Bridging the Gap between Charge Storage Site and Transportation Pathway in Molecular-Cage-Based Flexible Electrodes

[Image: see text] Porous materials have been widely applied for supercapacitors; however, the relationship between the electrochemical behaviors and the spatial structures has rarely been discussed before. Herein, we report a series of porous coordination cage (PCC) flexible supercapacitors with tunable three-dimensional (3D) cavities and redox centers. PCCs exhibit excellent capacitor performances with a superior molecular capacitance of 2510 F mmol(–1), high areal capacitances of 250 mF cm(–2), and unique cycle stability. The electrochemical behavior of PCCs is dictated by the size, type, and open–close state of the cavities. Both the charge binding site and the charge transportation pathway are unambiguously elucidated for PCC supercapacitors. These findings provide central theoretical support for the “structure–property relationship” for designing powerful electrode materials for flexible energy storage devices.