Emerging Frontiers for Next‐Generation Covalent Organic Framework (COFs)‐Based Electrode Materials for Supercapacitors

Covalent organic frameworks (COFs) have proven to be a radical class of porous crystalline materials that offer unprecedented opportunities for molecular‐level architecture in energy storage devices. COFs provide a unique design ability for supercapacitor (SC) electrodes at the molecular scale. Recently, COFs have advanced significantly in terms of capacitance, conductivity, and stability through redox‐active functionalization, heteroatom doping, and integration with conductive nanomaterials. In addition to incremental improvements in gravimetric performance, this review aims to map the horizon, identifying and critically discussing the emerging frontiers that will characterize the next generation of COF‐based SCs. The main argument is reforming new, underdeveloped pathways: (1) engineering ion‐specific pore electrochemistry to develop new charge storage mechanisms beyond double‐layers and traditional pseudocapacitance; (2) going beyond powder‐based electrodes and processing macroscopic structures, films, and 3D monoliths to attain higher areal density; and (3) seeking multifunctional integration which combines energy storage with sensing, catalysis. Finally, the key problems of scalable synthesis, long‐term operational stability, and the disconnect between material and device‐level innovation. This review aims to motivate the scientific community by laying out a roadmap to address these underlying challenges and unlock the full disruptive potential of COFs for flexible, sustainable, and high‐density energy‐storage technologies.