Jindal Swati, Tian Zhengnan, Mallick Arijit, Kandambeth Sharath, Liu Chen, Bhatt Prashant M, Zhang Xixiang, Shekhah Osama, Alshareef Husam N, Eddaoudi Mohamed
Functional Materials Design, Discovery, and Development Research Group (FMD3), Advanced Membranes and Porous Materials Center (AMPM), Physical Science and Engineering (PSE) Division, King Abdullah University of Science and Technology (KAUST), Thuwal, 23955-6900, Saudi Arabia.
Materials Science and Engineering, Physical Science and Engineering Division, King Abdullah University of Science and Technology (KAUST), Thuwal, 23955-6900, Saudi Arabia.
Small. 2025 Feb;21(8):e2407525. doi: 10.1002/smll.202407525. Epub 2024 Sep 13.
Covalent organic frameworks (COFs) are viewed as promising organic electrode materials for metal-ion batteries due to their structural diversity and tailoring capabilities. In this work, firstly using the monomers N,N,N',N'-tetrakis(4-aminophenyl)-1,4-phenylenediamine (TPDA) and terephthaldehyde (TA), p-type phenylenediamine-based imine-linked TPDA-TA-COF is synthesized. To construct a bipolar redox-active, porous and highly crystalline polyimide-linked COF, i.e., TPDA-NDI-COF, n-type 1,4,5,8-naphthalene tetracarboxylic dianhydride (NDA) molecules are incorporated into p-type TPDA-TA-COF structure via postsynthetic linker exchange method. This tailored COF demonstrated a wide potential window (1.03.6 V vs Na/Na) with dual redox-active centers, positioning it as a favorable cathode material for sodium-ion batteries (SIBs). Owing to the inheritance of multiple redox functionalities, TPDA-NDI-COF can deliver a specific capacity of 67 mAh g at 0.05 A g, which is double the capacity of TPDA-TA-COF (28 mAh g). The incorporation of carbon nanotube (CNT) into the TPDA-NDI-COF matrix resulted in an enhancement of specific capacity to 120 mAh g at 0.02 A g. TPDA-NDI-50%CNT demonstrated robust cyclic stability and retained a capacity of 92 mAh g even after 10 000 cycles at 1.0 A g. Furthermore, the COF cathode exhibited an average discharge voltage of 2.1 V, surpassing the performance of most reported COF as a host material.
共价有机框架（COFs）因其结构多样性和可定制性，被视为用于金属离子电池的有前景的有机电极材料。在这项工作中，首先使用单体N，N，N'，N'-四（4-氨基苯基）-1，4-苯二胺（TPDA）和对苯二甲醛（TA），合成了p型基于苯二胺的亚胺连接的TPDA-TA-COF。为了构建具有双极氧化还原活性、多孔且高度结晶的聚酰亚胺连接的COF，即TPDA-NDI-COF，通过后合成连接体交换方法将n型1，4，5，8-萘四甲酸二酐（NDA）分子引入p型TPDA-TA-COF结构中。这种定制的COF展示出具有双氧化还原活性中心的宽电位窗口（相对于Na/Na为1.0 - 3.6 V），使其成为钠离子电池（SIBs）的理想正极材料。由于多种氧化还原功能的继承，TPDA-NDI-COF在0.05 A g下可提供67 mAh g的比容量，这是TPDA-TA-COF（28 mAh g）容量的两倍。将碳纳米管（CNT）掺入TPDA-NDI-COF基体中，在0.02 A g下比容量提高到120 mAh g。TPDA-NDI-50%CNT表现出强大的循环稳定性，即使在1.0 A g下循环10000次后仍保留92 mAh g的容量。此外，该COF正极的平均放电电压为2.OV，超过了大多数报道的作为主体材料的COF的性能。
