构建准确可靠的热力学数据库对提钒过程优化以及钒酸盐材料的制备具有重要的应用价值和指导意义。采用封闭铂金坩埚,结合X射线衍射(XRD)与差热分析(DTA)技术,证实了K_(2)O-V_(2)O_(5)体系中K_(3)V_(5)O_(14)为稳定存在的化合物,并试验...构建准确可靠的热力学数据库对提钒过程优化以及钒酸盐材料的制备具有重要的应用价值和指导意义。采用封闭铂金坩埚,结合X射线衍射(XRD)与差热分析(DTA)技术,证实了K_(2)O-V_(2)O_(5)体系中K_(3)V_(5)O_(14)为稳定存在的化合物,并试验测定了K_(2)V_(8)O_(21)和KVO_(3)的熔化温度分别为532.4℃和516.5℃。随后采用修正的准化学模型(MQM),引入溶液中第二相邻阳离子短程有序对描述吉布斯自由能的变化。基于CALPHAD框架(CALculation of PHAse Diagram,相图计算),构建了Na_(2)O-K_(2)O-V_(2)O_(5)体系的热力学模型,重现了Na_(2)O-K_(2)O-V_(2)O_(5)体系全组分范围的实验数据和热力学性质,获得了该体系中所有物相一系列自洽的热力学模型参数,最终构建了可靠的热力学数据库。进一步探讨了当前数据库在钒渣钠化焙烧提钒中的应用,明确了含钒物相的迁移规律,确定了最佳的操作温度窗口。展开更多
A simplified CaO-V_(2)O_(5)-MnO_(2) system was established to qualitatively and quantitatively investigate the transformation behavior of vanadates.The results demonstrated dynamic transformations between calcium vana...A simplified CaO-V_(2)O_(5)-MnO_(2) system was established to qualitatively and quantitatively investigate the transformation behavior of vanadates.The results demonstrated dynamic transformations between calcium vanadate and manganese vanadate as n(CaO)/n(V_(2)O_(5))/n(MnO_(2))ratios and roasting temperatures varied.When MnO_(2) was incrementally added with n(CaO)/n(V_(2)O_(5))of 2,some Ca_(2)V_(2)O_(7) converted to Mn_(2)V_(2)O_(7).The mass of vanadium as calcium vanadate consistently exceeded that as manganese vanadate.Conversely,when CaO was gradually added with n(MnO_(2))/n(V_(2)O_(5))of 2,Mn_(2)V_(2)O_(7) tended to transform into Ca_(2)V_(2)O_(7) and Ca3V2O8.The affinity of vanadium for calcium was higher compared that of vanadium for manganese.The specific type of calcium vanadate formed depended on both n(CaO)/n(V_(2)O_(5))/n(MnO_(2))values and roasting temperatures,while manganese vanadate remained predominantly as Mn_(2)V_(2)O_(7).The influence of roasting temperature on the conversion between calcium vanadate and manganese vanadate was minimal.At n(CaO)/n(V_(2)O_(5))/n(MnO_(2))of 2/1/2 and temperatures ranging from 650 to 850°C,the mass ratio of vanadium present as calcium vanadate to manganese vanadate stabilized at approximately 2.展开更多
Aqueous batteries are an emerging next-generation technology for large-scale energy storage.Among various metal-ion systems,manganese-based batteries have attracted significant interest due to their superior theoretic...Aqueous batteries are an emerging next-generation technology for large-scale energy storage.Among various metal-ion systems,manganese-based batteries have attracted significant interest due to their superior theoretical energy density over zinc-based battery systems.This study demonstrates oxygen vacancy-engineered vanadium oxide(V_(2)O_(4.85))as a high-performance cathode material for aqueous manganese metal batteries.The V_(2)O_(4.85) cathode had a discharge capacity of 212.6 mAh g^(-1) at 0.1 A g^(-1),retaining 89.5%capacity after 500 cycles.Oxygen vacancies enhanced ion diffusion and reduced migration barriers,facilitating both Mn^(2+)and H^(+)ion intercalation.Proton intercalation dominated charge storage,forming Mn(OH)_(2) layers,whereas Mn^(2+)contributed to surface-limited reactions.Furthermore,manganese metal batteries had a significantly higher operating voltage than that of aqueous zinc battery systems.Despite challenges with hydrogen evolution reactions at the Mn metal anode,this study underscores the potential of manganese batteries for future energy storage systems.展开更多
The insulating nature and dissolution of vanadium-based oxides in aqueous electrolytes result in low capacity and lifespan during charge/discharge process, which is unable to meet the demands for the development and a...The insulating nature and dissolution of vanadium-based oxides in aqueous electrolytes result in low capacity and lifespan during charge/discharge process, which is unable to meet the demands for the development and application of high-energy-density aqueous zinc-ion batteries(AZIBs). Herein, a novel V_(2)O_(5-x)@C composite cathode consisting of conductive carbon coatings with abundant oxygen vacancies is specifically designed through plasma-enhanced chemical vapor deposition(PECVD) method. As expected,the ideal microstructure of V_(2)O_(5-x)@C cathode enables large specific surface areas, fast electron/ion diffusion kinetics, and superior interfacial stability, which can realize outstanding cycling stability and electrochemical performance. Consequently, the V_(2)O_(5-x)@C composite cathode delivers a high reversible rate capacity of 130.6 mAh/g at 10 A/g and remains 277.6 mAh/g when returned to 1 A/g. In addition, the Zn//V_(2)O_(5-x)@C full cell can stably cycle for 1000 cycles with a high initial specific capacity of 149.2 m Ah/g,possessing 83.8% capacity retention at 5 A/g. The process of constructing a conductive layer on the surface of cathode materials while increasing oxygen vacancies in the structure through PECVD provides new insight into the design of high-performance cathode materials for AZIBs.展开更多
文摘构建准确可靠的热力学数据库对提钒过程优化以及钒酸盐材料的制备具有重要的应用价值和指导意义。采用封闭铂金坩埚,结合X射线衍射(XRD)与差热分析(DTA)技术,证实了K_(2)O-V_(2)O_(5)体系中K_(3)V_(5)O_(14)为稳定存在的化合物,并试验测定了K_(2)V_(8)O_(21)和KVO_(3)的熔化温度分别为532.4℃和516.5℃。随后采用修正的准化学模型(MQM),引入溶液中第二相邻阳离子短程有序对描述吉布斯自由能的变化。基于CALPHAD框架(CALculation of PHAse Diagram,相图计算),构建了Na_(2)O-K_(2)O-V_(2)O_(5)体系的热力学模型,重现了Na_(2)O-K_(2)O-V_(2)O_(5)体系全组分范围的实验数据和热力学性质,获得了该体系中所有物相一系列自洽的热力学模型参数,最终构建了可靠的热力学数据库。进一步探讨了当前数据库在钒渣钠化焙烧提钒中的应用,明确了含钒物相的迁移规律,确定了最佳的操作温度窗口。
基金finally supported by the National Natural Science Foundation of China (Nos.52204309,52174277,52374300)。
文摘A simplified CaO-V_(2)O_(5)-MnO_(2) system was established to qualitatively and quantitatively investigate the transformation behavior of vanadates.The results demonstrated dynamic transformations between calcium vanadate and manganese vanadate as n(CaO)/n(V_(2)O_(5))/n(MnO_(2))ratios and roasting temperatures varied.When MnO_(2) was incrementally added with n(CaO)/n(V_(2)O_(5))of 2,some Ca_(2)V_(2)O_(7) converted to Mn_(2)V_(2)O_(7).The mass of vanadium as calcium vanadate consistently exceeded that as manganese vanadate.Conversely,when CaO was gradually added with n(MnO_(2))/n(V_(2)O_(5))of 2,Mn_(2)V_(2)O_(7) tended to transform into Ca_(2)V_(2)O_(7) and Ca3V2O8.The affinity of vanadium for calcium was higher compared that of vanadium for manganese.The specific type of calcium vanadate formed depended on both n(CaO)/n(V_(2)O_(5))/n(MnO_(2))values and roasting temperatures,while manganese vanadate remained predominantly as Mn_(2)V_(2)O_(7).The influence of roasting temperature on the conversion between calcium vanadate and manganese vanadate was minimal.At n(CaO)/n(V_(2)O_(5))/n(MnO_(2))of 2/1/2 and temperatures ranging from 650 to 850°C,the mass ratio of vanadium present as calcium vanadate to manganese vanadate stabilized at approximately 2.
基金supported by the Global Joint Research Program funded by Pukyong National University(202411790001)supported by the Nano&Material Technology Development Program through the National Research Foundation of Korea(NRF),funded by the Ministry of Science and ICT(RS-2024-00446825)by the Technology Innovation Program(RS-2024-00418815)funded by the Ministry of Trade,Industry&Energy(MOTIE,Korea).
文摘Aqueous batteries are an emerging next-generation technology for large-scale energy storage.Among various metal-ion systems,manganese-based batteries have attracted significant interest due to their superior theoretical energy density over zinc-based battery systems.This study demonstrates oxygen vacancy-engineered vanadium oxide(V_(2)O_(4.85))as a high-performance cathode material for aqueous manganese metal batteries.The V_(2)O_(4.85) cathode had a discharge capacity of 212.6 mAh g^(-1) at 0.1 A g^(-1),retaining 89.5%capacity after 500 cycles.Oxygen vacancies enhanced ion diffusion and reduced migration barriers,facilitating both Mn^(2+)and H^(+)ion intercalation.Proton intercalation dominated charge storage,forming Mn(OH)_(2) layers,whereas Mn^(2+)contributed to surface-limited reactions.Furthermore,manganese metal batteries had a significantly higher operating voltage than that of aqueous zinc battery systems.Despite challenges with hydrogen evolution reactions at the Mn metal anode,this study underscores the potential of manganese batteries for future energy storage systems.
基金financially supported by the National Natural Science Foundation of China (No. 52377222)Natural Science Foundation of Hunan Province (No. 2023JJ20064)。
文摘The insulating nature and dissolution of vanadium-based oxides in aqueous electrolytes result in low capacity and lifespan during charge/discharge process, which is unable to meet the demands for the development and application of high-energy-density aqueous zinc-ion batteries(AZIBs). Herein, a novel V_(2)O_(5-x)@C composite cathode consisting of conductive carbon coatings with abundant oxygen vacancies is specifically designed through plasma-enhanced chemical vapor deposition(PECVD) method. As expected,the ideal microstructure of V_(2)O_(5-x)@C cathode enables large specific surface areas, fast electron/ion diffusion kinetics, and superior interfacial stability, which can realize outstanding cycling stability and electrochemical performance. Consequently, the V_(2)O_(5-x)@C composite cathode delivers a high reversible rate capacity of 130.6 mAh/g at 10 A/g and remains 277.6 mAh/g when returned to 1 A/g. In addition, the Zn//V_(2)O_(5-x)@C full cell can stably cycle for 1000 cycles with a high initial specific capacity of 149.2 m Ah/g,possessing 83.8% capacity retention at 5 A/g. The process of constructing a conductive layer on the surface of cathode materials while increasing oxygen vacancies in the structure through PECVD provides new insight into the design of high-performance cathode materials for AZIBs.
