Rapid Charge Transfer Enabled by Noncovalent Interaction through Guest Insertion in Supercapacitors based on Covalent Organic Frameworks

Covalent organic frameworks (COFs) have been proposed for electrochemical energy storage, although the poor conductivity resulted from covalent bonds limits their practical performance. Here, we propose to introduce noncovalent bonds in COFs through a molecular insertion strategy for improving the conductivity of the COFs as supercapacitor. The synthesized COFs (MI−COFs) establish equilibriums between covalent bonds and noncovalent bonds, which construct a continuous charge transfer channel to enhance the conductivity. The rapid charge transfer rate enables the COFs to activate the redox sites, bringing about excellent electrochemical energy storage behavior. The results show that the MI−COFs exhibit much better performance in specific capacitance and capacity retention rate than those of most COFs‐based supercapacitors. Moreover, through simply altering inserted guests, the mode and strength of noncovalent bond can be adjusted to obtain different energy storage characteristics. The introduction of noncovalent bonds is an effective and flexible way to enhance and regulate the properties of COFs, providing a valuable direction for the development of novel COFs‐based energy storage materials. A molecular insertion strategy is used by introducing non‐covalent interactions in COFs to form a continuous charge transfer channel and accelerate the charge transfer rate. Meanwhile, the enhanced conductivity activates the redox sites in the COF skeleton, resulting in excellent energy storage performance. In addition, the energy storage behavior can be accurately regulated by changing the type of insertion guests.