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

Qing Han ¹Hao-Ran Xiao ¹Tao Zhou ¹Bing-Chuan Li ¹Liu Yang ²Ling-Ling Xie ³Xue-Jing Qiu ³Xian-Yong Wu ⁴Li-Min Zhu ¹Xiao-Yu Cao¹

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作者信息

1. School of Chemistry and Chemical Engineering,Henan University of Technology,Zhengzhou 450001,China;Key Laboratory of High Specific Energy Materials for Electrochemical Power Sources of Zhengzhou City,Zhengzhou 450001,China
2. College of Materials Engineering,Henan University of Engineering,Zhengzhou 450007,China
3. Key Laboratory of High Specific Energy Materials for Electrochemical Power Sources of Zhengzhou City,Zhengzhou 450001,China;School of Environmental Engineering,Henan University of Technology,Zhengzhou 450001,China
4. Department of Chemistry,University of Puerto Rico-Rio Piedras Campus,San Juan,PR 00925,USA
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Abstract

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[H6Mn3VⅣ15V-Ⅴ4O46(H2O)12](3D-MnVO).This innovative 3D-MnVO material is built from the alternate connections of {V19O46}"sphere-shaped"clusters and p2-{Mn(H2O)4} bridges,where each {V19O46} cluster is surrounded by three pairs of vertically distributed {Mn(H2O)4} units,thus resulting in the 3D interpenetrating grid-like network from the infi-nite[-{V19O46}-μ2-Mn(H2O)4-{V19O46}]∞ chains in three mutually perpendicular directions.The 3D framework structure of 3D-MnVO possesses abundant oxygen vacan-cies,spacious and multi-level interconnected channels for ion transport,which facilitates the efficient intercalation/deintercalation of hydrated Zn2+into the pores of the primary structure via the intercalation capacitance mecha-nism.As a result,the 3D-MnVO electrode exhibits excel-lent 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 of 170.5 mAh·g-1 with 81.6％capacity retention after 100 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 of 198.9 mAh·g-1.Our research results provide valuable insights into the development of advanced polyoxometa-late-based 3D inorganic framework electrode materials for high-performance rechargeable AZIBs.

Key words

Cathode/Poly oxometalate/3D inorganic framework/Zinc-ion batteries/Energy storage mechanism

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基金项目

National Natural Science Foundation of China(52071132)

National Natural Science Foundation of China(52261135632)

National Natural Science Foundation of China(U21A20284)

Zhongyuan Thousand People Plan-The Zhongyuan Youth Talent Support Program(in Science and Technology),China(ZYQR201810139)

Natural Science Foundation of Henan,China(232300421080)

Natural Science Foundation of Henan,China(222300420138)

Science and Technology Project of Henan Province,China(232102241038)

Science and Technology Project of Henan Province,China(232102241004)

Key Scientific Research Programs in Universities of Henan Province,China-Special Projects for Basic Research(23ZX008)

Innovative Funds Plan of Henan University of Technology,China(2020ZKCJ04)

Ph.D.Programs Foundation of Henan University of Technology,China(2021BS0027)

Doctoral Education Fund of Henan University of Engineering,China(DKJ2019004)

出版年

2024

稀有金属(英文版)

中国有色金属学会

稀有金属(英文版)

CSTPCDCSCDEI

影响因子：0.801

ISSN：1001-0521

参考文献量75

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