A Physical Organic Chemistry Approach to Developing Cyclopropenium-Based Energy Storage Materials for Redox Flow Batteries

ConspectusRedox flow batteries (RFBs) represent a promising modality for electrical energy storage. In these systems, energy is stored via paired redox reactions of molecules on opposite sides of an electrochemical cell. Thus, a central objective for the field is to design molecules with the optimal combination of properties to serve as energy storage materials in RFBs. The ideal molecules should undergo reversible redox reactions at relatively high potentials (for the molecule that is oxidized during battery charging, called the catholyte) or low potentials (for the species that is reduced during battery charging, called the anolyte). Furthermore, anolytes and catholytes must be highly soluble in the electrolyte solution and stable to extended electrochemical cycling in all battery-relevant redox states. The ideal candidates would undergo more than one reversible electron transfer event. Finally, the optimal structures should be resistant to crossover through a selective separator in order to maintain isolation of the two sides of the cell. This Account describes our design and optimization of organic molecules for this application. We first provide background for the metrics and experiments used to characterize anolytes/catholytes and to progress them toward deployment in flow batteries. We then use our studies of aminocyclopropenium-based catholytes to illustrate this workflow and approach.We identified tris(dimethylamino) cyclopropenium hexafluorophosphate as a first-generation catholyte for nonaqueous RFBs based on literature reports from the 1970s describing its reversible chemical and electrochemical oxidation. Cyclic voltammetry and electrochemical cycling experiments in acetonitrile/LiPF₆ confirmed that this molecule undergoes oxidation at relatively high potential (0.86 V versus ferrocene/ferrocenium) and exhibits moderate stability toward charge-discharge cycling. Replacing the methyl groups with isopropyl substituents led to enhanced cycling stability but poor solubility of the radical dication (<0.1 M in acetonitrile). Solubility was optimized using quantitative structure-property relationship modeling, which predicted derivatives with ≥10-fold enhanced solubility. Cyclopropeniums with 300-500 mV higher redox potentials were identified by replacing one of the dialkylamino substituents with a less electron-donating thioalkyl or aryl group. Multielectron catholytes were developed by creating hybrid structures that contain a di(amino) cyclopropenium conjugated with a phenothiazine moeity. Finally, oligomeric tris(amino) cyclopropeniums were designed as crossover resistant catholytes. Optimization of their solubility enabled the deployment of these oligomers in high concentration asymmetric redox flow batteries with energy densities that are comparable to the state-of-the-art commercial aqueous inorganic systems.