Manipulating Aggregate Electrochemistry for High‐Performance Organic Redox Flow Batteries

Abstract Organic molecule in solutions is the energy storage unit in the organic redox flow batteries (ORFBs), of which the aggregation is acknowledged pivotal but has been rarely investigated. By establishing a pyridinium library, the manipulation over the aggregation in solutions is investigated at the molecular level. Both theoretical calculations and physiochemical methods are used to characterize the aggregate's structure, and salient findings are as follows. First, the singly‐reduced monoradicals simultaneously aggregate in a concentrated solution, which is driven by the solvation effect, orbital overlap and dispersion interaction. Second, the aggregation can be manipulated by the molecular engineering strategy and counteracted by introducing either electrostatic repulsive force or twisted geometry. Third, the monoradical's aggregation yields a decrease in the molecular singly occupied molecular orbital energy level and a linear scaling relationship with its thermodynamic potential. As a result, the increase in the concentration lowers the battery's voltage, which counteracts its effort to increase the battery's energy density. The anti‐aggregation is proven effective in breaking the scaling relationship and accordingly, a molecular strategy to manipulate aggregate electrochemistry is developed. This work provides physical insights into the electrolytic solution and chemical strategy for optimizing the flow battery.