Inhibiting irreversible Zn^(2+)/H^(+)co-insertion chemistry in aqueous zinc-MoO_(x)batteries for enhanced capacity stability  

作　　者：Chen Zheng Xinwei Guan Zihang Huang Shuai Mao Xu Han Xiaoguang Duan Hui Li Tianyi Ma 

机构地区：[1]Institute of Clean Energy Chemistry,Key Laboratory for Green Synthesis and Preparative Chemistry of Advanced Materials of Liaoning Province,College of Chemistry,Liaoning University,Shenyang 110036,Liaoning,China [2]Centre for Atomaterials and Nanomanufacturing(CAN),School of Science,RMIT University,Melbourne,VIC 3000,Australia [3]Engineering Laboratory of Advanced Energy Materials,Ningbo Institute of Materials Technology and Engineering,Chinese Academy of Sciences,Ningbo 315201,Zhejiang,China [4]School of Chemical Engineering,The University of Adelaide,Adelaide,SA 5005,Australia

出　　处：《Journal of Energy Chemistry》2025年第3期98-106,共9页能源化学(英文版)

基　　金：supported by National Natural Science Foundation of China(22209064,52071171,and 52202248);the Fundamental Research Funds for Public Universities in Liaoning(LJKLJ202434);the Australian Research Council(ARC)through Future Fellowship(FT210100298);Discovery Project(DP220100603);Linkage Project(LP210200504,LP220100088,LP230200897);Industrial Transformation Research Hub(IH240100009)schemes;the Australian Government through the Cooperative Research Centres Projects(CRCPXIII000077);the Australian Renewable Energy Agency(ARENA)as part of ARENA’s Transformative Research Accelerating Commercialisation Program(TM021);European Commission’s Australia-Spain Network for Innovation and Research Excellence(AuSpire)。

摘　　要：Rechargeable aqueous Zn-MoO_(x)batteries are promising energy storage devices with high theoretical specific capacity and low cost.However,MoO_(3)cathodes suffer drastic capacity decay during the initial discharging/charging process in conventional electrolytes,resulting in a short cycle life and challenging the development of Zn-MoO_(x)batteries.Here we comprehensively investigate the dissolution mechanism of MoO_(3)cathodes and innovatively introduce a polymer to inhibit the irreversible processes.Our findings reveal that this capacity decay originates from the irreversible Zn^(2+)/H^(+)co-intercalation/extraction process in aqueous electrolytes.Even worse,during Zn^(2+)intercalation,the formed Zn_(x)MoO_(3-x)intermediate phase with lower valence states(Mo^(5+)/Mo^(4+))experiences severe dissolution in aqueous environments.To address these challenges,we developed a first instance of coating a polyaniline(PANI)shell around the MoO_(3)nanorod effectively inhibiting these irreversible processes and protecting structural integrity during long-term cycling.Detailed structural analysis and theoretical calculations indicate that=N-groups in PANI@MoO_(3-x)simultaneously weaken H+adsorption and enhance Zn^(2+)adsorption,which endowed the PANI@MoO_(3-x)cathode with reversible Zn^(2+)/H^(+)intercalation/extraction.Consequently,the obtained PANI@MoO_(3-x)cathode delivers an excellent discharge capacity of 316.86 mA h g^(-1)at 0.1 A g^(-1)and prolonged cycling stability of 75.49%capacity retention after 1000 cycles at 5 A g^(-1).This work addresses the critical issues associated with MoO_(3)cathodes and significantly advances the understanding of competitive multi-ion energy storage mechanisms in aqueous Zn-MoO_(3)batteries.

关 键 词：Co-insertion chemistry Surface modification engineering Molybdenum oxide Cycling stability Aqueous zincbattery 

分 类 号：TM911.1[电气工程—电力电子与电力传动]