钒化合物作为钒电池电极材料的稳定性及电化学行为研究  

Stability and electrochemical behaviour of vanadium compounds as electrode materials for vanadium batteries

作　　者：潘东 刘涛[1,2,3,4] 张一敏[1,2,3,4] 刘红 魏莲[1,2,3,4] PAN Dong;LIU Tao;ZHANG Yimin;LIU Hong;WEI Lian(School of Resources and Environmental Engineering,Wuhan University of Science and Technology,Wuhan 430081,China;State Environmental Protection Key Laboratory of Mineral Metallurgical Resources Utilization and Pollution Control,Wuhan 430081,China;Collaborative Innovation Center of Strategic Vanadium Resources Utilization,Wuhan 430081,China;Hubei Provincial Engineering Technology Research Center of High Efficient Cleaning Utilization for Shale Vanadium Resource,Wuhan 430081,China;School of Mining and Mechanical Engineering,Liupanshui Normal University,Liupanshui,553004,China)

机构地区：[1]武汉科技大学资源与环境工程学院,湖北武汉430081 [2]国家环境保护矿冶资源利用与污染控制重点实验室,湖北武汉430081 [3]战略钒资源利用省部共建协同创新中心,湖北武汉430081 [4]湖北省页岩钒资源高效清洁利用工程技术研究中心,湖北武汉430081 [5]六盘水师范学院矿业与机械工程学院,贵州六盘水553004

出　　处：《中国有色冶金》2023年第5期51-59,共9页China Nonferrous Metallurgy

基　　金：国家自然科学基金资助项目(51774216);湖北省科技创新专项资助项目(2017ACA185)。

摘　　要：钒化合物具有较好电化学活性,有望用于提升钒电池电极电化学活性,但目前对于钒化合物在电解液中的稳定性及电化学行为的研究有待开展。因此,本文利用E-pH图、开路电位法、循环伏安法等方法,研究了V_(2)O_(5)、VO_(2)、V_(2)O_(3)、NaV_(2)O_(5)、VN等钒化合物在酸性电解液中的稳定性及电化学行为。在稳定性方面,结合钒化合物的E-pH图、溶解试验以及开路电位分析,VO_(2)、NaV_(2)O_(5)在钒电池电解液中不稳定,会发生快速溶解;V_(2)O_(5)在钒电池电解液中相对稳定,会发生缓慢溶解;V_(2)O_(3)和VN在钒电池电解液中较稳定,仅发生少量溶解。在电化学行为方面,结合钒化合物在2.0 mol·L^(-1) H_(2)SO_(4)、0.1 mol·L^(-1) V^(3+)+2.0 mol·L^(-1) H_(2)SO_(4)、0.1 mol·L^(-1) V^(4+)+2.0 mol·L^(-1) H_(2)SO_(4)电解液中的循环伏安曲线分析,V_(2)O_(5)、V_(2)O_(3)、VN会在电势0.4-1.5 V发生显著的氧化还原反应,在电势-0.8--0.2 V不会发生明显的氧化还原反应;VN对V^(5+)/V^(4+)、V^(3+)/V^(2+)电对反应具有较好的催化作用,V_(2)O_(3)的催化作用次之,V_(2)O_(5)的催化作用最弱。因此,V_(2)O_(3)、VN可作为V^(3+)/V^(2+)电对反应催化材料用于提高钒电池负极电化学活性,实现钒电池性能的提升。Vanadium compounds have good electrochemical activity and are expected to be used to enhance the electrochemical activity of vanadium battery electrodes,but the stability and electrochemical behavior of vanadium compounds in electrolytes have not been investigated yet.Therefore,the stability and electrochemical behavior of vanadium compounds such as V_(2)O_(5),VO_(2),V_(2)O_(3),NaV_(2)O_(5)and VN in acidic electrolytes have been investigated using E-pH diagram,open circuit potential method and cyclic voltammetry in this paper.In terms of stability,the E-pH diagram,dissolution tests and open circuit potential analysis of vanadium compounds show that VO_(2)and NaV_(2)O_(5) are unstable in vanadium battery electrolytes and undergo rapid dissolution;V_(2)O_(5)is relatively stable in vanadium battery electrolytes and undergoes slow dissolution;V_(2)O_(3)and VN are more stable in vanadium battery electrolytes and undergo simall amounts of dissolution.In terms of electrochemical behavior,combined with cyclic voltametric analysis of vanadium compounds in 2.0 mol·L^(-1)H_(2)SO_(4),0.1 mol.L^(-1)V^(3+)+2.0 mol·L^(-1)H_(2)SO_(4),and 0.1 mol·L^(-1) V^(4+)+2.0 mol·L^(-1)H_(2)SO_(4) electrolytes,V_(2)O_(5),V_(2)O_(3)and VN undergo significant redox reactions at 0.4 to 1.5 V and no significant redox reactions at-0.8 to-0.2 V;VN has better catalytic effect on the V^(5+)/V^(4+)and V^(3+)/V^(2+) electro pair reactions,with V_(2)O_(3)being the next most catalytic and V_(2)O_(5)the weakest.Therefore,V_(2)O_(3)and VN can be used as catalytic materials for V^(3+)/V^(2+) electro pair reactions to improve the electrochemical activity of vanadium battery anodes to achieve improved performance of vanadium batteries.

关 键 词：钒化合物 电化学 全钒液流电池 E-pH 循环伏安 V_(2)O_(5) 电解液 开路电位 催化 

分 类 号：TM912[电气工程—电力电子与电力传动] TF841.3[冶金工程—有色金属冶金] TF801