Screening Ultra-Stable (Phenazine)dioxyalkanocic Acids with Varied Water-Solubilizing Chain Lengths for High-Capacity Aqueous Redox Flow Batteries

Aqueous redox flow batteries (ARFBs) hold great potential for large-scale energy storage. Recently, research on aqueous flow batteries has shifted toward water-soluble organic molecules with redox capabilities to reduce the use of mineral resources. The chemical and electrochemical stabilities of organic compounds are heavily influenced by their functional groups and reaction sites. In this study, we present a low-cost synthesis of the O-alkyl-carboxylate-functionalized derivatives of 2,3-dihydroxyphenazine, namely, phenazine-(2,3-diyl) dioxy dibutyric acid (DBEP) and phenazine-(2,3-diyl)dioxy diacetic acid (DAEP), which serve as negolytes and exhibit good reversibility and high redox kinetics. The evidence is provided to clarify the capacity degradation mechanisms of DAEP and DBEP by a series of comprehensive characterizations. Similar to anthraquinones functionalized with alkyl chains, the main degradation mechanism of DAEP modified with acetic acid is due to side chain loss. Longer side chains are more stable and can withstand long-term electrochemical reactions. DBEP modified with butyric acid exhibits superior chemical and electrochemical stability. Our results demonstrate that rational molecular design and suitable membranes, such as the alkaline ARFBs based on DBEP negolyte, potassium ferrocyanide (K₄Fe(CN)₆) posolyte, and custom sulfonated poly(ether ether ketone) membrane, can deliver a high open-circuit voltage of 1.17 V and high capacity retention of 99.997% per cycle for over 1000 cycles at 50 mA cm^-2. This study highlights the importance of not only considering the modification position of the molecules but also focusing on the influence of various side chains on the redox core's stability toward sustainable grid-scale energy storage applications.