LAUSR

Solvent free ionic liquid (IL) electrolytes facilitate high‐voltage supercapacitors with enhanced energy density, but their complex ion arrangement and through that the electrochemical properties, are limited by strong Coulombic ordering in the bulk state and like‐charged ion repulsion at electrified interfaces. Herein, a unique interfacial phenomenon resulting from the presence of carbon dioxide loaded in 1‐Ethyl‐3‐methylimidazoliumtetrafluorborate electrolyte that simultaneously couples to IL ions and nitrogen‐doped carbonaceous electrode is reported. The adsorbed CO2 molecule polarizes and mitigates the electrostatic repulsion among like‐charged ions near the electrified interface, leading to an ion “bridge effect” with increased interfacial ionic density and significantly enhanced charge storage capability. The unpolarized CO2 possessing a large quadrupole moment further reduces ion coupling, resulting in higher conductivity of the bulk IL and improved rate capability of the supercapacitor. This work demonstrates polarization‐controlled like‐charge attraction at IL–electrode–gas three‐phase boundaries, providing insights into manipulating complex interfacial ion ordering with small polar molecule mediators.