A mixed-valence polyoxometalate-based 3D inorganic framework cathode material for high-efficiency rechargeable AZIBs  

作　　者：Qing Han Hao-Ran Xiao Tao Zhou Bing-Chuan Li Liu Yang Ling-Ling Xie Xue-Jing Qiu Xian-Yong Wu Li-Min Zhu Xiao-Yu Cao 

机构地区：[1]School of Chemistry and Chemical Engineering,Henan University of Technology,Zhengzhou 450001,China [2]Key Laboratory of High Specific Energy Materials for Electrochemical Power Sources of Zhengzhou City,Zhengzhou 450001,China [3]College of Materials Engineering,Henan University of Engineering,Zhengzhou450007,China [4]School of Environmental Engineering,Henan University of Technology,Zhengzhou 450001,China [5]Department of Chemistry,University of Puerto Rico-Rio Piedras Campus,San Juan,PR 00925,USA

出　　处：《Rare Metals》2024年第8期3677-3691,共15页稀有金属（英文版）

基　　金：financially supported by the National Natural Science Foundation of China(Nos.52071132,52261135632 and U21A20284);Zhongyuan Thousand People PlanThe Zhongyuan Youth Talent Support Program(in Science and Technology),China(No.ZYQR201810139);the Natural Science Foundation of Henan,China(Nos.232300421080 and 222300420138);the Science and Technology Project of Henan Province,China(Nos.232102241038 and 232102241004);the Key Scientific Research Programs in Universities of Henan Province,China-Special Projects for Basic Research(No.23ZX008);the Innovative Funds Plan of Henan University of Technology,China(No.2020ZKCJ04);the Ph.D.Programs Foundation of HenanUniversity of Technology,China(No.2021BS0027);the Doctoral Education Fund of Henan University of Engineering,China(No.DKJ2019004)。

摘　　要：The global trend towards new energy storage systems has stimulated the development of electrochemical energy storage technologies.Among these technologies,rechargeable aqueous zinc-ion batteries(AZIBs)have attracted considerable interest as a potential alternative to lithium-ion batteries(LIBs)due to their affordable cost,environmental compatibility and high safety standards.In this study,a high-quality electrode for AZIBs has been successfully developed using a dehydrated mixed-valence polyoxometalate-based three-dimensional(3D)inorganic framework material known as[H_6Mn_(3)V^Ⅳ_(15)V-^Ⅴ_(4O)_(46)(H_2O)_(12)](3D-MnVO).This innovative 3D-MnVO material is built from the alternate connections of{V_(19)O_(46)}"sphere-shaped"clusters andμ_(2)-{Mn(H_(2)O)_(4)}bridges,where each{V_(19)O_(46)}cluster is surrounded by three pairs of vertically distributed{Mn(H_(2)O)_(4)}units,thus resulting in the 3D interpenetrating grid-like network from the infinite[-{V_(19)O_(46)}-μ_(2)-Mn(H_(2)O)_(4)-{V_(19)O_(46)}]_∞chains in three mutually perpendicular directions.The 3D framework structure of 3D-MnVO possesses abundant oxygen vacancies,spacious and multi-level interconnected channels for ion transport,which facilitates the efficient intercalation/deintercalation of hydrated Zn^(2+)into the pores of the primary structure via the intercalation capacitance mechanism.As a result,the 3D-MnVO electrode exhibits excellent diffusion rates and minimal interfacial resistance.At a current density of 0.1 A·g^(-1),the 3D-MnVO cathode delivers a commendable discharge capacity of170.5 mAh·g^(-1)with 81.6%capacity retention after100 charge/discharge cycles.Furthermore,even at a high current density of 1.0 A·g^(-1),the 3D-MnVO electrode delivers a remarkable reversible capacity of198.9 mAh·g^(-1).Our research results provide valuable insights into the development of advanced polyoxometalate-based 3D inorganic framework electrode materials for high-performance rechargeable AZIBs.

关 键 词：CATHODE POLYOXOMETALATE 3D inorganic framework Zinc-ion batteries Energy storage mechanism 

分 类 号：TM912[电气工程—电力电子与电力传动] TQ13[化学工程—无机化工]