Vanadium oxide cathode materials with stable crystal structure and fast Zn^(2+) storage capabilities are extremely important to achieving outstanding electrochemical performance in aqueous zinc‐ion batteries.In this ...Vanadium oxide cathode materials with stable crystal structure and fast Zn^(2+) storage capabilities are extremely important to achieving outstanding electrochemical performance in aqueous zinc‐ion batteries.In this work,a one‐step hydrothermal method was used to manipulate the bimetallic ion intercalation into the interlayer of vanadium oxide.The pre‐intercalated Cu ions act as pillars to pin the vanadium oxide(V‐O)layers,establishing stabilized two‐dimensional channels for fast Zn^(2+) diffusion.The occupation of Mn ions between V‐O interlayer further expands the layer spacing and increases the concentration of oxygen defects(Od),which boosts the Zn^(2+) diffusion kinetics.As a result,as‐prepared Cu_(0.17)Mn_(0.03)V_(2)O_(5−□)·2.16H_(2)O cathode shows outstanding Zn‐storage capabilities under room‐and lowtemperature environments(e.g.,440.3 mAh g^(−1) at room temperature and 294.3 mAh g^(−1)at−60°C).Importantly,it shows a long cycling life and high capacity retention of 93.4%over 2500 cycles at 2 A g^(−1) at−60°C.Furthermore,the reversible intercalation chemistry mechanisms during discharging/charging processes were revealed via operando X‐ray powder diffraction and ex situ Raman characterizations.The strategy of a couple of 3d transition metal doping provides a solution for the development of superior room‐/lowtemperature vanadium‐based cathode materials.展开更多
Low-temperature zinc batteries(LT-ZIBs)based on aqueous electrolytes show great promise for practical applications owing to their natural resource abundance and low cost.However,they suffer from sluggish kinetics with...Low-temperature zinc batteries(LT-ZIBs)based on aqueous electrolytes show great promise for practical applications owing to their natural resource abundance and low cost.However,they suffer from sluggish kinetics with elevated energy barriers due to the dissociation of bulky Zn(H2O)62+solvation structure and free Zn2+diffusion,resulting in unsatisfactory lifespan and performance.Herein,dissimilar to solvation shell tuning or layer spacing enlargement engineering,delocalized electrons in cathode through constructing intrinsic defect engineering is proposed to achieve a rapid electrocatalytic desolvation to obtain free Zn2+for insertion/extraction.As revealed by density functional theory calculations and interfacial spectroscopic characterizations,the intrinsic delocalized electron distribution propels the Zn(H2O)62+dissociation,forming a reversible interphase and facilitating Zn2+diffusion across the electrolyte/cathode interface.The as-fabricated oxygen defect-rich V2O5 on hierarchical porous carbon(ODVO@HPC)electrode exhibits high capacity robustness from 25 to20℃.Operating at-20℃,the ODVO@HPC delivers 191 mAh g-1 at 50 A g-1 and lasts for 50000 cycles at 10 A g-1,significantly enhancing the power density and lifespan under low-temperature environments in comparison to previous reports.Even with areal mass loading of-13 mg cm2,both coin cells and pouch batteries maintain excellent stability and areal capacities,realizing practical high-performance LT-ZIBs.展开更多
基金National Natural Science Foundation of China,Grant/Award Numbers:52372188,51902090,51922008,520721142023 Introduction of studying abroad talent program,the China Postdoctoral Science Foundation,Grant/Award Number:2019 M652546+3 种基金Xinxiang Major Science and Technology Projects,Grant/Award Number:21ZD001Henan Province Postdoctoral Start‐Up Foundation,Grant/Award Number:1901017Henan Center for Outstanding Overseas Scientists,Grant/Award Number:GZS2018003Overseas Expertise Introduction Project for Discipline Innovation,Grant/Award Number:D17007。
文摘Vanadium oxide cathode materials with stable crystal structure and fast Zn^(2+) storage capabilities are extremely important to achieving outstanding electrochemical performance in aqueous zinc‐ion batteries.In this work,a one‐step hydrothermal method was used to manipulate the bimetallic ion intercalation into the interlayer of vanadium oxide.The pre‐intercalated Cu ions act as pillars to pin the vanadium oxide(V‐O)layers,establishing stabilized two‐dimensional channels for fast Zn^(2+) diffusion.The occupation of Mn ions between V‐O interlayer further expands the layer spacing and increases the concentration of oxygen defects(Od),which boosts the Zn^(2+) diffusion kinetics.As a result,as‐prepared Cu_(0.17)Mn_(0.03)V_(2)O_(5−□)·2.16H_(2)O cathode shows outstanding Zn‐storage capabilities under room‐and lowtemperature environments(e.g.,440.3 mAh g^(−1) at room temperature and 294.3 mAh g^(−1)at−60°C).Importantly,it shows a long cycling life and high capacity retention of 93.4%over 2500 cycles at 2 A g^(−1) at−60°C.Furthermore,the reversible intercalation chemistry mechanisms during discharging/charging processes were revealed via operando X‐ray powder diffraction and ex situ Raman characterizations.The strategy of a couple of 3d transition metal doping provides a solution for the development of superior room‐/lowtemperature vanadium‐based cathode materials.
基金the National Key R&D Program of China(2021YFA1201503)National Natural Science Foundation of China(Nos.21972164,22279161,12264038,22309144)+7 种基金the Natural Science Foundation of Jiangsu Province(BK.20210130)China Postdoctoral Science Foundation(2023 M732561,2023 M731084)Innovative and Entrepreneurial Doctor in Jiangsu Province(JSSCBS20211428)J.W.and S.P.acknowledge the funding provided by the Alexander von Humboldt Foundation and the basic funding of the Helmholtz AssociationQ.Z.acknowledges the support of HZWTECH for providing computational facilitiesH.A.acknowledges the University of Hong Kong and the Hong Kong Quantum AI Lab Limited,AIR@Inno HK for supporting his fellowshipWe also thank Nano-X,Suzhou Institute of Nano-tech and Nano-bionics,Chinese Academy of Sciences for the material measurement analysisOpen Access funding enabled and organized by Projekt DEAL.
文摘Low-temperature zinc batteries(LT-ZIBs)based on aqueous electrolytes show great promise for practical applications owing to their natural resource abundance and low cost.However,they suffer from sluggish kinetics with elevated energy barriers due to the dissociation of bulky Zn(H2O)62+solvation structure and free Zn2+diffusion,resulting in unsatisfactory lifespan and performance.Herein,dissimilar to solvation shell tuning or layer spacing enlargement engineering,delocalized electrons in cathode through constructing intrinsic defect engineering is proposed to achieve a rapid electrocatalytic desolvation to obtain free Zn2+for insertion/extraction.As revealed by density functional theory calculations and interfacial spectroscopic characterizations,the intrinsic delocalized electron distribution propels the Zn(H2O)62+dissociation,forming a reversible interphase and facilitating Zn2+diffusion across the electrolyte/cathode interface.The as-fabricated oxygen defect-rich V2O5 on hierarchical porous carbon(ODVO@HPC)electrode exhibits high capacity robustness from 25 to20℃.Operating at-20℃,the ODVO@HPC delivers 191 mAh g-1 at 50 A g-1 and lasts for 50000 cycles at 10 A g-1,significantly enhancing the power density and lifespan under low-temperature environments in comparison to previous reports.Even with areal mass loading of-13 mg cm2,both coin cells and pouch batteries maintain excellent stability and areal capacities,realizing practical high-performance LT-ZIBs.
