Unraveling the Capacitive Behaviors in Nanoconfined Ionophilic Carbon Pores

Abstract Intensifying the synergy between confined carbon nanopores and ionic liquids (ILs) and a deep comprehension of the ion behavior is required for enhancing the capacitive storage performance. Despite many theoretical insights on the storage mechanism, experimental verification has remained lacking due to the intricate nature of pore texture. Here, a compressed micropore‐rich carbon framework (CMCF) with tailored monolayer and bilayer confinement pores is synthesized, which exhibits a compatible ionophilic interface to accommodate the IL [EMIM][BF 4 ]. By deploying in situ Raman spectroscopy, in situ Fourier‐transform infrared spectroscopy, and solid‐state nuclear magnetic resonance, the effect of the pore textures on ions storage behaviors is elucidated. A voltage‐induced ion gradient filling process in these ionophilic pores is proposed, in which ion exchange and co‐ion desorption dominate the charge storage process. Moreover, it is established that the monolayer confinement of ions enhances the capacity, and bilayer confinement facilitates the charging dynamics. This work may guide the design of nanoconfinement carbon for high‐energy‐density supercapacitors and deepen the understanding of the charge storage mechanism in ionophilic pores.