Hydrothermal synthesis of polyimide-linked covalent organic frameworks towards ultrafast and stable cathodic sodium storage  

作　　者：Xiya Yang Lei Gong Zhixin Liu Qianjun Zhi Baoqiu Yu Xin Chen Kang Wang Xiaofeng Li Dongdong Qi Jianzhuang Jiang 

机构地区：[1]Beijing Advanced Innovation Center for Materials Genome Engineering,Beijing Key Laboratory for Science and Application of Functional Molecular and Crystalline Materials,Department of Chemistry and Chemical Engineering,School of Chemistry and Biological Engineering,University of Science and Technology Beijing,Beijing 100083,China [2]State Key Laboratory of Organic-Inorganic Composites,College of Materials Science and Engineering,Beijing University of Chemical Technology,Beijing 100029,China

出　　处：《Science China Chemistry》2024年第4期1300-1310,共11页中国科学（化学英文版）

基　　金：supported by the National Natural Science Foundation of China(22235001,22175020)。

摘　　要：Redox-active organic materials are capturing growing attention as cathode materials for sustainable alkaline metal ion batteries.However,the storage of Na+in most organic materials-based cathodes is plagued by low capacity and unsatisfying rate performance due to their low active site densities and limited exposed active sites.Herein,two polyimide-linked covalent organic frameworks(COFs),namely HATN-PD-COF and HATN-TAB-COF,were fabricated from hydrothermal synthesis with redoxactive triphenylene-2,3,6,7,10,11-hexacarboxylic acid and aromatic amines as starting materials.Powder X-ray diffraction and electron microscopy analysis indicate the high crystalline nature of these COFs with AA stacking configuration and orderly mesoporous tunnel.N_(2) sorption measurement discloses the permanent porosity of these two COFs with a Brunauer-EmmettTeller surface area of 1,065-1,200 m^(2)g^(-1)and a large pore size of 2.0-3.1 nm.Galvanostatic intermittent titration technique and density functional theory calculations reveal the facile Na+ion diffusion along the mesoporous tunnel of these COFs with a small energy barrier of 0.13-0.40 e V.In particular,the as-prepared COFs based-cathodes show ultrafast and stable Na+storage associated with their conjugated electronic structure,highly ordered mesoporous tunnel,robust structure,and redox-active C=N/C=O-rich framework as exemplified by the high reversible capacity of 210 m A h g^(-1)at 200 m A g^(-1),record-high rate performance(195 m A h g^(-1)at a high current density of 10,000 m A g^(-1))among organic electrodes and the capacity retention of nearly 91%at 10,000 m A g^(-1)after 7,000 cycles for HATN-PD-COF.

关 键 词：covalent organic framework sodium ion battery cathode high rate organic electrode 

分 类 号：TM912[电气工程—电力电子与电力传动] TB34[一般工业技术—材料科学与工程]