Imine‐Induced Metal‐Organic and Covalent Organic Coexisting Framework with Superior Li‐Storage Properties and Activation Mechanism

Abstract

Due to the adjustable structure and the broad application prospects in energy and other fields, the exploration of porous organic materials [metal‐organic polymers (MOPs), covalent organic frameworks (COFs), etc.] has attracted extensive attention. In this work, an imine‐induced metal‐organic and covalent organic coexisting framework (Co−MOP@COF) hybrid was designed based on the combination between the amino units from the organic ligands of Co−MOP and the aldehyde groups from COF. The obtained Co−MOP@COF hybrid with layer‐decorated microsphere morphology exhibited good electrochemical cycling performance (a large reversible capacity of 1020 mAh g−1 after 150 cycles at 100 mA g−1 and a reversible capacity of 396 mAh g−1 at 500 mA g−1) as the anode for Li‐ion batteries. The coexisting framework structure endowed the Co–MOP@COF hybrid with more surface area exposed in the exfoliated COF structure, which provided rapid Li‐ion diffusion, better electrolyte infiltration, and effective activation of functional groups. Therefore, the Co−MOP@COF hybrid material achieved an enhanced Li storage mechanism involving multi‐electron redox reactions, related to the CoII center and organic groups (C=C groups of benzene rings and C=N groups), and furthermore improved electrochemical performance.

Construction of Macroporous Co2SnO4 with Hollow Skeletons as Anodes for Lithium-Ion Batteries

“…On this basis, the pseudo-capacitance behavior of Co 2 SnO 4 electrode was improved. The dynamic evaluation further explains the reason for the high-rate performance under high current [39].…”

Covalent organic frameworks and their composites for rechargeable batteries

“…Based on the coordination between the N atom of COF and the metal center of MOF, hybridization between COF and MOF has been achieved, resulting in excellent lithium storage performance, which is attributed to the activated aromatic benzene ring and metal center. Zhao et al 145 successfully prepared metal–organic and COF composites, and the coexisting framework structures endowed Co-MOP@COF with layered-modified microsphere morphology to expose more specific surface area in the stripped COF structure, which effectively enhanced the lithium storage mechanism. However, Long and co-workers prepared Fe 2 O 3 @COF-LZU1 (FO@LZU1) anodes by covering metal oxides on imine-based COFs (COF-LZU1).…”

Progress in Hybridization of Covalent Organic Frameworks and Metal–Organic Frameworks

“…[149][150][151][152][153][154][155][156][157][158][159][160][161][162] COF and MOF have also been widely applied in the field of energy storage in the form of Li-ion batteries, supercapacitors, and hydrogen storage for their porous structure and atom-level designability. [163][164][165][166][167][168][169][170][171][172][173][174][175] Intimate hybridization between the two components was highly desirable by combining the merits of COF and MOF to acquire the maximum performance. Wang and co-workers report a facile bottom-up strategy to prepare highly dispersed Co 3 O 4 supported on N-doped porous carbon (NPC).…”