·Cr2O3 during coal-based direct reduction have a decisive impact on the efficient utilization of high-chromium vanadium-bearing titanomagnetite concentrates. The ef...The reduction behaviors of FeO·V2O3 and FeO·Cr2O3 during coal-based direct reduction have a decisive impact on the efficient utilization of high-chromium vanadium-bearing titanomagnetite concentrates. The effects of molar ratio of C to Fe n(C)/n(Fe) and temperature on the behaviors of vanadium and chromium during direct reduction and magnetic separation were investigated. The reduced samples were characterized by X-ray diffraction(XRD), scanning election microscopy(SEM) and energy dispersive spectrometry(EDS) techniques. Experimental results indicate that the recoveries of vanadium and chromium rapidly increase from 10.0% and 9.6% to 45.3% and 74.3%, respectively, as the n(C)/n(Fe) increases from 0.8 to 1.4. At n(C)/n(Fe) of 0.8, the recoveries of vanadium and chromium are always lower than 10.0% in the whole temperature range of 1100-1250 °C. However, at n(C)/n(Fe) of 1.2, the recoveries of vanadium and chromium considerably increase from 17.8% and 33.8% to 42.4% and 76.0%, respectively, as the temperature increases from 1100 °C to 1250 °C. At n(C)/n(Fe) lower than 0.8, most of the FeO·V2O3 and FeO·Cr2O3 are not reduced to carbides because of the lack of carbonaceous reductants, and the temperature has little effect on the reduction behaviors of FeO·V2O3 and FeO·Cr2O3, resulting in very low recoveries of vanadium and chromium during magnetic separation. However, at higher n(C)/n(Fe), the reduction rates of FeO·V2O3 and FeO·Cr2O3 increase significatly because of the excess amount of carbonaceous reductants. Moreover, higher temperatures largely induce the reduction of FeO·V2O3 and FeO·Cr2O3 to carbides. The newly formed carbides are then dissolved in the γ(FCC) phase, and recovered accompanied with the metallic iron during magnetic separation.展开更多
The effect of vanadium(V)element on the microstructure and mechanical properties of anchor steel was explored by microstructural characterization and mechanical property tests of anchor steels with different V content...The effect of vanadium(V)element on the microstructure and mechanical properties of anchor steel was explored by microstructural characterization and mechanical property tests of anchor steels with different V contents.The results indicated that the trace addition of V element can generate dispersed VC nanoparticles in the anchor steel and then refine microstructure by inhibiting austenite grain growth.The increase in V content leads to the formation of a larger amount of smaller VC nanoparticles and more refined microstructure.Moreover,the increasing V content in anchor steel causes the volume fraction of ferrite to increase and that of pearlite to decrease continuously,and even leads to the formation of bainite.Accompanied by the microstructure change,the V-treated anchor steels exhibit higher strength compared with the anchor steel without V addition.However,the increased hardness difference between ferrite and pearlite results in poor coordination of deformation between them,leading to a decrease in their plasticity.The impact toughness of anchor steel first increases but then significantly decreases with the increase in V content.The improvement in impact toughness of trace V-treated anchor steel benefits from the enhancement in the band structure after hot rolling,which consumes more energy during the vertical crack propagation process.However,when the V content further increases,the hard and brittle bainite in the anchor steel can facilitate crack initiation and propagation,ultimately resulting in a reduced toughness.展开更多
Vanadium nitride(VN)is a promising pseudocapacitive material due to the high theoretical capacity,rapid redox Faradaic kinetics,and appropriate potential window.Although VN shows large pseudocapacitance in alkaline el...Vanadium nitride(VN)is a promising pseudocapacitive material due to the high theoretical capacity,rapid redox Faradaic kinetics,and appropriate potential window.Although VN shows large pseudocapacitance in alkaline electrolytes,the electrochemical instability and capacity degradation of VN electrode materials present significant challenges for practical applications.Herein,the capacitance decay mechanism of VN is investigated and a simple strategy to improve cycling stability of VN supercapacitor electrodes is proposed by introducing VO_(4)^(3-)anion in KOH electrolytes.Our results show that the VN electrode is electrochemical stabilization between-1.0and-0.4 V(vs.Hg/Hg O reference electrode)in 1.0 MKOH electrolyte,but demonstrates irreversible oxidation and fast capacitance decay in the potential range of-0.4 to0 V.In situ electrochemical measurements reveal that the capacitance decay of VN from-0.4 to 0 V is ascribed to the irreversible oxidation of vanadium(V)of N–V–O species by oxygen(O)of OH^(-).The as-generated oxidization species are subsequently dissolved into KOH electrolytes,thereby undermining the electrochemical stability of VN.However,this irreversible oxidation process could be hindered by introducing VO_(4)^(3-)in KOH electrolytes.A high volumetric specific capacitance of671.9 F.cm^(-3)(1 A.cm^(-3))and excellent cycling stability(120.3%over 1000 cycles)are achieved for VN nanorod electrode in KOH electrolytes containing VO_(4)^(3-).This study not only elucidates the failure mechanism of VN supercapacitor electrodes in alkaline electrolytes,but also provides new insights into enhancing pseudocapacitive energy storage of VN-based electrode materials.展开更多
A series of imido-vanadium(Ⅴ)complexes bearing bidentate phenoxy-phosphine ligands were synthesized and characterized by NMR,elemental analysis,and single-crystal X-ray diffraction.These complexes demonstrated excell...A series of imido-vanadium(Ⅴ)complexes bearing bidentate phenoxy-phosphine ligands were synthesized and characterized by NMR,elemental analysis,and single-crystal X-ray diffraction.These complexes demonstrated excellent catalytic performance in ethylene/1-hexene copolymerization,achieving high activities of 12.0×10~6–49.0×10~6 g_(polymer)·(mol_(V))^(-1)·h^(-1)and affording random copolymers with tunable 1-hexene incorporations.These catalysts also exhibited ultrahigh activity,up to 112.2×10~6 g_(polymer)·(mol_(V))^(-1)·h^(-1),in ethylene/norbornene(NB)copolymerization,yielding cyclic olefin copolymers with adjustable NB incorporations.Remarkably,these catalysts demonstrated exceptional tolerance toward polar functional groups,enabling efficient copolymerization of ethylene with both 10-undecen-1-ol(U-OH)and 5-norbornene-2-methanol(NB-OH),incorporating about 2 mol%polar comonomers with high efficiency.Different with the catalytic behaviors in copolymerization of ethylene with nonpolar comonomers,the catalytic activities in E/U-OH copolymerization(25.7×10~6 g_(polymer)·(mol_(V))^(-1)·h^(-1))were much higher than those in E/NB-OH copolymerization(8.6×10^(6) g_(polymer)·(mol_(V))^(-1)·h^(-1)).DFT calculations revealed that the catalytic performance is governed by synergistic electronic and steric effects.For E/NB copolymerization,strong preference for cyclic olefins was attributed to favorable transition state stabilization.In polar comonomer systems,steric effects were predominant,with NB-OH exhibiting a larger buried volume around vanadium center upon coordination compared to U-OH.Overall,this work provides fundamental insights into vanadium-catalyzed(co)polymerization and offers new strategies for tailored polyolefin design.展开更多
The sticking behavior of pellets affects the continuity of production in hydrogen-based shaft furnace.The coupling influences of V_(2)O_(5) and reduction temperature on reduction sticking behavior and mechanism evolut...The sticking behavior of pellets affects the continuity of production in hydrogen-based shaft furnace.The coupling influences of V_(2)O_(5) and reduction temperature on reduction sticking behavior and mechanism evolution of pellets under hydrogen atmosphere are investigated.The increase in V_(2)O_(5) addition aggravated the reduction sticking behavior,which is attributed to the combined functions of the development of unique interwoven structure in the metallic iron interconnections at the reduction sticking interface and the deterioration of reduction swelling behavior of pellets.In addition,the strength of metallic iron interconnections enhanced and reduction sticking behavior aggravated with the increase in reduction temperature.Importantly,compared to other reduction temperatures,the reduction sticking behavior of pellets was most significantly aggravated with the increase in V_(2)O_(5) addition at 1000℃.And the values of sticking index increased from 10.22%to 15.36% as the V_(2)O_(5) addition increased from 0 to 1.00 wt.%at 1000℃.展开更多
基金supported by National Natural Science Foundation of China(Nos.52204309,52174277 and 52374300)Fundamental Funds for the Central Universities(No.N2425026)。
文摘Manganese is a major impurity in acidic vanadium-bearing leaching solutions,but its effects on vanadium precipitation via hydrolysis and acidic ammonium salts remain unclear.In this study,vanadium-bearing leachates with varying manganese concentrations(VL-cMn)were prepared through calcium,a calcium-manganese composite,and manganese-based roasting of vanadium slag(VS)to investigate the influence of manganese on vanadium precipitation behavior during hydrolysis precipitation(HP)and ammonium salt precipitation(AP),as well as the microscopic characteristics and purity of the resulting V_(2)O_(5) products.The results showed that increasing the pH mitigated the negative effects of Mn on the V precipitation rate during HP.However,as the manganese concentration increased from 5.69 to 15.38 g/L,the V precipitation rate gradually declined at higher temperatures and longer reaction times.The precipitates exhibited increased microstructural density,which might had contributed to the formation of Mn-bearing phases.Additionally,the average grain size of V_(2)O_(5) was reduced and the particles were increasingly agglomerated,leading to a 2.55%decrease in product purity.For AP,as manganese concentration increased,raising the pH counteracted the negative impact of Mn on the V precipitation rate and reduced the required amount of ammonium sulfate.Moreover,Mn was unevenly adsorbed on the surface of the precipitates.Although V_(2)O_(5) grains gradually shrank and became denser,there was no significant effect on the final product purity,which remained above 99.3%.In conclusion,roasting with added manganese salts influenced the hydrolysis of vanadium but had no significant effect on acidic ammonium salt precipitation.
基金supported by the University of Seoul’s 2025 Research Fund.
文摘Vanadium redox flow batteries(VRFBs)are a means of large-scale energy storage due to their excellent scalability,safety,long cycling life,and decoupled power and energy capacities.However,the slow redox kinetics of vanadium species on conventional carbon electrodes remains a major limitation to their performance.We investigated the deposition of carbon black,carbon nanotubes,and electrochemically exfoliated graphene(Exf-Gr)onto thermally-activated carbon paper(ACP)by spray coating to increase the electrode electrocatalytic activity.The modified electrodes were characterized using scanning electron microscopy,X-ray diffraction,Raman spectroscopy,X-ray photoelectron microscopy,and surface area analysis,while their electrochemical properties were evaluated by cyclic voltammetry,electrochemical impedance spectroscopy,and singlecell VRFB testing.Among the modified electrodes,Exf-Gr/ACP had the best performance,achieving a 2.9-fold reduction in charge transfer resistance compared to pristine ACP and delivering 2.5 times the discharge capacity in single-cell tests.This improvement is attributed to Exf-Gr’s high surface area,favorable catalytic activity,and excellent dispersion on the ACP substrate.Surface modification with electrochemically exfoliated graphene is a highly effective strategy for improving the electrode performance in VRFB systems,with significant implications for large-scale energy storage.
基金financially supported by the National Natural Science Foundation of China(52204309,52174277 and 52374300)Fundamental Funds for the Central Universities(N2425026)Liaoning Province Science and Technology Plan Joint Fund(2023-MSBA-052)。
文摘The current vanadium extraction process from sodium roasted vanadium slag poses risks such as ammonia pollution.This study proposes a novel calcium-based vanadium extraction and hydrolysis precipitation process,achieving clean and efficient vanadium recovery.The introduction of Ca O facilitates the targeted reconstruction and conversion of vanadium and calcium in the solution,forming acidsoluble calcium vanadate intermediates.Under optimal conditions,n(Ca)/n(V)ratio of 1.75,extraction temperature of 90℃,and extraction time of 90 min,the vanadium extraction ratio reached 99.83%.This process also separates vanadium from sodium and silicon,enabling one-step purification of the vanadium solution.Subsequent sulfuric acid leaching,conducted at p H of 4.0,90℃,and 60 min,achieved a vanadium leaching ratio of 99.72%,further separating vanadium from calcium and other impurities.Finally,the purified vanadium solution underwent hydrolysis precipitation at p H of 2.1 and 95℃for60 min,achieving a precipitation ratio of 98.69%.The calcined product yielded V_(2)O_(5) with a purity of 98.60%.Compared to the conventional sodium roasting—water leaching along with ammonium salt precipitation process,this innovative method eliminates ammonia-nitrogen wastewater emissions.This study provides a foundation for the development of new vanadium extraction technologies from vanadium slag.
基金supported by the National Key Research and Development Program of China(No.2023YFC2908304).
文摘Vanadium is a strategic metal in many countries,and it is mainly extracted from vanadium slag produced in titanomagnetite metallurgy.The traditional sodium roasting process for vanadium extraction poses environmental threats,and a green calcification pro-cess has been proposed.However,the vanadium extraction rate in the calcification process is much lower than in the sodium roasting pro-cess,which is related to vanadium solid solubility in Fe_(2)TiO_(5).Previous studies about vanadium behavior in Fe_(2)TiO_(5) were conducted in air,with a vanadium oxidation state of V5+.Vanadium with lower oxidation states has been detected in the tailings in the calcification process.The present paper studied the effects of vanadium oxidation states on the solid solubility in Fe_(2)TiO_(5) through solid-state reaction,X-ray diffraction characterization,transmission electron microscopy characterization,X-ray photoelectron spectroscopy analysis,and solid solu-tion modeling.The relative interaction values between vanadium oxides and Fe_(2)TiO_(5) are obtained as|L_(V_(2)O_(3))|>|L_(V_(2)O_(4))|>|L_(V_(2)O_(5)),indicating that vanadium with lower valence is preferable to be solid dissolved in Fe_(2)TiO_(5).The results imply that insufficiently oxidized vanadium increases the vanadium content in the Fe_(2)TiO_(5) phase during vanadium slag’s calcification roasting.Besides,experimental conditions op-timization shows that higher experimental temperature,vanadium introduction as V2O3,and a high-purity argon atmosphere would lead to higher vanadium solubility in Fe_(2)TiO_(5),and high temperature is beneficial for the release of vanadium from vanadium-containing Fe_(2)TiO_(5) when dissociated in air.
基金supported by the National Natural Science Foundation of China(Nos.52074050,52222407)。
文摘China is the world’s largest producer of vanadium products,whose major vanadium resource is vanadium slag obtained by smelting vanadium−titanium magnetite ores.The vanadium extraction techniques from vanadium slag have progressed stepwise toward greenization during the past 30 years in China.This review has systematically summarized these developments and classified the developments into three stages.The early stage is the efficient vanadium extraction techniques such as the sodium roasting−water leaching technique.The developed stage is the clean vanadium extraction techniques including the calcification roasting−acid leaching technique and sub-molten salt technique.The advanced stage is the green vanadium extraction techniques,for example the magnesiation roasting−acid leaching technique.The mechanisms,advantages and disadvantages of industrially applied and literature reported vanadium extraction techniques in each development stage are elaborated from multiple perspectives.Finally,future development directions are pointed out,aiming to inspire green extraction technique of vanadium worldwide.
基金the financial support provided by the National Key R&D Program of China(Grant No.2023YFC3903900)the Science and Technology Innovation Talent Program of Hubei Province(Grant No.2022EJD002)+1 种基金the Sichuan Science and Technology Program(Grant No.2025ZNSFSC0378)the Key Laboratory of Green Chemistry of Sichuan Institutes of Higher Education(Grant No.LZJ2303).
文摘Specialized vanadium(V)-iron(Fe)-based alloy additives utilized in the production of V-containing steels were investigated.Vanadium slag from the Panzhihua region of China was utilized as a raw material to optimize process parameters for the preparation of V-Fe-based alloy via silicon thermal reduction.Experiments were conducted to investigate the effects of reduction temperature,holding time,and slag composition on alloy-slag separation,alloy microstructure,and the oxide content of residual slag,with an emphasis on the recovery of valuable metal elements.The results indicated that the optimal process conditions for silicon thermal reduction were achieved at reduction temperature of 1823 K,holding time of 240 min,and slag composition of 45 wt.%SiO_(2),40 wt.%CaO,and 15 wt.%Al_(2)O_(3).The resulting V-Fe-based alloy predominantly consisted of Fe-based phases such as Fe,titanium(Ti),silicon(Si)and manganese(Mn),with Si,V,as well as chromium(Cr)concentrated in the intercrystalline phase of the Fe-based alloy.The recoveries of Fe,Mn,Cr,V,and Ti under the optimal conditions were 96.30%,91.96%,86.53%,80.29%,and 74.82%,respectively.The key components of the V-Fe-based alloy obtained were 41.96 wt.%Si,27.55 wt.%Fe,12.13 wt.%Mn,5.53 wt.%V,4.86 wt.%Cr,and 3.74 wt.%Ti,thereby enabling the comprehensive recovery of the valuable metal from vanadium slag.
基金supported by the National Natural Science Foundation of China(52204309,52374300 and 52174277)the Opening Foundation of State Key Laboratory of Vanadium and Titanium Resources Comprehensive Utilization,China(2022P4FZG11A).
文摘The ammonium salt precipitation method is frequently utilized for extracting vanadium from the leaching solution obtained through sodium roasting of vanadium slag.However,Na^(+)and NH_(4)^(+)ions in the vanadium precipitation solution can not be effectively separated,leading to a large amount of ammonia-nitrogen wastewater which is difficult to treat.In this study,the manganese salt pretreatment process is used to extract vanadium from a sodium roasting leaching solution,enabling the separation of vanadium and sodium.The vanadium extraction product of manganese salt is dissolved in acid to obtain vanadium-containing leaching solution,then vanadium is extracted by hydrolysis and vanadium precipitation,and V_(2)O_(5)is obtained after impurity removal and calcination.The results show that the rate of vanadium extraction by manganese salt is 98.23%.The vanadium extraction product by manganese salt is Mn_(2)V_(2)O_(7),and its sodium content is only 0.167%.Additionally,the acid solubility of vanadium extraction products by manganese salt is 99.52%,and the vanadium precipitation rate of manganese vanadate solution is 92.34%.After the removal of manganese and calcination process,the purity of V_(2)O_(5)product reached 97.73%,with a mere 0.64%loss of vanadium.The Mn_(2)^(+)and NH_(4)^(+)ions in the solution after vanadium precipitation are separated by precipitation method,which reduces the generation of ammonia-nitrogen wastewater.This is conducive to the green and sustainable development of the vanadium industry.
基金supported by the Guangdong Major Project of Basic and Applied Basic Research(2023B0303000002)the National Natural Science Foundation of China(No.52206089)+3 种基金the Guangdong Basic and Applied Basic Research Foundation(2024A1515010288,2023B1515120005)the Natural Science Foundation of Shenzhen(JCYJ20230807093315033)the Shenzhen Engineering Research Center,Southern University of Science and Technology(No.XMHT20230208003)high level of special funds(G03034K001)。
文摘All-vanadium flow batteries(VFBs)are one of the most promising large-scale energy storage technologies.Conducting an operando quantitative analysis of the polarizations in VFBs under different conditions is essential for developing high power density batteries.Here,we employ an operando decoupling method to quantitatively analyze the polarizations in each electrochemical and chemical reaction of VFBs under different catalytic conditions.Results show that the reduction reaction of V^(3+)presents the largest activation polarization,while the reduction reaction of VO_(2)^(+)primarily contributes to concentration polarizations due to the formation of the intermediate product V_(2)O_(3)^(3+).Additionally,it is found that the widely used electrode catalytic methods,incorporating oxygen functional groups and electrodepositing Bi,not only enhance the reaction kinetics but also exacerbate concentration polarizations simultaneously,especially during the discharge process.Specifically,in the battery with the high oxygen-containing electrodes,the negative side still accounts for the majority of activation loss(75.3%)at 200 mA cm^(-2),but it comes down to 36,9% after catalyzing the negative reactions with bismuth.This work provides an effective way to probe the limiting steps in flow batteries under various working conditions and offers insights for effectively enhancing battery performance for future developments.
基金founded by National Natural Science Foundations of China(Nos.52231003,52201084,and U21A20113)Major Program(JD)of Hubei Province(No.2023BAA019)+1 种基金Natural Science Foundation of Guangdong Province(No.2024A1515011022)Guangdong Province Basic and Applied Basic Research Fund Offshore Wind Power Joint Fund(No.2023B1515250006).
文摘The addition of vanadium substantially enhances the strength of the high-nitrogen austenitic stainless steel(HNASS),while maintaining excellent ductility and pitting corrosion resistance.The effects of vanadium microalloying on the microstructure,mechanical properties,and pitting resistance of HNASS were systematically analyzed with a focus on the role of VN during the pitting process.The results suggest that vanadium promoted the precipitation of VN,contributing to grain boundary pinning and grain refinement.As vanadium content increased,the number of precipitates rose,and the average grain size decreased.At lower vanadium content(0-0.2 wt.%),the strength of the material was significantly reinforced with increasing vanadium content,while maintaining excellent ductility and pitting resistance.However,when the vanadium content reached 0.3-0.4 wt.%,precipitates demonstrated a substantially increased number and coarsened,accompanied by the formation of numerous dislocations around the precipitates.This brought about further strength reinforcement but a marked decline in ductility and pitting resistance.Additionally,pitting corrosion was initiated at the matrix-VN interface.Compared to the matrix,VN exhibited higher reactivity and preferentially reacted with Cl−ions,provoking dissolution.However,NH4+generated during the dissolution of VN facilitated repassivation of the material,suppressing further pitting propagation.
基金supported the National Key Research and Development Program of China(No.2024YFA1409900)the National Natural Science Foundation of China(Nos.62101296 and 52303335)+2 种基金the China Postdoctoral Science Foundation(Nos.2021M702656 and 2023M730099)the Natural Science Foundation of Shaanxi Province(Nos.2021JQ-756 and 2021M702656)the Graduate Innovation Fund of the School of Mechanical Engineering,Shaanxi University of Technology(No.SLGJX202404)。
文摘The Jahn-Teller effect of Mn^(3+)brings drastic structural changes to MnO_(2)-based materials and accelerates the destruction and deactivation of the internal structure of the materials,thus leading to severe capacity fading and phase change of MnO_(2)-based materials in aqueous zinc ion batteries(AZIBs).Here,this study doped high valent vanadium ions into MnO_(2)(VMO-x)to inhibit manganese's Jahn-Teller effect.Through a series of characterizations,such as X-ray diffraction(XRD),Raman spectroscopy,and scanning electron microscopy(SEM),it was discovered that the introduction of vanadium ions effectively increased the interlayer spacing of MnO_(2),facilitating the transport of ions into the interlayer.Additionally,Fourier transform infrared spectroscopy(FTIR)and X-ray photoelectron spectroscopy(XPS)demonstrated vanadium doped could effectively adjust the electronic structure,decreasing the average oxidation state of manganese,thereby inhibiting the Jahn-Teller effect and significantly enhancing the stability of the VMO-x cathode.The theoretical calculation showed that introducing vanadium ions enhanced the interaction between the main material and Zn^(2+),optimized its electron transport capacity,and led to better electrical conductivity and reaction kinetics of the VMO-5.Benefiting from this,the VMO-5 cathode exhibited an outstanding capacity of 283 mAh/g and maintained a capacity retention rate of 79%after 2000 cycles,demonstrating excellent electrochemical performance.Furthermore,the mechanism of H^(+)/Zn^(2+)co-intercalation/deintercalation was demonstrated through mechanism analysis.Finally,the test results of the pouch cell demonstrated the excellent flexibility and safety exhibited by the VMO-5 make it have great potential in flexible devices.This work presented a novel approach to doping high valence metal ions into manganese-based electrodes for AZIBs.
基金supported by the National Natural Science Foundation of China(No.42377415)the Natural Science Foundation of Sichuan Province(No.2023NSFSC0811),Sichuan Science and Technology Program(Nos.2021JDTD0013 and 2021YFQ0066)+1 种基金the Science and Technology Major Project of Xizhang Autonomous Region of China(No.XZ202201ZD0004G06)the Everest Scientific Research Program(No.80000-2023ZF11405).
文摘The large-scale exploitation of vanadium(Ⅴ) bearing minerals has led to a massive accumulation of Ⅴ tailings, of which Ⅴ pollution poses severe ecological risks. Although the mechanisms of Ⅴ stress to the microbial community have been reported, the influential pathways in a multi-medium-containing system, for example, the soil-tailings-groundwater system,are unknown. The dynamic redox conditions and substance exchange within the system exhibited complex Ⅴ stress on the local microbial communities. In this study, the influence pathways of Ⅴ stress to the microbial community in the soil-tailings-groundwater system were first investigated. High Ⅴ contents were observed in groundwater(139.2 ± 0.15 μg/L) and soil(98.0–323.8 ± 0.02 mg/kg), respectively. Distinct microbial composition was observed for soil and groundwater, where soil showed the highest level of diversity and richness. Firmicutes, Proteobacteria, Actinobacteria, and Acidobacteria were dominant in soil and groundwater with a sum relative abundance of around 80 %. Based on redundancy analysis and structural equation models, Ⅴ was one of the vital driving factors affecting microbial communities. Groundwater microbial communities were influenced by Ⅴ via Cr, dissolved oxygen, and total nitrogen, while Fe, Mn, and total phosphorus were the key mediators for Ⅴ to affect soil microbial communities. Ⅴ affected the microbial community via metabolic pathways related to carbonaceous matter, which was involved in the establishment of survival strategies for metal stress. This study provides novel insights into the influence pathways of Ⅴ on the microorganisms in tailings reservoir for pollution bioremediation.
基金finally supported by the National Natural Science Foundation of China (Nos.52204309,52174277,52374300)。
文摘A simplified CaO-V_(2)O_(5)-MnO_(2) system was established to qualitatively and quantitatively investigate the transformation behavior of vanadates.The results demonstrated dynamic transformations between calcium vanadate and manganese vanadate as n(CaO)/n(V_(2)O_(5))/n(MnO_(2))ratios and roasting temperatures varied.When MnO_(2) was incrementally added with n(CaO)/n(V_(2)O_(5))of 2,some Ca_(2)V_(2)O_(7) converted to Mn_(2)V_(2)O_(7).The mass of vanadium as calcium vanadate consistently exceeded that as manganese vanadate.Conversely,when CaO was gradually added with n(MnO_(2))/n(V_(2)O_(5))of 2,Mn_(2)V_(2)O_(7) tended to transform into Ca_(2)V_(2)O_(7) and Ca3V2O8.The affinity of vanadium for calcium was higher compared that of vanadium for manganese.The specific type of calcium vanadate formed depended on both n(CaO)/n(V_(2)O_(5))/n(MnO_(2))values and roasting temperatures,while manganese vanadate remained predominantly as Mn_(2)V_(2)O_(7).The influence of roasting temperature on the conversion between calcium vanadate and manganese vanadate was minimal.At n(CaO)/n(V_(2)O_(5))/n(MnO_(2))of 2/1/2 and temperatures ranging from 650 to 850°C,the mass ratio of vanadium present as calcium vanadate to manganese vanadate stabilized at approximately 2.
基金Project(2013CB632605)supported by the National Basic Research Program of ChinaProjects(51274178,51090382)supported by theNational Natural Science Foundation of ChinaProject(KGCX2-EW-215)supported by the Key Deployment Program of ChineseAcademy of Sciences
文摘A series of innovative green metallurgical processes using novel reaction media including the NaOH/KOH sub-molten salt media and the NaOH-NaNO3 binary molten salt medium, for the extraction of vanadium and chromium from the vanadium slag have been developed. In comparison with the traditional sodium salt roasting technology, which operates at 850 ℃, the operation temperatures of these new processes drop to 200-400 ℃. Further, the extraction rates of vanadium and chromium utilizing the new approaches could reach 95% and 90%, respectively, significantly higher than those in the traditional roasting process, which are 75% and approximate zero, respectively. Besides, no hazardous gases and toxic tailings are discharged during the extraction process. Compared with the conventional roasting method, these new technologies show obvious advantages in terms of energy, environments, and the mineral resource utilization efficiency, providing an attractive alternative for the green technology upgrade of the vanadium production industries.
基金Project(2013CB632600)supported by the National Basic Research and Development Program of China
文摘A novel process of vanadium extraction from vanadium slag in its molten state was conducted at the laboratory scale by oxidation with pure oxygen in the presence of CaO. The effect of mass ratio of CaO to V2O5 on the recovery of vanadium was studied. The sintered samples were leached by H2SO4 solution and characterized by XRD, XPS, SEM and EDS techniques. Compared with the roasting process, the energy saving effect of the proposed process was also discussed. The results showed that vanadium-rich phases were formed and vanadium mainly existed in the forms of CaV2O5 and Ca2V2O7. The formation mechanism of calcium vanadates in the molten vanadium bearing slag was explained. The XRD and XPS results implied that there was a limit to the oxidation reaction of V(IV) to V(V) under the high temperatures even though oxygen-supply was sufficient. An increase in the CaO content led to an increase in the formation of Ca2V2O7. About 90%of the vanadium recovery was obtained under optimal experiment conditions (mass ratio of CaO to V2O5 of 0.6, particle size 120 to 150μm, leaching temperature 90 °C, leaching time 2 h, H2SO4 concentration 20%, liquid to solid ratio 5:1 mL/g, stirring speed 500 r/min). The energy of 1.85×106 kJ could be saved in every 1000 kg of vanadium bearing slag using the proposed process from the theoretical calculation results. Recovery of vanadium from the molten vanadium bearing slag and utilisation of its heat energy are important not only for saving metal resources, but also for energy saving and emission reduction.
基金Project (2008AA031104) supported by the National High-tech Research and Development Program of China Project (2010063003) supported by the Sharing Fund of Large-scale Equipment of Chongqing University,China
文摘The oxidation process of low-grade vanadium slag in the presence of Na2CO3 was investigated by XRD,SEM/EDS and TG-DSC techniques.The results show that the vanadium slag is oxidized in a temperature range from 273 to 700 °C.Olivine phases and spinel phases are completely decomposed at 500 and 600 °C,respectively.Most of water-soluble sodium vanadates are formed between 500 and 600 °C.When roasting temperature reaches above 700 °C,the vanadium-rich phases of sodium vanadates can be obviously observed.However,at temperature above 800 °C,the samples are sintered.Most of the vanadium is enwrapped by glassy phase compounds which lead to the decrease of the leaching rate of vanadium.At the same time,the effect of roasting temperature on extraction of vanadium and characterization of leach residues were discussed.
基金Projects(2013CB632601,2013CB632604)supported by the National Basic Research Program of ChinaProject(51125018)supported by the National Science Foundation for Distinguished Young Scholars of China+1 种基金Project(KGZD-EW-201-2)supported by the Key Research Program of the Chinese Academy of SciencesProjects(51374191,21106167,51104139)supported by the National Natural Science Foundation of China
文摘The reduction behaviors of FeO·V2O3 and FeO·Cr2O3 during coal-based direct reduction have a decisive impact on the efficient utilization of high-chromium vanadium-bearing titanomagnetite concentrates. The effects of molar ratio of C to Fe n(C)/n(Fe) and temperature on the behaviors of vanadium and chromium during direct reduction and magnetic separation were investigated. The reduced samples were characterized by X-ray diffraction(XRD), scanning election microscopy(SEM) and energy dispersive spectrometry(EDS) techniques. Experimental results indicate that the recoveries of vanadium and chromium rapidly increase from 10.0% and 9.6% to 45.3% and 74.3%, respectively, as the n(C)/n(Fe) increases from 0.8 to 1.4. At n(C)/n(Fe) of 0.8, the recoveries of vanadium and chromium are always lower than 10.0% in the whole temperature range of 1100-1250 °C. However, at n(C)/n(Fe) of 1.2, the recoveries of vanadium and chromium considerably increase from 17.8% and 33.8% to 42.4% and 76.0%, respectively, as the temperature increases from 1100 °C to 1250 °C. At n(C)/n(Fe) lower than 0.8, most of the FeO·V2O3 and FeO·Cr2O3 are not reduced to carbides because of the lack of carbonaceous reductants, and the temperature has little effect on the reduction behaviors of FeO·V2O3 and FeO·Cr2O3, resulting in very low recoveries of vanadium and chromium during magnetic separation. However, at higher n(C)/n(Fe), the reduction rates of FeO·V2O3 and FeO·Cr2O3 increase significatly because of the excess amount of carbonaceous reductants. Moreover, higher temperatures largely induce the reduction of FeO·V2O3 and FeO·Cr2O3 to carbides. The newly formed carbides are then dissolved in the γ(FCC) phase, and recovered accompanied with the metallic iron during magnetic separation.
基金supported by the National Natural Science Foundation of China(Nos.52101165,52031013 and 52071322).
文摘The effect of vanadium(V)element on the microstructure and mechanical properties of anchor steel was explored by microstructural characterization and mechanical property tests of anchor steels with different V contents.The results indicated that the trace addition of V element can generate dispersed VC nanoparticles in the anchor steel and then refine microstructure by inhibiting austenite grain growth.The increase in V content leads to the formation of a larger amount of smaller VC nanoparticles and more refined microstructure.Moreover,the increasing V content in anchor steel causes the volume fraction of ferrite to increase and that of pearlite to decrease continuously,and even leads to the formation of bainite.Accompanied by the microstructure change,the V-treated anchor steels exhibit higher strength compared with the anchor steel without V addition.However,the increased hardness difference between ferrite and pearlite results in poor coordination of deformation between them,leading to a decrease in their plasticity.The impact toughness of anchor steel first increases but then significantly decreases with the increase in V content.The improvement in impact toughness of trace V-treated anchor steel benefits from the enhancement in the band structure after hot rolling,which consumes more energy during the vertical crack propagation process.However,when the V content further increases,the hard and brittle bainite in the anchor steel can facilitate crack initiation and propagation,ultimately resulting in a reduced toughness.
基金financially supported by the National Natural Science Foundation of China(No.U2004210)Application Foundation Frontier Project of Wuhan Science and Technology Program(No.2020010601012199)City University of Hong Kong Strategic Research Grant,Hong Kong,China(No.7005505)。
文摘Vanadium nitride(VN)is a promising pseudocapacitive material due to the high theoretical capacity,rapid redox Faradaic kinetics,and appropriate potential window.Although VN shows large pseudocapacitance in alkaline electrolytes,the electrochemical instability and capacity degradation of VN electrode materials present significant challenges for practical applications.Herein,the capacitance decay mechanism of VN is investigated and a simple strategy to improve cycling stability of VN supercapacitor electrodes is proposed by introducing VO_(4)^(3-)anion in KOH electrolytes.Our results show that the VN electrode is electrochemical stabilization between-1.0and-0.4 V(vs.Hg/Hg O reference electrode)in 1.0 MKOH electrolyte,but demonstrates irreversible oxidation and fast capacitance decay in the potential range of-0.4 to0 V.In situ electrochemical measurements reveal that the capacitance decay of VN from-0.4 to 0 V is ascribed to the irreversible oxidation of vanadium(V)of N–V–O species by oxygen(O)of OH^(-).The as-generated oxidization species are subsequently dissolved into KOH electrolytes,thereby undermining the electrochemical stability of VN.However,this irreversible oxidation process could be hindered by introducing VO_(4)^(3-)in KOH electrolytes.A high volumetric specific capacitance of671.9 F.cm^(-3)(1 A.cm^(-3))and excellent cycling stability(120.3%over 1000 cycles)are achieved for VN nanorod electrode in KOH electrolytes containing VO_(4)^(3-).This study not only elucidates the failure mechanism of VN supercapacitor electrodes in alkaline electrolytes,but also provides new insights into enhancing pseudocapacitive energy storage of VN-based electrode materials.
基金financially supported by the National Natural Science Foundation of China(No.52130307)。
文摘A series of imido-vanadium(Ⅴ)complexes bearing bidentate phenoxy-phosphine ligands were synthesized and characterized by NMR,elemental analysis,and single-crystal X-ray diffraction.These complexes demonstrated excellent catalytic performance in ethylene/1-hexene copolymerization,achieving high activities of 12.0×10~6–49.0×10~6 g_(polymer)·(mol_(V))^(-1)·h^(-1)and affording random copolymers with tunable 1-hexene incorporations.These catalysts also exhibited ultrahigh activity,up to 112.2×10~6 g_(polymer)·(mol_(V))^(-1)·h^(-1),in ethylene/norbornene(NB)copolymerization,yielding cyclic olefin copolymers with adjustable NB incorporations.Remarkably,these catalysts demonstrated exceptional tolerance toward polar functional groups,enabling efficient copolymerization of ethylene with both 10-undecen-1-ol(U-OH)and 5-norbornene-2-methanol(NB-OH),incorporating about 2 mol%polar comonomers with high efficiency.Different with the catalytic behaviors in copolymerization of ethylene with nonpolar comonomers,the catalytic activities in E/U-OH copolymerization(25.7×10~6 g_(polymer)·(mol_(V))^(-1)·h^(-1))were much higher than those in E/NB-OH copolymerization(8.6×10^(6) g_(polymer)·(mol_(V))^(-1)·h^(-1)).DFT calculations revealed that the catalytic performance is governed by synergistic electronic and steric effects.For E/NB copolymerization,strong preference for cyclic olefins was attributed to favorable transition state stabilization.In polar comonomer systems,steric effects were predominant,with NB-OH exhibiting a larger buried volume around vanadium center upon coordination compared to U-OH.Overall,this work provides fundamental insights into vanadium-catalyzed(co)polymerization and offers new strategies for tailored polyolefin design.
基金supported by the authors are especially grateful to the National Natural Science Foundation of China(Grant No.51904063)the Key Program of National Natural Science Foundation of China(No.U23A20608)+6 种基金Fundamental Research Funds for the Central Universities(N2025023,N2225046)Postdoctoral Followship Program of CPSF(GZC20230392)Science&Technology Plan Project of Liaoning Province(2022JH24/10200027)Science&Technology Plan Project of Hebei Province(23314601L)Science and Technology Program of Liaoning of China(2023JH2/101700304)China Postdoctoral Science Foundation(2023M740551)Liaoning Province Science and Technology Plan Joint Program(Key Research and Development Program Project)(2023JH2/101800058).
文摘The sticking behavior of pellets affects the continuity of production in hydrogen-based shaft furnace.The coupling influences of V_(2)O_(5) and reduction temperature on reduction sticking behavior and mechanism evolution of pellets under hydrogen atmosphere are investigated.The increase in V_(2)O_(5) addition aggravated the reduction sticking behavior,which is attributed to the combined functions of the development of unique interwoven structure in the metallic iron interconnections at the reduction sticking interface and the deterioration of reduction swelling behavior of pellets.In addition,the strength of metallic iron interconnections enhanced and reduction sticking behavior aggravated with the increase in reduction temperature.Importantly,compared to other reduction temperatures,the reduction sticking behavior of pellets was most significantly aggravated with the increase in V_(2)O_(5) addition at 1000℃.And the values of sticking index increased from 10.22%to 15.36% as the V_(2)O_(5) addition increased from 0 to 1.00 wt.%at 1000℃.
