Development of High Energy Density Diaminocyclopropenium‐Phenothiazine Hybrid Catholytes for Non‐Aqueous Redox Flow Batteries

This report describes the design of diaminocyclopropenium‐phenothiazine hybrid catholytes for non‐aqueous redox flow batteries. The molecules are synthesized in a rapid and modular fashion by appending a diaminocyclopropenium (DAC) substituent to the nitrogen of the phenothiazine. Combining a versatile C‐N coupling protocol (which provides access to diverse derivatives) with computation and structure‐property analysis enabled the identification of a catholyte that displays stable two‐electron cycling at potentials of 0.64 and 1.00 V vs. Fc/Fc+ as well as high solubility in all oxidation states (≥0.45 M in TBAPF6/MeCN). This catholyte was deployed in a high energy density two‐electron RFB, exhibiting >90 % capacity retention over 266 hours of flow cell cycling at >0.5 M electron concentration. Through rational molecular design, simple chemical synthesis, and structure–property computation analysis, a new catholyte with high potential, two‐electron transfer, and high solubility is developed for non‐aqueous redox flow batteries.