Ionic Effect on Electrochemical Behavior of Water-Soluble Radical Polyelectrolytes

Water-soluble redox-active polymers (RAPs) have emerged as attractive electroactive materials for aqueous redox flow batteries because these systems rely on readily available size-exclusion membranes rather than expensive ion-selective membranes. While incorporating ionic units is the most effective strategy for forming water-soluble redox polyelectrolytes, little is known about how charges dictate their electrochemical behavior. Here, we design a series of water-soluble TEMPO (2,2,6,6-tetramethylpiperidyl-1-oxy) radical polyelectrolytes with identical radical distribution but various ionic groups through a sequential postmodification method. Physical and electrochemical characterizations show disparate diffusion coefficients (D) and charge transfer kinetics (k(0)) of these radical polyelectrolytes at various pH. Particularly, pH exerts a strong impact on k(0) of the negatively charged polymer (i.e., with carboxylic acid groups). The bimolecular reaction rate k(ex) determined from redox-induced polymer films shows electrostatic interactions between charged segments can enhance the electron self-exchange reaction rate by ten folds. The results suggest that charge effects are of great importance when designing water-soluble redox polymers for electrochemical applications.