Herein, we present a novel copolymer (1), which incorporates (2,2,6,6-tetramethylpiperidin-1-yl)oxyl (TEMPO) as a redox-active compound and the zwitterionic [(2-(methacryloxy)- ethyl)dimethyl-(3-sulfopropyl)]ammonium hydroxide as a solubilizing comonomer, for the application as catholyte species within aqueous redox flow batteries (RFBs). The presented polymer-based redox-active material exhibits a high degree of oxidation and, compared to other commonly utilized active polymeric materials, a high solubility exceeding 20 Ah L-1, while still featuring a low viscosity in 1.5 M NaClaq solution. The electrochemical behavior was investigated by cyclic voltammetry, and a reversible redox reaction at E-0 = 0.7 V versus the Ag/AgCl reference electrode of the TEMPO/TEMPO+ redox pair was observed. Symmetric design battery studies with two different types of membranes, a size-exclusion versus an anion-exchange membrane, were used to evaluate the applicability of this polymer in the RFB setup. Long-term stability tests over 1000 cycles indicate good stability with a capacity loss of ca. 0.08% per cycle utilizing a size-exclusion and an anion-exchange membrane, respectively. Finally, an all- organic aqueous RFB was operated utilizing 1 as the catholyte species and N,N'-dimethyl-4,4'-bipyridinium dichloride (MV) as the anolyte species. Such RFB exhibits Coulombic efficiencies of 99.01 +/- 1.40% over 125 consecutive cycles, an energy efficiency of ca. 93%, and an initial energy density of 5.33 Wh L-1 during the studied discharge process.
