Vanadium oxides,par-ticularly hydrated forms like V_(2)O_(5)·nH_(2)O(VOH),stand out as promising cathode candidates for aqueous zinc ion batteries due to their adjustable layered structure,unique electronic chara...Vanadium oxides,par-ticularly hydrated forms like V_(2)O_(5)·nH_(2)O(VOH),stand out as promising cathode candidates for aqueous zinc ion batteries due to their adjustable layered structure,unique electronic characteristics,and high theoretical capacities.However,challenges such as vanadium dissolution,sluggish Zn^(2+)diffusion kinetics,and low operating voltage still hinder their direct application.In this study,we present a novel vanadium oxide([C_(6)H_(6)N(CH_(3))_(3)]_(1.08)V_(8)O_(20)·0.06H_(2)O,TMPA-VOH),developed by pre-inserting trimethylphenylammonium(TMPA+)cations into VOH.The incorporation of weakly polarized organic cations capitalizes on both ionic pre-intercalation and molecular pre-intercalation effects,resulting in a phase and morphology transition,an expansion of the interlayer distance,extrusion of weakly bonded interlayer water,and a substantial increase in V^(4+)content.These modifications synergistically reduce the electrostatic interactions between Zn^(2+)and the V-O lattice,enhancing structural stability and reaction kinetics during cycling.As a result,TMPA-VOH achieves an elevated open circuit voltage and operation voltage,exhibits a large specific capacity(451 mAh g^(-1)at 0.1 A g^(-1))coupled with high energy efficiency(89%),the significantly-reduced battery polarization,and outstanding rate capability and cycling stability.The concept introduced in this study holds great promise for the development of high-performance oxide-based energy storage materials.展开更多
Extraction of vanadium（IV） from sulphate acid solution was studied using organophosphorous-based extractants D2EHPA, EHEHPA and CYANEX 272 in kerosene. The different parameters affecting the extraction of vanadium...Extraction of vanadium（IV） from sulphate acid solution was studied using organophosphorous-based extractants D2EHPA, EHEHPA and CYANEX 272 in kerosene. The different parameters affecting the extraction of vanadium（IV） under equilibrium conditions were separately investigated to elucidate the stoichiometry of the extracted species. The distribution ratio of vanadium increased with increasing equilibrium pH of the aqueous phase, concentration of the extractants and temperature. D2EHPA was found to be a stronger extractant, having greater pH functionality than EHEHPA and CYANEX 272. Extraction of vanadium（IV） by these organophosphorous-based extractants involved cation exchange mechanism, and the extracted species appear to be VOR2（HR）2 in the low equilibrium pH and VOR2 in the higher equilibrium pH, where HR refers to the three acidic extractants.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
To analyze the thermodynamic characteristics of leaching process of converter slag, φ-pH diagram of V-Ti-H2O system at oxygen partial pressure of 0.5 MPa, ionic mass concentration of 0.1 mol/kg and temperatures rangi...To analyze the thermodynamic characteristics of leaching process of converter slag, φ-pH diagram of V-Ti-H2O system at oxygen partial pressure of 0.5 MPa, ionic mass concentration of 0.1 mol/kg and temperatures ranging from 60 to 200 ℃ was obtained by recently published critically assessed standard Gibbs energies and activity coefficients of various species. When pH2, stable regions of V3＋, VO2＋ and VO2＋ exist in the stable region of TiO2. The pH values of stable regions of vanadium and titanium decrease and redox potentials become more positive with the temperature increasing. Vanadium and titanium could be separated by one-step leaching based on thermodynamics. The experiment results of pressure acid leaching of converter slag show that leaching rates of vanadium and titanium are 96.87% and 8.76% respectively, at 140 ℃ of temperature, 0.5 MPa of oxygen partial pressure, 0.055-0.075mm of particle size, 15：1 of liquid to solid ratio, 120 min of leaching time, 500 r/min of stirring speed and 200 g/L of initial acid concentration. Vanadium and titanium could be selectively separated in the pressure acid leaching process, and the experiment result is in agreement with thermodynamic calculation result.展开更多
基金This work was supported by the National Science Foundation(CBET-1803256)Dr.C.Liu acknowledges the support from National Natural Science Foundation of China(52102277)the Fundamental Research Funds for the Central Universities,conducted by Tongji University.
文摘Vanadium oxides,par-ticularly hydrated forms like V_(2)O_(5)·nH_(2)O(VOH),stand out as promising cathode candidates for aqueous zinc ion batteries due to their adjustable layered structure,unique electronic characteristics,and high theoretical capacities.However,challenges such as vanadium dissolution,sluggish Zn^(2+)diffusion kinetics,and low operating voltage still hinder their direct application.In this study,we present a novel vanadium oxide([C_(6)H_(6)N(CH_(3))_(3)]_(1.08)V_(8)O_(20)·0.06H_(2)O,TMPA-VOH),developed by pre-inserting trimethylphenylammonium(TMPA+)cations into VOH.The incorporation of weakly polarized organic cations capitalizes on both ionic pre-intercalation and molecular pre-intercalation effects,resulting in a phase and morphology transition,an expansion of the interlayer distance,extrusion of weakly bonded interlayer water,and a substantial increase in V^(4+)content.These modifications synergistically reduce the electrostatic interactions between Zn^(2+)and the V-O lattice,enhancing structural stability and reaction kinetics during cycling.As a result,TMPA-VOH achieves an elevated open circuit voltage and operation voltage,exhibits a large specific capacity(451 mAh g^(-1)at 0.1 A g^(-1))coupled with high energy efficiency(89%),the significantly-reduced battery polarization,and outstanding rate capability and cycling stability.The concept introduced in this study holds great promise for the development of high-performance oxide-based energy storage materials.
基金Project (2009AA06Z106) supported by the High-tech Research and Development Program of ChinaProject (51174104) supported by the National Natural Science Foundation of ChinaProject (20115314110001) supported by the Doctoral Fund of Ministry of Education of China
文摘Extraction of vanadium（IV） from sulphate acid solution was studied using organophosphorous-based extractants D2EHPA, EHEHPA and CYANEX 272 in kerosene. The different parameters affecting the extraction of vanadium（IV） under equilibrium conditions were separately investigated to elucidate the stoichiometry of the extracted species. The distribution ratio of vanadium increased with increasing equilibrium pH of the aqueous phase, concentration of the extractants and temperature. D2EHPA was found to be a stronger extractant, having greater pH functionality than EHEHPA and CYANEX 272. Extraction of vanadium（IV） by these organophosphorous-based extractants involved cation exchange mechanism, and the extracted species appear to be VOR2（HR）2 in the low equilibrium pH and VOR2 in the higher equilibrium pH, where HR refers to the three acidic extractants.
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Project(2007CB613504)supported by the National Key Basic Research Program of ChinaProjects(51004033,50974035,51074047)supported by the National Natural Science Foundation of ChinaProject(2008BAB34B01)supported by National Science and Technology Support Plan of China during the 11th Five-Year Plan
文摘To analyze the thermodynamic characteristics of leaching process of converter slag, φ-pH diagram of V-Ti-H2O system at oxygen partial pressure of 0.5 MPa, ionic mass concentration of 0.1 mol/kg and temperatures ranging from 60 to 200 ℃ was obtained by recently published critically assessed standard Gibbs energies and activity coefficients of various species. When pH2, stable regions of V3＋, VO2＋ and VO2＋ exist in the stable region of TiO2. The pH values of stable regions of vanadium and titanium decrease and redox potentials become more positive with the temperature increasing. Vanadium and titanium could be separated by one-step leaching based on thermodynamics. The experiment results of pressure acid leaching of converter slag show that leaching rates of vanadium and titanium are 96.87% and 8.76% respectively, at 140 ℃ of temperature, 0.5 MPa of oxygen partial pressure, 0.055-0.075mm of particle size, 15：1 of liquid to solid ratio, 120 min of leaching time, 500 r/min of stirring speed and 200 g/L of initial acid concentration. Vanadium and titanium could be selectively separated in the pressure acid leaching process, and the experiment result is in agreement with thermodynamic calculation result.
