Covalent Organic Framework with Highly Accessible Carbonyls and π‐Cation Effect for Advanced Potassium‐Ion Batteries

Covalent organic frameworks (COF) possess a robust and porous crystalline structure, making them an appealing candidate for energy storage. Herein, we report an exfoliated polyimide COF composite (P-COF@SWCNT) prepared by an in situ condensation of anhydride and amine on the single-walled carbon nanotubes as advanced anode for potassium-ion batteries (PIBs). Numerous active sites exposed on the exfoliated frameworks and the various open pathways promote the highly efficient ion diffusion in the P-COF@SWCNT while preventing irreversible dissolution in the electrolyte. During the charging/discharging process, K+ is engaged in the carbonyls of imide group and naphthalene rings through the enolization and π-K+ effect, which is demonstrated by the DFT calculation and XPS, ex-situ FTIR, Raman. As a result, the prepared P-COF@SWCNT anode enables an incredibly high reversible specific capacity of 438 mA h g-1 at 0.05 A g-1 and extended stability. The structural advantage of P-COF@SWCNT enables more insights into the design and versatility of COF as an electrode.