Driven by safety issues,environmental concerns,and high costs,rechargeable aqueous zinc-ion batteries(ZIBs)have received increasing attention in recent years owing to their unique advantages.However,the sluggish kinet...Driven by safety issues,environmental concerns,and high costs,rechargeable aqueous zinc-ion batteries(ZIBs)have received increasing attention in recent years owing to their unique advantages.However,the sluggish kinetics of divalent charge Zn^(2+)in the cathode materials caused by the strong electrostatic interaction and their unsatisfactory cycle life hinder the development of ZIBs.Herein,organic cations and Zn^(2+)ions co-pre-inserted vanadium oxide([N(CH_(3))_(4)]_(0.77),Zn_(0.23))V_(8)O_(20)·3.8H_(2)O are reported as the cathode for ultra-stable aqueous ZIBs,in which the weaker electrostatic interactions between Zn^(2+)and organic ion-pinned vanadium oxide can induce the high reversibility of Zn^(2+)insertion and extraction,thereby improving the cycle life.It is demonstrated that([N(CH_(3))_(4)]_(0.77),Zn_(0.23))V_(8)O_(20)·3.8H_(2)O cathodes deliver a discharge capacity of 181 mA h g^(-1)at8 A g^(-1)and ultra-long life span(99.5%capacity retention after 2000 cycles).A reversible Zn^(2+)/H^(+)ions(de)intercalation storage process and pseudocapacitive charge storage are characterized.The weaker interactions between organic ion and Zn^(2+)open a novel avenue for the design of highly reversible cathode materials with long-term cycling stability.展开更多
Zn(CF_(3)SO_(3))_(2)as an electrolyte has been widely used to improve the electrochemical performance for ZIBs due to that the bulky CF_(3)SO_(3)-can reduce the solvation effect of Zn^(2+)and promote the ionic diffusi...Zn(CF_(3)SO_(3))_(2)as an electrolyte has been widely used to improve the electrochemical performance for ZIBs due to that the bulky CF_(3)SO_(3)-can reduce the solvation effect of Zn^(2+)and promote the ionic diffusion.Herein,we found that Zn(CF_(3)SO_(3))_(2)electrolyte can induce different electrochemical mechanisms from ZnSO_(4)electrolyte.Compared to the ZnSO^(4)electrolyte,the HNaV_(6)O_(16)·4H2_(O)electrode with Zn(CF_(3)SO_(3))_(2)electrolyte exhibits a high capacity of 444 mAh·g^(-1)at 500 mA·g^(-1)with a capacity retention of 92.3%after 80 cycles.Even,at a high rate of 5 Ag-1,the HNaV_(6)O_(16)·4H_(2)O electrode delivers an initial discharge capacity of 328 mAh·g^(-1)with a capacity retention of 93.7%after 1000 cycles.Differing from the mechanism with ZnSO4 electrolyte,the excellent cycle stability of HNaV_(6)O_(16)·4H_(2)Oelectrode can be attributed to the in-situ phase transformation to ZnxV_(2)O_(5)·nH_(2)O based on the co-intercalation of Zn^(2+)/H^(+).展开更多
开发高性能正极材料是限制锌离子电池发展的重要因素.Na_(3)V_(2)(PO_(4))_(3)(NVP)是一种典型NASICON结构的材料,其作为锌离子电池正极材料具有较高的工作电压,然而其循环性能较差,通常仅200圈.本文首次系统地研究了该材料储锌性能的...开发高性能正极材料是限制锌离子电池发展的重要因素.Na_(3)V_(2)(PO_(4))_(3)(NVP)是一种典型NASICON结构的材料,其作为锌离子电池正极材料具有较高的工作电压,然而其循环性能较差,通常仅200圈.本文首次系统地研究了该材料储锌性能的衰退机理.研究表明,在水系电解液中NVP的自发溶解及首圈放电过程中材料的不可逆相变是其容量衰退的主要原因.采用含锌有机电解液虽可避免其溶解,但锌离子的嵌入易导致晶体结构的坍塌.本文首次引入钠离子作为新的载流子并构建有机Na/Zn混合离子电解液.其中,两种金属离子在NVP中高度可逆的共插层反应助力Zn/Na_(3)V_(2)-(PO_(4))_(3)电池实现了84 mA h g^(−1)的较高容量以及在大电流密度下循环600圈容量零衰减的高稳定性.展开更多
基金supported by the funding from the National Natural Science Foundation of China(grant nos.51902187,52072224,and 51732007)the Natural Science Foundation of Shandong Province(ZR2018BEM010)+3 种基金the Science Fund for Distinguished Young Scholars of Shandong Province(ZR2019JQ16)the Fundamental Research Funds of Shandong UniversityYoung Elite Scientist Sponsorship Program by CAST(YESS)the support from Collaborative Innovation Center of Technology and Equipment for Biological Diagnosis and Therapy in Universities of Shandong
文摘Driven by safety issues,environmental concerns,and high costs,rechargeable aqueous zinc-ion batteries(ZIBs)have received increasing attention in recent years owing to their unique advantages.However,the sluggish kinetics of divalent charge Zn^(2+)in the cathode materials caused by the strong electrostatic interaction and their unsatisfactory cycle life hinder the development of ZIBs.Herein,organic cations and Zn^(2+)ions co-pre-inserted vanadium oxide([N(CH_(3))_(4)]_(0.77),Zn_(0.23))V_(8)O_(20)·3.8H_(2)O are reported as the cathode for ultra-stable aqueous ZIBs,in which the weaker electrostatic interactions between Zn^(2+)and organic ion-pinned vanadium oxide can induce the high reversibility of Zn^(2+)insertion and extraction,thereby improving the cycle life.It is demonstrated that([N(CH_(3))_(4)]_(0.77),Zn_(0.23))V_(8)O_(20)·3.8H_(2)O cathodes deliver a discharge capacity of 181 mA h g^(-1)at8 A g^(-1)and ultra-long life span(99.5%capacity retention after 2000 cycles).A reversible Zn^(2+)/H^(+)ions(de)intercalation storage process and pseudocapacitive charge storage are characterized.The weaker interactions between organic ion and Zn^(2+)open a novel avenue for the design of highly reversible cathode materials with long-term cycling stability.
基金This study was financially supported by the National Natural Science Foundation of China(No.51772193)China Postdoctral Science Foundation(No.2019T250254).
文摘Zn(CF_(3)SO_(3))_(2)as an electrolyte has been widely used to improve the electrochemical performance for ZIBs due to that the bulky CF_(3)SO_(3)-can reduce the solvation effect of Zn^(2+)and promote the ionic diffusion.Herein,we found that Zn(CF_(3)SO_(3))_(2)electrolyte can induce different electrochemical mechanisms from ZnSO_(4)electrolyte.Compared to the ZnSO^(4)electrolyte,the HNaV_(6)O_(16)·4H2_(O)electrode with Zn(CF_(3)SO_(3))_(2)electrolyte exhibits a high capacity of 444 mAh·g^(-1)at 500 mA·g^(-1)with a capacity retention of 92.3%after 80 cycles.Even,at a high rate of 5 Ag-1,the HNaV_(6)O_(16)·4H_(2)O electrode delivers an initial discharge capacity of 328 mAh·g^(-1)with a capacity retention of 93.7%after 1000 cycles.Differing from the mechanism with ZnSO4 electrolyte,the excellent cycle stability of HNaV_(6)O_(16)·4H_(2)Oelectrode can be attributed to the in-situ phase transformation to ZnxV_(2)O_(5)·nH_(2)O based on the co-intercalation of Zn^(2+)/H^(+).
基金This work was supported by the National Natural Science Foundation of China(91963210,U1801255,and 51872340)the Fundamental Research Funds for the Central Universities,China(18lgpy06).
文摘开发高性能正极材料是限制锌离子电池发展的重要因素.Na_(3)V_(2)(PO_(4))_(3)(NVP)是一种典型NASICON结构的材料,其作为锌离子电池正极材料具有较高的工作电压,然而其循环性能较差,通常仅200圈.本文首次系统地研究了该材料储锌性能的衰退机理.研究表明,在水系电解液中NVP的自发溶解及首圈放电过程中材料的不可逆相变是其容量衰退的主要原因.采用含锌有机电解液虽可避免其溶解,但锌离子的嵌入易导致晶体结构的坍塌.本文首次引入钠离子作为新的载流子并构建有机Na/Zn混合离子电解液.其中,两种金属离子在NVP中高度可逆的共插层反应助力Zn/Na_(3)V_(2)-(PO_(4))_(3)电池实现了84 mA h g^(−1)的较高容量以及在大电流密度下循环600圈容量零衰减的高稳定性.
