Phenediamine bridging phthalocyanine-based covalent organic framework polymers used as anode materials for...

In this study, phenediamine bridging phthalocyanine-based covalent organic framework materials (CoTAPc-PDA, CoTAPc-BDA and CoTAPc-TDA) with increasingly-widening pore sizes are prepared by reacting cobalt octacarboxylate phthalocyanine with p-phenylenediamine (PDA), benzidine (BDA) and 4,4''-diamino-p-terphenyl (TDA), respectively. The effects of frame size on the morphology structure and its electrochemical properties were explored. X-ray diffraction (XRD), Brunauer-Emmett-Teller (BET) and transmission electron microscopy (TEM) images show that the pore sizes of the CoTAPc-PDA, CoTAPc-BDA and CoTAPc-TDA are about 1.7 nm, 2.0 nm and 2.3 nm, respectively, which are close to the simulated results after geometric conformation optimization using Material Studio software. In addition, the specific surface areas of CoTAPc-PDA, CoTAPc-BDA and CoTAPc-TDA are 62, 81 and 137 m² g^-1, respectively. With increase in the frame size, the specific surface area of the corresponding material increases, which is bound to produce different electrochemical behaviors. Consequently, the initial capacities of the CoTAPc-PDA, CoTAPc-BDA and CoTAPc-TDA electrodes in lithium-ion batteries (LIBs) are 204, 251 and 382 mA h g^-1, respectively. As the charge and discharge processes continue, the active points in the electrode material are continuously activated, leading to a continuous increase in charge and discharge capacities. After 300 cycles, the CoTAPc-PDA, CoTAPc-BDA and CoTAPc-TDA electrodes exhibit capacities of 519, 680 and 826 mA h g^-1, respectively, and after 600 cycles, the capacities are maintained at 602, 701 and 865 mA h g^-1, respectively, with a stable capacity retention rate at a current density of 100 mA g^-1. The results show that the large-size frame structure materials have a larger specific surface area and more favorable lithium ion transmission channels, which produce greater active point utilization and smaller charge transmission impedance, thus showing larger charge and discharge capacity and superior rate capability. This study fully confirms that frame size is a key factor affecting the properties of organic frame electrodes, providing design ideas for the development of high-performance organic frame electrode materials.