Templated Synthesis of 2D Polyimide Covalent Organic Framework for Rechargeable Sodium‐Ion Batteries

Abstract Covalent organic frameworks (COFs) hold great promise for electrochemical energy storage because of their high surface area, readily accessible redox‐active sites, and environment‐friendly chemical composition. In this study, the synthesis of a redox‐active pyrene‐containing polyimide COF (PICOF‐1) by linker exchange using an imine‐linked COF as a template is reported and its performance in sodium‐ion batteries (SIBs) is demonstrated. The reported synthetic route based on linker exchange mitigates the challenges typically encountered with crystallizing chemically stable polyimide COFs from typical condensation reactions; thus, facilitating their rapid synthesis and purification. Using this approach, PICOF‐1 exhibits high crystallinity with very low refinement parameters R P and R WP of 0.415% and 0.326%, respectively. PICOF‐1 has a high Brunauer–Emmette–Teller (BET) surface area of 924 m 2 g −1 and well‐defined one‐dimentional (1D) channels of 2.46 × 1.90 nm, which enable fast ion transport and charge transfer, reaching a capacity at 0.1 C of almost nearly as its theoretical capacity and maintaining 99% Coulombic efficiency over 175 cycles at 0.3 C. The study demonstrates that imine‐linked COFs are effective templates for integrating carbonyl‐rich polyimide moieties into high‐surface COFs to advance electrochemical energy storage applications.