Grotthuss Proton‐Conductive Covalent Organic Frameworks for Efficient Proton Pseudocapacitors

Abstract Herein, we describe the synthesis of two highly crystalline, robust, hydrophilic covalent organic frameworks (COFs) that display intrinsic proton conduction by the Grotthuss mechanism. The enriched redox‐active azo groups in the COFs can undergo a proton‐coupled electron transfer reaction for energy storage, making the COFs ideal candidates for pseudocapacitance electrode materials. After in situ hybridization with carbon nanotubes, the composite exhibited a high three‐electrode specific capacitance of 440 F g −1 at the current density of 0.5 A g −1 , among the highest for COF‐based supercapacitors, and can retain 90 % capacitance even after 10 000 charge–discharge cycles. This is the first example using Grotthuss proton‐conductive organic materials to create pseudocapacitors that exhibited both high power density and energy density. The assembled asymmetric two‐electrode supercapacitor showed a maximum energy density of 71 Wh kg −1 with a maximum power density of 42 kW kg −1 , surpassing that of all reported COF‐based systems.