The electro-deoxidation of TiO2 was investigated in molten CaCl2.Back electromotive force measurements,constant voltage electrolytic experiments,contrast experiments of different cathodes,and cyclic voltammograms were...The electro-deoxidation of TiO2 was investigated in molten CaCl2.Back electromotive force measurements,constant voltage electrolytic experiments,contrast experiments of different cathodes,and cyclic voltammograms were carried out for solving the puzzle of reduction mechanism.The results showed that the reduction process proceeded step by step.TiO2 was first reduced to Ti3O5 or Ti2O3,and then further reduced to Ti3O,Ti2O,TiO and Ti.In addition,direct electrochemical reduction of titanium dioxide was the primary cathodic reaction;meanwhile,some calciothermic reduction reactions also happened at the cathode.Cyclic voltammograms of solid titanium dioxide and molybdenum wire in molten salts with different compositions were also studied.展开更多
ZrMn2 alloy was electro-synthesized directly from cathode pellets compacted with powdered mixture of MnO2 and ZrO2 in molten calcium chloride. Sintering temperature, cell voltage and electrolysis time were the dominan...ZrMn2 alloy was electro-synthesized directly from cathode pellets compacted with powdered mixture of MnO2 and ZrO2 in molten calcium chloride. Sintering temperature, cell voltage and electrolysis time were the dominant factors that affected the characteristics of the final product. The results confirmed the formation of pure ZrMn2 alloy through the electro-deoxidation of the mixed oxide pellets at 3.1 V for 12 h in 900 °C CaCl2 melt. The X-ray diffraction（XRD） and cyclic voltammetry analysis suggested that the electro-deoxidation proceeded from the reduction of manganese oxides to Mn, followed by ZrO2 or CaZrO3 reduction on the pre-formed Mn to ZrMn2 alloy. The cyclic voltammetry measurements using powder microelectrode showed that the prepared ZrMn2 alloy has a good electrochemical hydrogen storage property.展开更多
The electro-deoxidation of V2O3 precursors was studied. Experiments were carried out with a two-terminal electrochemical cell, which was comprised of a molten electrolyte of CaCl2 and NaC1 with additions of CaO, a cat...The electro-deoxidation of V2O3 precursors was studied. Experiments were carried out with a two-terminal electrochemical cell, which was comprised of a molten electrolyte of CaCl2 and NaC1 with additions of CaO, a cathode of compact V2O3, and a graphite anode under the potential of 3.0 V at 1173 K. The phase constitution and composition as well as the morphology of the samples were studied by X-ray diffraction （XRD） and scanning electron microscopy （SEM）. 3 g of V2O3 could be converted to vanadium metal powder within the processing time of 8 h. The kinetic pathway was investigated by analyzing the product phase in samples prepared at different reduction stages. CaO added in the reduction path of V2O3 formed the intermediate product CaV2O4.展开更多
A study was carried out on the preparation of YAl_(2) intermetallics from mixed oxide precursors using the method of electro-deoxidation.Y2O_(3) and Al_(2)O_(3) mixed in molar proportions of 1:2 were sintered at tempe...A study was carried out on the preparation of YAl_(2) intermetallics from mixed oxide precursors using the method of electro-deoxidation.Y2O_(3) and Al_(2)O_(3) mixed in molar proportions of 1:2 were sintered at temperatures ranging from 800 to 12000C for different hours.The sintered pellet was then electrolyzed in a molten CaCl_(2) at850℃using a graphite anode at a potential of 3.1 V.In this work,effects of sintering on the composition and the oxygen content in cathodic products were studied by X-ray diffraction(XRD)and oxygen-nitrogen analyzer.Sintering mainly affects the porosity of the pellets,and it is found that porosity decreases gradually with the increase in sintering temperature and the extension of sintering time.When sintered at 9000C for 4 h,the oxygen content in the cathodic product decreases to 1.85 wt%,and the efficiency of electro-deoxidation is 94.48%.At the same time,the mechanism of electrolysis was speculated.The results suggest that the formation of YAl_(2) is a multi-step process.During the reduction process from mixed oxides Y2O_(3)/Al_(2)O_(3) to YAl_(2) included many intermediate materials,such as YAlO_(3),Y3Al5O12 and YAl3,YAl_(2) intermediate alloy was prepared finally.展开更多
A combined process of molten salt electro-deoxidation and vacuum hot-pressing sintering was proposed to prepare AlCrFeNiTi_(x) high-entropy alloy(HEA)-TiN ceramic coating composites on low-carbon steel surfaces,where ...A combined process of molten salt electro-deoxidation and vacuum hot-pressing sintering was proposed to prepare AlCrFeNiTi_(x) high-entropy alloy(HEA)-TiN ceramic coating composites on low-carbon steel surfaces,where nitrides were introduced from BN isolater between graphite mold and HEA powders.The effect of Ti content on the microstructure,ultimate tensile strength,hardness,and wear resistance of the composites was investigated,and the bonding mechanism was elucidated.Results demonstrate that the composites have excellent hardness and wear resistance.The hardness of composites is significantly increased with the increase in Ti content.The extremely high wear resistance is attributed to the extremely high melting point and high thermal hardness of TiN,which can effectively prevent oxidation deformation of the worn surface.展开更多
CeCo5 alloy was prepared from the mixture of cobalt oxide （Co3O4） and cerium oxide （CeO2） powders by electro-deoxidation in molten calcium chloride. The effects of the cell voltage and sintering temperature on the...CeCo5 alloy was prepared from the mixture of cobalt oxide （Co3O4） and cerium oxide （CeO2） powders by electro-deoxidation in molten calcium chloride. The effects of the cell voltage and sintering temperature on the electrolysis process were reported. The electro-deoxidation mechanism was investigated by potentiodynamic polarization using a molybdenum cavity electrode in conjunction with characterization of the products from constant voltage electrolysis under different conditions by XRD and SEM. The electrochemical property of CeCo5 alloy was investigated by cyclic voltammetry measurements. The results show that the electro-deoxidation rate increases with increasing the cell voltage and decreasing the sintering temperature. The pure CeCo5 can be prepared by direct electro-deoxidation of mixed CeO2/Co3O4 pellets sintered at 850 °C when the cell voltage of 3.1 V is applied. The electro-deoxidation proceeds by the simultaneous reduction of Co3O4 to Co and reduction of CeO2 to CeOCl, followed by CeOCl reduction on the pre-formed Co to form CeCo5 alloy which shows a good cycling stability.展开更多
(La;Mg;);(Ni;Co;);（x = 0.125, 0.25, 0.5） alloys were synthesized from the sintered mixture of La;O;+ Ni O + Co O + Mg O in the molten CaCl;electrolyte at 750 °C and the electrochemical hydrogen storage capaciti...(La;Mg;);(Ni;Co;);（x = 0.125, 0.25, 0.5） alloys were synthesized from the sintered mixture of La;O;+ Ni O + Co O + Mg O in the molten CaCl;electrolyte at 750 °C and the electrochemical hydrogen storage capacities of the synthesized alloys were measured. Non-hygroscopic LaNiO;phase formed during sintering（at 1200 °C for 2 h） as a result of the reaction of hygroscopic La;O;with NiO. Another sinter product was Mg;Ni;O phase. Both mixed oxide sinter products facilitated the La-Ni and Mg-Ni phase formations. X-ray diffraction peaks indicated that the first stable phase appeared in the alloy structure was LaNi;which formed upon reduction of La;NiO;phase. Increase in Mg content caused formation of La;Mg;Ni;phase in the alloy structure and the presence of this phase improved the hydrogen storage performance of the electrodes. It was observed that(La;Mg;);(Ni;Co;);（x = 0.125, 0.25, 0.5） alloys have promising discharge capacities change between 319 m Ah/g and 379 m Ah/g depending on the alloy Mg content.展开更多
new method is proposed for the recovery of Mn via the direct electrochemical reduction of LiMn_(2)O_(4) from the waste of lithium-ion batteries in NaCl−CaCl_(2) melts at 750°C.The results show that the LiMn_(2)O_...new method is proposed for the recovery of Mn via the direct electrochemical reduction of LiMn_(2)O_(4) from the waste of lithium-ion batteries in NaCl−CaCl_(2) melts at 750°C.The results show that the LiMn_(2)O_(4) reduction process by the electrochemical method on the coated electrode surface occurs in three steps:Mn(IV)→Mn(III)→Mn(II)→Mn.The products of this electro-deoxidation are CaMn2O4,MnO,(MnO)x(CaO)1−x,and Mn.Metal Mn appears when the electrolytic voltage increases to 2.6 V,which indicates that increasing the voltage may promote the deoxidation reaction process.With the advancement of the three-phase interline(3PI),electric deoxygenation gradually proceeds from the outer area of the crucible to the core.At high voltage,the kinetic process of the reduction reaction is accelerated,which generates double 3PIs at different stages.展开更多
Direct electrochemical extraction of TisSia from pressed cathode pellets comprising of powdered Ti/Si- containing metal oxide compounds was investigated by using molten salt electro-deoxidation technology. Three group...Direct electrochemical extraction of TisSia from pressed cathode pellets comprising of powdered Ti/Si- containing metal oxide compounds was investigated by using molten salt electro-deoxidation technology. Three groups of mixtures including TiO2 mixed with SiO2, Ti-bearing blast furnace slag （TBFS） mixed with TiO2, and TBFS mixed with high-titanium slag （HTS） were prepared at the same stoichiometric ratio （Ti ： Si = 5 ： 3） corresponding to the target composition of Ti5Si3, and used as the starting materials in this experiment, respec- tively. The pressed porous cylindrical pellet of the Ti/Si-contalning compounds served as a cathode, and two different anode systems, i.e., the inert solid oxide oxygen-ion-conducting membrane （SOM） based anode system and graphite-based anode system were used contrastively. The electrochemical experiment was carried out at 900--1050℃ and 3.0--4.0V in molten CaCl2 electrolyte. The results show that the oxide components were electro-deoxidized effectively and Ti5Si3 could be directly extracted from these complex Ti/Si-containing metal oxide compounds.展开更多
The formation of a rust layer on iron and steels surfaces accelerates their degradation and eventually causes material failure.In addition to fabricating a protective layer or using a sacrificial anode, repairing or r...The formation of a rust layer on iron and steels surfaces accelerates their degradation and eventually causes material failure.In addition to fabricating a protective layer or using a sacrificial anode, repairing or removing the rust layer is another way to reduce the corrosion rate and extend the lifespans of iron and steels.Herein, an electrochemical healing approach was employed to repair the rust layer in molten Na_(2)CO_(3)-K_(2)CO_(3).The rusty layers on iron rods and screws were electrochemically converted to iron in only several minutes and a metallic luster appeared.Scanning electron microscopy(SEM) and energy dispersive X-ray spectroscopy(EDS) analyses showed that the structures of the rust layer after healing were slightly porous and the oxygen content reached a very low level.Thus, high-temperature molten-salt electrolysis may be an effective way to metalize iron rust of various shapes and structures in a short time, and could be used in the repair of cultural relics and even preparing a three-dimensional porous structures for other applications.展开更多
Aluminum-selenium(Al-Se)batteries have been considered as one of the most promising energy storage systems owing to their high capacity,energy density,and cost effectiveness,but Se falls challenges in addressing the s...Aluminum-selenium(Al-Se)batteries have been considered as one of the most promising energy storage systems owing to their high capacity,energy density,and cost effectiveness,but Se falls challenges in addressing the shuttle effect of soluble intermediate product and sluggish reaction kinetics in the solid-solid conversion process during cycling.Herein,we propose an unprecedented design concept for fabricating uniform Se/C hollow microspheres with controllable morphologies through low-temperature electro-deoxidation in neutral NaCl-AlCl_(3) molten salt system.Such Se/C hollow microspheres are demonstrated to hold a favorable hollow structure for hosting Se,which can not only suppress the dissolution of soluble intermediate products into the electrolyte,thereby maintaining the structural integrity and maximizing Se utilization of the active material,but also promote the electrical/ionic conductivity,thus facilitating the rapid reaction kinetics during cycling.Accordingly,the as-prepared Se/C hollow microspheres exhibit a high reversible capacity of 720.1 mAh g^(−1)at 500 mA g^(−1).Even at the high current density of 1000 mA g^(−1),Se/C delivers a high discharge capacity of 564.0 mAh g^(−1),long-term stability over 1100 cycles and high Coulombic efficiency of 98.6%.This present work provides valuable insights into short-process recovery of advanced Se-containingmaterials and value-added utilization for energy storage.展开更多
基金Project(2006AA068128)supported by the Hi-tech Research and Development Program of China
文摘The electro-deoxidation of TiO2 was investigated in molten CaCl2.Back electromotive force measurements,constant voltage electrolytic experiments,contrast experiments of different cathodes,and cyclic voltammograms were carried out for solving the puzzle of reduction mechanism.The results showed that the reduction process proceeded step by step.TiO2 was first reduced to Ti3O5 or Ti2O3,and then further reduced to Ti3O,Ti2O,TiO and Ti.In addition,direct electrochemical reduction of titanium dioxide was the primary cathodic reaction;meanwhile,some calciothermic reduction reactions also happened at the cathode.Cyclic voltammograms of solid titanium dioxide and molybdenum wire in molten salts with different compositions were also studied.
基金Project(51201058)supported by the National Natural Science Foundation of ChinaProjects(E2010000941,E2014209009)supported by Hebei Provincial Natural Science Foundation of China
文摘ZrMn2 alloy was electro-synthesized directly from cathode pellets compacted with powdered mixture of MnO2 and ZrO2 in molten calcium chloride. Sintering temperature, cell voltage and electrolysis time were the dominant factors that affected the characteristics of the final product. The results confirmed the formation of pure ZrMn2 alloy through the electro-deoxidation of the mixed oxide pellets at 3.1 V for 12 h in 900 °C CaCl2 melt. The X-ray diffraction（XRD） and cyclic voltammetry analysis suggested that the electro-deoxidation proceeded from the reduction of manganese oxides to Mn, followed by ZrO2 or CaZrO3 reduction on the pre-formed Mn to ZrMn2 alloy. The cyclic voltammetry measurements using powder microelectrode showed that the prepared ZrMn2 alloy has a good electrochemical hydrogen storage property.
基金financially supported by the National Natural Science Foundation of China (Nos.51154002 and 50834001)Panzhihua New Steel and Vanadium Co.Ltd
文摘The electro-deoxidation of V2O3 precursors was studied. Experiments were carried out with a two-terminal electrochemical cell, which was comprised of a molten electrolyte of CaCl2 and NaC1 with additions of CaO, a cathode of compact V2O3, and a graphite anode under the potential of 3.0 V at 1173 K. The phase constitution and composition as well as the morphology of the samples were studied by X-ray diffraction （XRD） and scanning electron microscopy （SEM）. 3 g of V2O3 could be converted to vanadium metal powder within the processing time of 8 h. The kinetic pathway was investigated by analyzing the product phase in samples prepared at different reduction stages. CaO added in the reduction path of V2O3 formed the intermediate product CaV2O4.
基金financially supported by the Major State Basic Research Development Program of China(No.2012BA01207)。
文摘A study was carried out on the preparation of YAl_(2) intermetallics from mixed oxide precursors using the method of electro-deoxidation.Y2O_(3) and Al_(2)O_(3) mixed in molar proportions of 1:2 were sintered at temperatures ranging from 800 to 12000C for different hours.The sintered pellet was then electrolyzed in a molten CaCl_(2) at850℃using a graphite anode at a potential of 3.1 V.In this work,effects of sintering on the composition and the oxygen content in cathodic products were studied by X-ray diffraction(XRD)and oxygen-nitrogen analyzer.Sintering mainly affects the porosity of the pellets,and it is found that porosity decreases gradually with the increase in sintering temperature and the extension of sintering time.When sintered at 9000C for 4 h,the oxygen content in the cathodic product decreases to 1.85 wt%,and the efficiency of electro-deoxidation is 94.48%.At the same time,the mechanism of electrolysis was speculated.The results suggest that the formation of YAl_(2) is a multi-step process.During the reduction process from mixed oxides Y2O_(3)/Al_(2)O_(3) to YAl_(2) included many intermediate materials,such as YAlO_(3),Y3Al5O12 and YAl3,YAl_(2) intermediate alloy was prepared finally.
基金National Natural Science Foundation of China(52174315)Youth Scholars Promotion Plan of North China University of Science and Technology(QNTJ202304)。
文摘A combined process of molten salt electro-deoxidation and vacuum hot-pressing sintering was proposed to prepare AlCrFeNiTi_(x) high-entropy alloy(HEA)-TiN ceramic coating composites on low-carbon steel surfaces,where nitrides were introduced from BN isolater between graphite mold and HEA powders.The effect of Ti content on the microstructure,ultimate tensile strength,hardness,and wear resistance of the composites was investigated,and the bonding mechanism was elucidated.Results demonstrate that the composites have excellent hardness and wear resistance.The hardness of composites is significantly increased with the increase in Ti content.The extremely high wear resistance is attributed to the extremely high melting point and high thermal hardness of TiN,which can effectively prevent oxidation deformation of the worn surface.
基金Project (E2010000941) supported by Hebei Provincial Natural Science Foundation of ChinaProject (11212119D) supported by Hebei Provincial Science and Technology Support Program of China
文摘CeCo5 alloy was prepared from the mixture of cobalt oxide （Co3O4） and cerium oxide （CeO2） powders by electro-deoxidation in molten calcium chloride. The effects of the cell voltage and sintering temperature on the electrolysis process were reported. The electro-deoxidation mechanism was investigated by potentiodynamic polarization using a molybdenum cavity electrode in conjunction with characterization of the products from constant voltage electrolysis under different conditions by XRD and SEM. The electrochemical property of CeCo5 alloy was investigated by cyclic voltammetry measurements. The results show that the electro-deoxidation rate increases with increasing the cell voltage and decreasing the sintering temperature. The pure CeCo5 can be prepared by direct electro-deoxidation of mixed CeO2/Co3O4 pellets sintered at 850 °C when the cell voltage of 3.1 V is applied. The electro-deoxidation proceeds by the simultaneous reduction of Co3O4 to Co and reduction of CeO2 to CeOCl, followed by CeOCl reduction on the pre-formed Co to form CeCo5 alloy which shows a good cycling stability.
基金Financial assistance from The Scientific and Technological Research Council of Turkey is gratefully acknowledged(Project No:MAG 113M139)
文摘(La;Mg;);(Ni;Co;);（x = 0.125, 0.25, 0.5） alloys were synthesized from the sintered mixture of La;O;+ Ni O + Co O + Mg O in the molten CaCl;electrolyte at 750 °C and the electrochemical hydrogen storage capacities of the synthesized alloys were measured. Non-hygroscopic LaNiO;phase formed during sintering（at 1200 °C for 2 h） as a result of the reaction of hygroscopic La;O;with NiO. Another sinter product was Mg;Ni;O phase. Both mixed oxide sinter products facilitated the La-Ni and Mg-Ni phase formations. X-ray diffraction peaks indicated that the first stable phase appeared in the alloy structure was LaNi;which formed upon reduction of La;NiO;phase. Increase in Mg content caused formation of La;Mg;Ni;phase in the alloy structure and the presence of this phase improved the hydrogen storage performance of the electrodes. It was observed that(La;Mg;);(Ni;Co;);（x = 0.125, 0.25, 0.5） alloys have promising discharge capacities change between 319 m Ah/g and 379 m Ah/g depending on the alloy Mg content.
基金the National Nat-ural Science Foundation of China(No.51774143).
文摘new method is proposed for the recovery of Mn via the direct electrochemical reduction of LiMn_(2)O_(4) from the waste of lithium-ion batteries in NaCl−CaCl_(2) melts at 750°C.The results show that the LiMn_(2)O_(4) reduction process by the electrochemical method on the coated electrode surface occurs in three steps:Mn(IV)→Mn(III)→Mn(II)→Mn.The products of this electro-deoxidation are CaMn2O4,MnO,(MnO)x(CaO)1−x,and Mn.Metal Mn appears when the electrolytic voltage increases to 2.6 V,which indicates that increasing the voltage may promote the deoxidation reaction process.With the advancement of the three-phase interline(3PI),electric deoxygenation gradually proceeds from the outer area of the crucible to the core.At high voltage,the kinetic process of the reduction reaction is accelerated,which generates double 3PIs at different stages.
基金the National Natural Science Foundation of China(No.51074105)the China Postdoctoral Science Foundation(No.2012M520873)China National Funds for Distinguished Young Scientists (No.51225401)
文摘Direct electrochemical extraction of TisSia from pressed cathode pellets comprising of powdered Ti/Si- containing metal oxide compounds was investigated by using molten salt electro-deoxidation technology. Three groups of mixtures including TiO2 mixed with SiO2, Ti-bearing blast furnace slag （TBFS） mixed with TiO2, and TBFS mixed with high-titanium slag （HTS） were prepared at the same stoichiometric ratio （Ti ： Si = 5 ： 3） corresponding to the target composition of Ti5Si3, and used as the starting materials in this experiment, respec- tively. The pressed porous cylindrical pellet of the Ti/Si-contalning compounds served as a cathode, and two different anode systems, i.e., the inert solid oxide oxygen-ion-conducting membrane （SOM） based anode system and graphite-based anode system were used contrastively. The electrochemical experiment was carried out at 900--1050℃ and 3.0--4.0V in molten CaCl2 electrolyte. The results show that the oxide components were electro-deoxidized effectively and Ti5Si3 could be directly extracted from these complex Ti/Si-containing metal oxide compounds.
基金financially supported by the Fundamental Research Funds for the Central Universities (No.N172505002)the National Natural Science Foundation of China (No.51704060)+1 种基金the National Thousand Youth Talent Program of Chinathe 111 Project (No.B16009)。
文摘The formation of a rust layer on iron and steels surfaces accelerates their degradation and eventually causes material failure.In addition to fabricating a protective layer or using a sacrificial anode, repairing or removing the rust layer is another way to reduce the corrosion rate and extend the lifespans of iron and steels.Herein, an electrochemical healing approach was employed to repair the rust layer in molten Na_(2)CO_(3)-K_(2)CO_(3).The rusty layers on iron rods and screws were electrochemically converted to iron in only several minutes and a metallic luster appeared.Scanning electron microscopy(SEM) and energy dispersive X-ray spectroscopy(EDS) analyses showed that the structures of the rust layer after healing were slightly porous and the oxygen content reached a very low level.Thus, high-temperature molten-salt electrolysis may be an effective way to metalize iron rust of various shapes and structures in a short time, and could be used in the repair of cultural relics and even preparing a three-dimensional porous structures for other applications.
基金National Natural Science Foundation of China,Grant/Award Number:51874019Fundamental Research Funds for the Central Universities,Grant/Award Number:FRF-TP-19-079A1State Scholarship Fund。
文摘Aluminum-selenium(Al-Se)batteries have been considered as one of the most promising energy storage systems owing to their high capacity,energy density,and cost effectiveness,but Se falls challenges in addressing the shuttle effect of soluble intermediate product and sluggish reaction kinetics in the solid-solid conversion process during cycling.Herein,we propose an unprecedented design concept for fabricating uniform Se/C hollow microspheres with controllable morphologies through low-temperature electro-deoxidation in neutral NaCl-AlCl_(3) molten salt system.Such Se/C hollow microspheres are demonstrated to hold a favorable hollow structure for hosting Se,which can not only suppress the dissolution of soluble intermediate products into the electrolyte,thereby maintaining the structural integrity and maximizing Se utilization of the active material,but also promote the electrical/ionic conductivity,thus facilitating the rapid reaction kinetics during cycling.Accordingly,the as-prepared Se/C hollow microspheres exhibit a high reversible capacity of 720.1 mAh g^(−1)at 500 mA g^(−1).Even at the high current density of 1000 mA g^(−1),Se/C delivers a high discharge capacity of 564.0 mAh g^(−1),long-term stability over 1100 cycles and high Coulombic efficiency of 98.6%.This present work provides valuable insights into short-process recovery of advanced Se-containingmaterials and value-added utilization for energy storage.
