Highly Water-Soluble Phenothiazine-Based Quaternary Ammonium Salt Organic Cathode Materials for Organic Flow Batteries

Organic redox-active molecules are promising catholyte materials for aqueous organic redox flow batteries (AORFBs), yet they often suffer from low solubility and poor cycling stability. Herein, we report a series of water-soluble phenothiazine derivatives functionalized with quaternary ammonium groups. The optimized compound, N,N,N-trimethyl-1-(10H-phenothiazin-10-yl) propan-2-aminium chloride (TMiPrPTCl), exhibits exceptional solubility (2.69 M in water) and a high redox potential (0.902 V vs. SHE). A comparative study of four derivatives reveals that side-chain length and branching critically modulate both solubility and degradation pathways: while three-carbon-linked analogs N,N,N-trimethyl-3-(10H-phenothiazin-10-yl)propan-1-aminium chloride (TMPrPTCl) degrade primarily via irreversible oxidation to sulfoxide, two-carbon-linked species (TMiPrPTCl) undergo additional side-chain cleavage, leading to rapid capacity fade. Although the quaternization strategy successfully achieves record solubility, the electrochemical stability remains a key challenge. Post-cycling analysis confirms the loss of redox activity and the formation of inert products. This work highlights the delicate balance between solubility enhancement and molecular stability, providing clear design guidelines for future phenothiazine-based catholytes.