Toward the Experimental Understanding of the Energy Storage Mechanism and Ion Dynamics in Ionic Liquid Based Supercapacitors

Abstract A series of salt‐templated carbons with gradually changed pore structure and their corresponding nitrogen‐doped analogues are synthesized and applied as model systems to thoroughly study the ion migration dynamics and energy storage mechanism in hierarchical pore structures with different surface functionalization in electric double‐layer capacitors with a model ionic liquid electrolyte (1‐ethyl‐3‐methylimidazolium tetrafluoroborate). Ion conformation and phase variation during the charging/discharging process and their contribution to the energy storage mechanism are investigated. A significant contribution of structural changes in the bulk of the ionic liquid electrolyte strengthening charge storage in the electric double‐layer beyond the usual expectations is uncovered. Furthermore, a quantitative model of the structure–dynamics relationship is proposed, in which the optimal ratio of mesopores to micropores is determined to be 3:1 in pore volume. Below this ratio, the ion dynamics can be promoted by increasing mesopore content and/or doping with nitrogen, while those parameters show only minor influence when the ratio is surpassing 3:1. Nitrogen doping in this system improves the rate capability (due to the enhanced ion transport dynamics) rather than the amount of energy stored.