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 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
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
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
An approach for coal-based direct reduction of vanadium−titanium magnetite(VTM)raw ore was proposed.Under the optimal reduction conditions with reduction temperature of 1140℃,reduction time of 3 h,C-to-Fe molar ratio...An approach for coal-based direct reduction of vanadium−titanium magnetite(VTM)raw ore was proposed.Under the optimal reduction conditions with reduction temperature of 1140℃,reduction time of 3 h,C-to-Fe molar ratio of 1.2꞉1,and pre-oxidation temperature of 900℃,the iron metallization degree is 97.8%.Ultimately,magnetic separation yields an iron concentrate with an Fe content of 76.78 wt.%and efficiency of 93.41%,while the magnetic separation slag has a Ti grade and recovery of 9.36 wt.%and 87.07%,respectively,with a titanium loss of 12.93%.This new strategy eliminates the beneficiation process of VTM raw ore,effectively reduces the Ti content in the iron concentrate,and improves the comprehensive utilization of valuable metals.展开更多
The issue of water molecule activity in aqueous zinc-ion batteries presents a significant challenge.During the charging and discharging process,the strong polarity of water molecules tends to cause the dissolution of ...The issue of water molecule activity in aqueous zinc-ion batteries presents a significant challenge.During the charging and discharging process,the strong polarity of water molecules tends to cause the dissolution of cathode materials,which reduces the cycle stability and specific capacity,consequently limiting the practical application of zinc-ion batteries.In this work,hydroxypropylβ-cyclodextrin(HP-β-CD),a special stereo cyclic organic molecule with hydrophobic inner cavity and hydrophilic outer cavity,is used as the intercalator for hydrated vanadium oxide(VOH)to enlarge the layer spacing and enhance the hydrophobicity of the cathode material.The larger interlayer spacing(13.9Å)of HP-β-CD-VOH is beneficial for improving ion mobility and the intrinsic electrochemical reaction kinetics.HP-β-CD-VOH delivers a discharge capacity of 336.7 mAh g^(-1)at 0.2 A g^(-1)and high-rate capability(242 mAh g^(-1)at 5 A g^(-1)).Due to the hydrophobic property of HP-β-CD in the interlayer pillar,the vanadium dissolution effect of polar water molecules can be reduced during charge and discharge;HP-β-CDVOH demonstrates sustained high efficiency and extended cycle longevity,maintaining a remarkable durability of 6000 cycles at a current density of 10 A g^(-1).This study presents an effective strategy for developing high-performance aqueous zinc-ion battery cathode materials.展开更多
This investigation evaluated the impact of as-is biochar(BC)and phosphorous(P)-loaded biochar(PBC)(3%)on the growth and biochemical characteristics of rice under exposure to vanadium(V)(60 mg L^(-1)).The results indic...This investigation evaluated the impact of as-is biochar(BC)and phosphorous(P)-loaded biochar(PBC)(3%)on the growth and biochemical characteristics of rice under exposure to vanadium(V)(60 mg L^(-1)).The results indicate that rice plants exposed to a V-only treatment experienced declines in several growth parameters.Conversely,the inclusion of BC and PBC caused noteworthy increases in physiological traits.PBC performed well in stress environments.Specifically,the shoot and root fresh weights increased by 82.86 and 53.33%,respectively,when compared to the V-only treatment.In addition,the SPAD chlorophyll of the shoot increased by 13.05%relative to the V-amended plants.Moreover,including BC and PBC improved the antioxidant enzyme traits of plant shoot and root,such as significant increases in superoxide dismutase(SOD by 56.11 and 117.35%),catalase(CAT by 34.19 and 35.77%),and peroxidase(POD by 25.90 and 18.74%)when compared to V-only amended plants,respectively.These findings strongly suggest that the application of BC and PBC can trigger biochemical pathways that facilitate biomass accumulation in meristematic cells.However,further investigations are required to elucidate the underlying mechanisms responsible for this growth promotion.展开更多
The development of appropriate cathode materials with stable structures and fast diffusion kinetics of zinc ions is crucial for aqueous zinc-ion batteries(AZIBs)but remains significantly challenging.Herein,the design ...The development of appropriate cathode materials with stable structures and fast diffusion kinetics of zinc ions is crucial for aqueous zinc-ion batteries(AZIBs)but remains significantly challenging.Herein,the design and synthesis of defect-rich and prismatic-shaped nanohybrids composed of vanadium oxynitride nanoparticles confined in the porous nitrogen-doped carbon framework(VN_(x)O_(y)@NC)are reported.Its unique structural advantages,including enriched defect sites that effectively enhance electrical conductivity,accelerate charge transfer kinetics,and improve structural stability.Additionally,the introduction of structural defects in VN_(x)O_(y)@NC increases the adsorption energy and reduces the hopping barrier of Zn ion,as evidenced by density functional theory(DFT)calculations.The H^(+)and Zn^(2+)co-insertion/extraction mechanism was systematically validated by ex-situ X-ray diffraction and ex-situ X-ray photoelectron spectroscopy tests.Consequently,the VN_(x)O_(y)@NC//Zn batteries exhibit an exceptional capacity of 570.9 mAh g^(-1)at 0.2 A g^(-1),a superior rate capability of 446.7 mAh g^(-1)at 20 A g^(-1),and long cycling life.Furthermore,the corresponding quasisolid-state battery delivers an ultra-high energy density of 271.9 Wh kg^(-1),demonstrating potential for practical applications.This work presents an effective structural and defect engineering strategy for designing advanced electrode materials with promising applications in AZIBs.展开更多
Microbial vanadate(V(V))reduction is a key process for environmental geochemistry and detoxification of vanadium(V).However,the electron transfer pathways and V isotope fractionation involved in this process are not y...Microbial vanadate(V(V))reduction is a key process for environmental geochemistry and detoxification of vanadium(V).However,the electron transfer pathways and V isotope fractionation involved in this process are not yet fully understood.In this study,the V(V)reduction mechanisms with concomitant V isotope fractionation by the Gram-positive bacterium Bacillus subtilis(B.subtilis)and the Gramnegative bacterium Thauera humireducens(T.humireducens)were investigated.Both strains could effectively reduce V(V),removing(90.5%±1.6%)and(93.0%±1.8%)of V(V)respectively from an initial concentration of 50 mg L^(-1) during a 10-day incubation period.V(V)was bioreduced to insoluble vanadium(IV),which was distributed both inside and outside the cells.Electron transfer via cytochrome C,nicotinamide adenine dinucleotide,and glutathione played critical roles in V(V)reduction.Metabolomic analysis showed that differentially enriched metabolites(quinone,biotin,and riboflavin)mediated electron transfer in both strains.The aqueous V in the remaining solution became isotopically heavier as V(V)bioreduction proceeded.The obtained V isotope composition dynamics followed a Rayleigh fractionation model,and the isotope enrichment factor(e)was(–0.54‰±0.04‰)for B.subtilis and(–0.32‰±0.03‰)for T.humireducens,with an insignificant difference.This study provides molecular insights into electron transfer for V(V)bioreduction and reveals V isotope fractionation during this bioprocess,which is helpful for understanding V biogeochemistry and developing novel strategies for V remediation.展开更多
Aqueous zinc-ion batteries(AZBs)are considered safer and potential substitutes for large-scale energy storage and conversion devices.The conventional vanadium pentoxide(V_(2)O_(5))cathode material has attracted widesp...Aqueous zinc-ion batteries(AZBs)are considered safer and potential substitutes for large-scale energy storage and conversion devices.The conventional vanadium pentoxide(V_(2)O_(5))cathode material has attracted widespread attention duo to its typical layered structure and high theoretical capacity.Unfortunately,it still suffers from severe structural collapse,sluggish diffusion dynamics,and fast capacity fading.Herein,we rationally designed and prepared trivalent Al^(3+)and H_(2)O co-intercalated V_(2)O_(5)(AlVO),in which Al^(3+)plays a“pillar”role and forms strong Al−O bonds,while H_(2)O acts as the“lubricant”,synergistically maintaining the structural stability and accelerating the diffusion of zinc ions.The Zn//AlVO battery is found to possess not only an impressive reversible capacity of 390.7 mAh·g^(−1) at 0.5 A·g^(−1),5.13 times that of Zn//c-V_(2)O_(5),but also excellent rate capability and long-term cycling performance(with the residual capacity of 138.2 mAh·g^(−1) over 10000 cycles at 10 A·g^(−1)).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
Vanadium redox flow batteries(VRFBs)hold significant promise for large-scale energy storage applications.However,the sluggish reaction kinetics on the electrode surface considerably limit their performance.Implementat...Vanadium redox flow batteries(VRFBs)hold significant promise for large-scale energy storage applications.However,the sluggish reaction kinetics on the electrode surface considerably limit their performance.Implementation of efficient surface modification on carbon electrodes through an economically viable production method is crucial for the practical application of VRFBs.Herein,a nano-carbon layer with morphology of fine nanoparticles(<90 nm)and rich oxygen functional groups was constructed on carbon felts by unbalanced magnetron sputtering coupled with thermal treatment.This modified carbon felt served as both anode and cathode in cell,enabling an improved wettability of electrolyte and high reversibility of the active mass,and promoted kinetics of redox reactions.The optimized carbon felt,achieved through one hour of deposition(1C-CF),demonstrated outstanding electrochemical performance in a single cell.The cell exhibited a high energy efficiency of 82.4%at a current density of 100 m A cm^(-2)and maintained 71.8%at a high current density of 250 mA cm^(-2).Furthermore,the energy efficiency remained at 77.2%during long-term cycling(450 cycles)at a current density of 150 mA cm^(-2),indicating good electrode stability.Our results shed light on the surface design of carbon felt electrodes for the broad application interest of VRFB energy storage systems.展开更多
In recent years,aqueous aluminum ion batteries have been widely studied owing to their abundant energy storage and high theo retical capacity.An in-depth study of vanadium oxide materials is necessary to address the p...In recent years,aqueous aluminum ion batteries have been widely studied owing to their abundant energy storage and high theo retical capacity.An in-depth study of vanadium oxide materials is necessary to address the precipitation of insoluble products covered cathode surface and the slow reaction kinetics.Therefore,a method using a simple one-step hydrothermal preparation and oxalic acid to regulate oxygen vacancies has been reported.A high starting capacity(400 mAh g^(-1))can be achieved by Ov-V2O5,and it is capable of undergoing 200 cycles at 0.4 A g^(-1),with a termination discharge capacity of103 mAh g^(-1).Mechanism analysis demonstrated that metastable structures(AlxV2O5and HxV2O5)were constructed through the insertion of Al^(3+)/H^(+)during discharging,which existed in the lattice intercalation with V2O5.The incorporation of oxygen vacancies lowers the reaction energy barrier while improving the ion transport efficiency.In addition,the metastable structure allows the electrostatic interaction between Al3+and the main backbone to establish protection and optimize the transport channel.In parallel,this work exploits ex-situ characterization and DFT to obtain a profound insight into the instrumental effect of oxygen vacancies in the construction of metastable structures during in-situ electrochemical activation,with a view to better understanding the mechanism of the synergistic participation of Al3+and H+in the reaction.This work not only reports a method for cathode materials to modulate oxygen vacancies,but also lays the foundation for a deeper understanding of the metastable structure of vanadium oxides.展开更多
The all-vanadium redox flow battery(VRFB)plays an important role in the energy transition toward renewable technologies by providing grid-scale energy storage.Their deployment,however,is limited by the lack of membran...The all-vanadium redox flow battery(VRFB)plays an important role in the energy transition toward renewable technologies by providing grid-scale energy storage.Their deployment,however,is limited by the lack of membranes that provide both a high energy efficiency and capacity retention.Typically,the improvement of the battery’s energy efficiency comes at the cost of its capacity retention.Herein,novel N-alkylated and N-benzylated meta-polybenzimidazole(m-PBI)membranes are used to understand the molecular requirements of the polymer electrolyte in a vanadium redox flow battery,providing an important toolbox for future research toward next-generation membrane materials in energy storage devices.The addition of an ethyl side chain to the m-PBI backbone increases its affinity toward the acidic electrolyte,thereby increasing its ionic conductivity and the corresponding energy efficiency of the VRFB cell from 70%to 78%at a current density of 200 mA cm^(-2).In addition,cells equipped with ethylated m-PBI showed better capacity retention than their pristine counterpart,respectively 91%versus 87%,over 200 cycles at 200 mA cm^(-2).The outstanding VRFB cycling performance,together with the low-cost and fluorine-free chemistry of the N-alkylated m-PBI polymer,makes this material a promising membrane to be used in next-generation VRFB systems.展开更多
The melting and separation behavior of vanadium-titanium magnetite pellets directed at an efficient extraction of vanadium and titanium was systematically investigated.Applying FactSage simulations and experiments,the...The melting and separation behavior of vanadium-titanium magnetite pellets directed at an efficient extraction of vanadium and titanium was systematically investigated.Applying FactSage simulations and experiments,the smelting separation of three pre-reduced pellets from different regions was analyzed.The simulations demonstrate that FeTi2O5 is converted to TiC at low temperatures,necessitating suppression of this step.Experiments under optimized conditions(1590-1690°C,20-25 min,2%coke,basicity 0.4-0.6,and 3.0%-6.0%MgO)yield iron grade of 92.35%-95.06%,titanium grade of 34.37%-39.89%,and vanadium grade of 0.56%-1.52%,with recoveries of 99.52%-99.60%,94.08%-98.96%,and 92.63%-94.38%for iron,titanium and vanadium,respectively.The titanium in the slag,primarily in the form of anosovite,is suitable for sulfuric acid-based titanium white production.An increase in basicity,MgO content,and pellet metallization serves to improve vanadium recovery in melted iron but lowers the titanium grade in the slag.The overall process effectively utilizes vanadium and titanium resources under optimized conditions.展开更多
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℃.
基金funded by the National Natural Science Foundation of China(Nos.U20A20145,51774205)the Open Project from Engineering Research Center of the Ministry of Education,Sichuan University,China.
文摘An approach for coal-based direct reduction of vanadium−titanium magnetite(VTM)raw ore was proposed.Under the optimal reduction conditions with reduction temperature of 1140℃,reduction time of 3 h,C-to-Fe molar ratio of 1.2꞉1,and pre-oxidation temperature of 900℃,the iron metallization degree is 97.8%.Ultimately,magnetic separation yields an iron concentrate with an Fe content of 76.78 wt.%and efficiency of 93.41%,while the magnetic separation slag has a Ti grade and recovery of 9.36 wt.%and 87.07%,respectively,with a titanium loss of 12.93%.This new strategy eliminates the beneficiation process of VTM raw ore,effectively reduces the Ti content in the iron concentrate,and improves the comprehensive utilization of valuable metals.
基金financially supported by the Science and Technology Research Program of Chongqing Municipal Education Commission(No.KJQN202300759)the Vanadium Titanium Materials Engineering Technology Research Center Foundation Project of Sichuan(No.2022FTGC07)+5 种基金the National Key R&D Program of China(No.2023YFC3009500)the National Natural Science Foundation of China(No.22379103)the Science and Technology Projects of Suzhou City(No.SYC2022043)the Campus Science Fund Project of Chongqing Jiaotong University(Nos.2020020086 and 2020023032)the Graduate Tutor Team Construction Project of Chongqing(No.JDDSTD2022006)the Graduate Student Research Innovation Project of Chongqing(No.2024S0110)
文摘The issue of water molecule activity in aqueous zinc-ion batteries presents a significant challenge.During the charging and discharging process,the strong polarity of water molecules tends to cause the dissolution of cathode materials,which reduces the cycle stability and specific capacity,consequently limiting the practical application of zinc-ion batteries.In this work,hydroxypropylβ-cyclodextrin(HP-β-CD),a special stereo cyclic organic molecule with hydrophobic inner cavity and hydrophilic outer cavity,is used as the intercalator for hydrated vanadium oxide(VOH)to enlarge the layer spacing and enhance the hydrophobicity of the cathode material.The larger interlayer spacing(13.9Å)of HP-β-CD-VOH is beneficial for improving ion mobility and the intrinsic electrochemical reaction kinetics.HP-β-CD-VOH delivers a discharge capacity of 336.7 mAh g^(-1)at 0.2 A g^(-1)and high-rate capability(242 mAh g^(-1)at 5 A g^(-1)).Due to the hydrophobic property of HP-β-CD in the interlayer pillar,the vanadium dissolution effect of polar water molecules can be reduced during charge and discharge;HP-β-CDVOH demonstrates sustained high efficiency and extended cycle longevity,maintaining a remarkable durability of 6000 cycles at a current density of 10 A g^(-1).This study presents an effective strategy for developing high-performance aqueous zinc-ion battery cathode materials.
基金funded by the Launch Fund of Hainan University High Level Talent,China(RZ2100003226)the National Natural Science Foundation of China(NSFC-31860728).
文摘This investigation evaluated the impact of as-is biochar(BC)and phosphorous(P)-loaded biochar(PBC)(3%)on the growth and biochemical characteristics of rice under exposure to vanadium(V)(60 mg L^(-1)).The results indicate that rice plants exposed to a V-only treatment experienced declines in several growth parameters.Conversely,the inclusion of BC and PBC caused noteworthy increases in physiological traits.PBC performed well in stress environments.Specifically,the shoot and root fresh weights increased by 82.86 and 53.33%,respectively,when compared to the V-only treatment.In addition,the SPAD chlorophyll of the shoot increased by 13.05%relative to the V-amended plants.Moreover,including BC and PBC improved the antioxidant enzyme traits of plant shoot and root,such as significant increases in superoxide dismutase(SOD by 56.11 and 117.35%),catalase(CAT by 34.19 and 35.77%),and peroxidase(POD by 25.90 and 18.74%)when compared to V-only amended plants,respectively.These findings strongly suggest that the application of BC and PBC can trigger biochemical pathways that facilitate biomass accumulation in meristematic cells.However,further investigations are required to elucidate the underlying mechanisms responsible for this growth promotion.
基金financially supported by the National Natural Science Foundation of China(Nos.22225902,U22A20436,and 22209185)the National key Research&Development Program of China(Nos.2022YFE0115900 and 2021YFA1501500)+1 种基金the Postdoctoral Fellowship Program of CPSF,China(No.GZB20230758)Fujian Key Laboratory of Green Extraction and High-value Utilization of New Energy Metals(No.2023-KFKT-2)
文摘The development of appropriate cathode materials with stable structures and fast diffusion kinetics of zinc ions is crucial for aqueous zinc-ion batteries(AZIBs)but remains significantly challenging.Herein,the design and synthesis of defect-rich and prismatic-shaped nanohybrids composed of vanadium oxynitride nanoparticles confined in the porous nitrogen-doped carbon framework(VN_(x)O_(y)@NC)are reported.Its unique structural advantages,including enriched defect sites that effectively enhance electrical conductivity,accelerate charge transfer kinetics,and improve structural stability.Additionally,the introduction of structural defects in VN_(x)O_(y)@NC increases the adsorption energy and reduces the hopping barrier of Zn ion,as evidenced by density functional theory(DFT)calculations.The H^(+)and Zn^(2+)co-insertion/extraction mechanism was systematically validated by ex-situ X-ray diffraction and ex-situ X-ray photoelectron spectroscopy tests.Consequently,the VN_(x)O_(y)@NC//Zn batteries exhibit an exceptional capacity of 570.9 mAh g^(-1)at 0.2 A g^(-1),a superior rate capability of 446.7 mAh g^(-1)at 20 A g^(-1),and long cycling life.Furthermore,the corresponding quasisolid-state battery delivers an ultra-high energy density of 271.9 Wh kg^(-1),demonstrating potential for practical applications.This work presents an effective structural and defect engineering strategy for designing advanced electrode materials with promising applications in AZIBs.
基金supported by the National Natural Science Foundation of China(U21A2033)the Fundamental Research Funds for the Central Universities(2652022103).
文摘Microbial vanadate(V(V))reduction is a key process for environmental geochemistry and detoxification of vanadium(V).However,the electron transfer pathways and V isotope fractionation involved in this process are not yet fully understood.In this study,the V(V)reduction mechanisms with concomitant V isotope fractionation by the Gram-positive bacterium Bacillus subtilis(B.subtilis)and the Gramnegative bacterium Thauera humireducens(T.humireducens)were investigated.Both strains could effectively reduce V(V),removing(90.5%±1.6%)and(93.0%±1.8%)of V(V)respectively from an initial concentration of 50 mg L^(-1) during a 10-day incubation period.V(V)was bioreduced to insoluble vanadium(IV),which was distributed both inside and outside the cells.Electron transfer via cytochrome C,nicotinamide adenine dinucleotide,and glutathione played critical roles in V(V)reduction.Metabolomic analysis showed that differentially enriched metabolites(quinone,biotin,and riboflavin)mediated electron transfer in both strains.The aqueous V in the remaining solution became isotopically heavier as V(V)bioreduction proceeded.The obtained V isotope composition dynamics followed a Rayleigh fractionation model,and the isotope enrichment factor(e)was(–0.54‰±0.04‰)for B.subtilis and(–0.32‰±0.03‰)for T.humireducens,with an insignificant difference.This study provides molecular insights into electron transfer for V(V)bioreduction and reveals V isotope fractionation during this bioprocess,which is helpful for understanding V biogeochemistry and developing novel strategies for V remediation.
基金supported by National Natural Science Foundation of China(Grant No.22369006)Key Talent Projects in Gansu Province(2025RCXM011)+2 种基金College Students’Innovation and Entrepreneurship Training Program Project(S202310740033)Science and Technology Innovation Project for College Students(Grant Nos.Z10 and 146)Open Research Fund of the State Key Laboratory of Molecular Engineering of Polymers(K2025-21,Fudan University).
文摘Aqueous zinc-ion batteries(AZBs)are considered safer and potential substitutes for large-scale energy storage and conversion devices.The conventional vanadium pentoxide(V_(2)O_(5))cathode material has attracted widespread attention duo to its typical layered structure and high theoretical capacity.Unfortunately,it still suffers from severe structural collapse,sluggish diffusion dynamics,and fast capacity fading.Herein,we rationally designed and prepared trivalent Al^(3+)and H_(2)O co-intercalated V_(2)O_(5)(AlVO),in which Al^(3+)plays a“pillar”role and forms strong Al−O bonds,while H_(2)O acts as the“lubricant”,synergistically maintaining the structural stability and accelerating the diffusion of zinc ions.The Zn//AlVO battery is found to possess not only an impressive reversible capacity of 390.7 mAh·g^(−1) at 0.5 A·g^(−1),5.13 times that of Zn//c-V_(2)O_(5),but also excellent rate capability and long-term cycling performance(with the residual capacity of 138.2 mAh·g^(−1) over 10000 cycles at 10 A·g^(−1)).
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 by National Natural Science Foundation of China(U21B2057)。
文摘Vanadium redox flow batteries(VRFBs)hold significant promise for large-scale energy storage applications.However,the sluggish reaction kinetics on the electrode surface considerably limit their performance.Implementation of efficient surface modification on carbon electrodes through an economically viable production method is crucial for the practical application of VRFBs.Herein,a nano-carbon layer with morphology of fine nanoparticles(<90 nm)and rich oxygen functional groups was constructed on carbon felts by unbalanced magnetron sputtering coupled with thermal treatment.This modified carbon felt served as both anode and cathode in cell,enabling an improved wettability of electrolyte and high reversibility of the active mass,and promoted kinetics of redox reactions.The optimized carbon felt,achieved through one hour of deposition(1C-CF),demonstrated outstanding electrochemical performance in a single cell.The cell exhibited a high energy efficiency of 82.4%at a current density of 100 m A cm^(-2)and maintained 71.8%at a high current density of 250 mA cm^(-2).Furthermore,the energy efficiency remained at 77.2%during long-term cycling(450 cycles)at a current density of 150 mA cm^(-2),indicating good electrode stability.Our results shed light on the surface design of carbon felt electrodes for the broad application interest of VRFB energy storage systems.
基金financially supported by the National Natural Science Foundation of China(52102233)Science and Technology Project of Hebei Education Department(QN2023019).
文摘In recent years,aqueous aluminum ion batteries have been widely studied owing to their abundant energy storage and high theo retical capacity.An in-depth study of vanadium oxide materials is necessary to address the precipitation of insoluble products covered cathode surface and the slow reaction kinetics.Therefore,a method using a simple one-step hydrothermal preparation and oxalic acid to regulate oxygen vacancies has been reported.A high starting capacity(400 mAh g^(-1))can be achieved by Ov-V2O5,and it is capable of undergoing 200 cycles at 0.4 A g^(-1),with a termination discharge capacity of103 mAh g^(-1).Mechanism analysis demonstrated that metastable structures(AlxV2O5and HxV2O5)were constructed through the insertion of Al^(3+)/H^(+)during discharging,which existed in the lattice intercalation with V2O5.The incorporation of oxygen vacancies lowers the reaction energy barrier while improving the ion transport efficiency.In addition,the metastable structure allows the electrostatic interaction between Al3+and the main backbone to establish protection and optimize the transport channel.In parallel,this work exploits ex-situ characterization and DFT to obtain a profound insight into the instrumental effect of oxygen vacancies in the construction of metastable structures during in-situ electrochemical activation,with a view to better understanding the mechanism of the synergistic participation of Al3+and H+in the reaction.This work not only reports a method for cathode materials to modulate oxygen vacancies,but also lays the foundation for a deeper understanding of the metastable structure of vanadium oxides.
基金supported by the Swiss National Science Foundation(grant number 188631).
文摘The all-vanadium redox flow battery(VRFB)plays an important role in the energy transition toward renewable technologies by providing grid-scale energy storage.Their deployment,however,is limited by the lack of membranes that provide both a high energy efficiency and capacity retention.Typically,the improvement of the battery’s energy efficiency comes at the cost of its capacity retention.Herein,novel N-alkylated and N-benzylated meta-polybenzimidazole(m-PBI)membranes are used to understand the molecular requirements of the polymer electrolyte in a vanadium redox flow battery,providing an important toolbox for future research toward next-generation membrane materials in energy storage devices.The addition of an ethyl side chain to the m-PBI backbone increases its affinity toward the acidic electrolyte,thereby increasing its ionic conductivity and the corresponding energy efficiency of the VRFB cell from 70%to 78%at a current density of 200 mA cm^(-2).In addition,cells equipped with ethylated m-PBI showed better capacity retention than their pristine counterpart,respectively 91%versus 87%,over 200 cycles at 200 mA cm^(-2).The outstanding VRFB cycling performance,together with the low-cost and fluorine-free chemistry of the N-alkylated m-PBI polymer,makes this material a promising membrane to be used in next-generation VRFB systems.
基金support from the National Key R&D Program of China(Nos.2023YFC3903900,2023YFC3903904)the National Natural Science Foundation of China(Nos.52274343,52174329).
文摘The melting and separation behavior of vanadium-titanium magnetite pellets directed at an efficient extraction of vanadium and titanium was systematically investigated.Applying FactSage simulations and experiments,the smelting separation of three pre-reduced pellets from different regions was analyzed.The simulations demonstrate that FeTi2O5 is converted to TiC at low temperatures,necessitating suppression of this step.Experiments under optimized conditions(1590-1690°C,20-25 min,2%coke,basicity 0.4-0.6,and 3.0%-6.0%MgO)yield iron grade of 92.35%-95.06%,titanium grade of 34.37%-39.89%,and vanadium grade of 0.56%-1.52%,with recoveries of 99.52%-99.60%,94.08%-98.96%,and 92.63%-94.38%for iron,titanium and vanadium,respectively.The titanium in the slag,primarily in the form of anosovite,is suitable for sulfuric acid-based titanium white production.An increase in basicity,MgO content,and pellet metallization serves to improve vanadium recovery in melted iron but lowers the titanium grade in the slag.The overall process effectively utilizes vanadium and titanium resources under optimized conditions.
