Spatial Confinement Strategy for Micelle-Size-Mediated Modulation of Mesopores in Hierarchical Porous Carbon Nanosheets with an Efficient Capacitive Response

Commercial supercapacitors using available carbon products have long been criticized for the under-utilization of their prominent specific surface area (SSA). In terms of carbonaceous electrode optimization, excessive improvement in SSA observed in the gaseous atmosphere might have little effect on the final performance because cracked/inaccessible pore alleys considerably block the direct electrolyte ion transport in a practical electrochemical environment. Herein, mesopore-adjustable hierarchically porous carbon nanosheets are fabricated based on a micelle-size-mediated spatial confinement strategy. In this strategy, hydrophobic trimethylbenzene in different volumes of the solvent can mediate the interfacial assembly with a carbon precursor and porogen segment through π–π bonding and van der Waals interaction to yield micelles with good dispersity and the diameter varying from 119 to 30 nm. With an increasing solvent volume, the corresponding diffusion coefficient (3.1–14.3 m2 s–1) of as-obtained smaller micelles increases, which makes adjacent micelles gather rapidly and then grow along the radial direction of oligomer aggregates to eventually form mesopores on hierarchically porous carbon nanosheets (MNC150-4.5). Thanks to the pore-expansion effect of trimethylbenzene, the mesoporous volume can be adjusted from 28.8 to 40.0%. Mesopores on hierarchically porous carbon nanosheets endow MNC150-4.5 with an enhanced electrochemically active surface area of 819.5 m2 g–1, which gives rise to quick electrolyte accessibility and a correspondingly immediate capacitive response of 338 F g–1 at 0.5 A g–1 in a three-electrode system. Electrolyte transport through pathways within MNC150-4.5 ultimately enables the symmetric cell to deliver a high energy output of 50.4 Wh kg–1 at 625 W kg–1 in a 14 m LiOTF electrolyte and 95% capacitance retention after 100,000 cycles, which show its superior electrochemical performance over representative carbon-based supercapacitors with aqueous electrolytes in recent literature.