A solubility limited pyrene-4,5,9,10-tetraone-based covalent organic framework for high-performance aqueous zinc-organic batteries  

作　　者：Min Cheng Shibing Zheng Tianjiang Sun Diantao Li Weijia Zhang Zhengtai Zha Qiong Sun Jing Tian Kai Zhang Zhanliang Tao 

机构地区：[1]Frontiers Science Center for New Organic Matter,State Key Laboratory of Advanced Chemical Power Sources,Key Laboratory of Advanced Energy Materials Chemistry(Ministry of Education),Collaborative Innovation Center of Chemical Science and Engineering(Tianjin),Renewable Energy Conversion and Storage Centre,Nankai University,Tianjin 300071,China [2]Haihe Laboratory of Sustainable Chemical Transformations,Tianjin 300192,China

出　　处：《Nano Research》2024年第6期5095-5103,共9页纳米研究（英文版）

基　　金：the National Natural Science Foundation of China(Nos.22279063 and 52001170);the Fundamental Research Funds for the Central Universities,and Tianjin Natural Science Foundation(No.22JCYBJC00590);Shanxi Supercomputing Center of China,and the calculations were performed on TianHe-2.K.Z.would like to acknowledge for the National Key Research and Development Program of China(No.2022YFB2402200);the National Natural Science Foundation of China(Nos.22121005,22005155,and 52072186);the Fundamental Research Funds for the Central Universities(Nos.63233017,63231002,and 63231198);J.T.would like to acknowledge for the Development Project of Large-scale Instrument Experiment Technology of Nankai University(No.23NKSYJS02).

摘　　要：Pyrene-4,5,9,10-tetraone(PTO),with a high theoretical capacity of 408 mAh·g^(−1),is a promising candidate for rechargeable aqueous zinc-ion batteries(RAZIBs),but its zincated products during discharge process suffer from high solubility in electrolytes.Herein,aβ-ketoenamine-linked two-dimensional(2D)covalent organic framework(COF)based on a 2,7-diaminopyrene-4,5,9,10-tetraone(4KT-BD)monomer and a 2,4,6-trihydroxy-benzene-1,3,5-tricarbaldehyde(Tp)node(4KT-Tp-COF)is synthesized to address the above issue.The well-designed 4KT-Tp-COF displays low solubility in 3 M Zn(CF3SO3)2 owing to the favorableπ-πstacking as well as extended structure.Besides,the ingenious structural design of the active molecule and the long-range ordered nano-channels alter the intramolecular electron distribution,which facilitates the ionic diffusion.Consequently,the 4KT-Tp-COF cathode exhibits a stable capacity of 181 mAh·g^(−1)at 0.2 A·g^(−1),superior rate capability of 139 mAh·g^(−1)at 20 A·g^(−1),and a long lifetime of 1000 cycles without capacity loss at 30 A·g^(−1).Even at a low temperature of−20°C,the electrode also performs an ultralong cycling life of 9000 cycles with a capacity of 106 mAh·g^(−1)at 5 A·g^(−1).The comprehensive characterizations of ex-situ analyses together with the theoretical calculations validate that the groups of C=O can contribute highly accessible redox-active sites for Zn^(2+)storage.The ultra-stable 4KT-Tp-COF cathode provides important insights for designing robust organic electrodes for sustainable and large-scale electrochemical energy storage.

关 键 词：pyrene-4 5 9 10-tetraone solubility limited covalent organic framework zinc batteries 

分 类 号：TM912[电气工程—电力电子与电力传动]