Redox electrolytes for supercapacitors (SCs) have recently sparked widespread interest. Due to the redox reactions within electrolytes, they can achieve high capacitance and long cycle stability. However, the energy density of SCs with redox electrolytes is limited by the narrow applied electrochemical window due to the irreversible side reaction of redox mediators at high potential. To overcome this issue, a redox mediator with a high redox potential, tetrachloridehydroquinone (TCHQ), is added to organic electrolytes to obtain a broad electrochemical window. TCHQ is designed to undergo a dehydrogenation reaction catalyzed by N-doped activated carbon to provide capacitance. The pyrrole N atoms have the highest electrocatalytic activity based on the theoretical calculation of reaction overpotential with predicted reaction pathways due to their Lewis basicity. Benefitting from that, TCHQ shows promising reversibility with a larger electrochemical window (up to 2.7 V). As a result, a higher energy density is obtained when compared to commercial SCs. This study proposes a strategy for designing redox mediators and interfaces of SCs with high energy density and a calculation method of dehydrogenation reaction electrocatalysis.
Keywords: Lewis bases; ab initio calculation; carbon material; electrocatalysis; supercapacitor.