Investigation of Iron(III) Tetraphenylporphyrin as a Redox Flow Battery Anolyte: Unexpected Side Reactivity with the Electrolyte

Redox flow batteries (RFBs) present an opportunity to bridge the gap between the intermittent availability of green energy sources and the need for on-demand grid level energy storage. While aqueous vanadium-based redox flow batteries have been commercialized, they are limited by the constraints of using water as an electrochemical solvent. Nonaqueous redox flow battery systems can be used to produce high voltage batteries due to the larger electrochemical window in nonaqueous solvents and the ability to tune the redox properties of active materials through functionalization. Iron porphyrins, a class of organometallic macrocycles, have been the subject of many studies for their photocatalytic and electrocatalytic properties in nonaqueous solvents. Often, iron porphyrins can undergo multiple redox events making them interesting candidates for use as anolytes in asymmetrical redox flow batteries or as both catholyte and anolyte in symmetrical redox flow battery systems. Here the electrochemical properties of Fe(III)TPP species relevant to redox flow battery electrolytes are investigated including solubility, electrochemical properties, and charge/discharge cycling. Commonly used support electrolyte salts can have reactivities that are often overlooked beyond their conductivity properties in nonaqueous solvents. Parasitic reactions with the cations of common support electrolytes are highlighted herein, which underscore the careful balance required to fully assess the potential of novel RFB electrolytes.