Characterization of an Aqueous Flow Battery Utilizing a Hydroxylated Tetracationic Viologen and a Simple Cationic Ferrocene Derivative

Abstract

Herein, a new semi‐organic aqueous flow battery based on a hydroxylated tetracationic viologen, 1,1′‐bis(3‐((2‐hydroxyethyl)dimethylammonio)propyl)‐[4,4′‐bipyridine]‐1,1′‐diium tetrachloride ([(DMAE‐Pr)2‐Vi]Cl4), and the ferrocene derivative, (ferrocenylmethyl)trimethylammonium chloride (FcNCl), is demonstrated. Efficiency, accessible capacity, and capacity retention of the battery are investigated at two concentrations of the active redox species: 0.1 and 0.5 mol dm−3 in 1 mol dm−3 KCl near‐neutral electrolytes. The implementation of the ferrocene‐derivative posolyte decreases the capacity fade rate by a factor of ≈4 with respect to previous work using 4‐hydroxy‐2,2,6,6‐tetramethylpiperidin‐1‐oxyl (TEMPOL) as posolyte. Capacity loss is driven by crossover of the positive redox couple into the negolyte, in particular at high concentrations, indicating the need for more selective membranes and less permeable ferrocene derivatives. Discussions are supported by conductivity measurements, cell resistance, and postmortem analysis of the electrolytes using cyclic voltammetry and nuclear magnetic resonance (NMR) spectroscopy. The characterization of [(DMAE‐Pr)2‐Vi]Cl4 is expanded as a high‐energy negolyte and future scaleup requirements for aqueous organic flow batteries are informed.