Tailoring Dihydroxyphthalazines to Enable Their Stable and Efficient Use in the Catholyte of Aqueous Redox Flow Batteries

To enable cost-efficient stationary energy storage, organic active materials are the subject of current investigations with regard to their application in aqueous redox flow batteries. Especially quinones with their beneficial electrochemical properties and natural abundance pose a promising class of compounds for this challenging endeavor. Yet, there are not many active materials available for the catholyte side to realize solely quinone-based systems. Herein we introduce the novel hydroquinone 5,8-dihydroxy-2,3-phthalazine together with two of its derivatives and propose it as a promising active material for the catholyte side of aqueous redox flow batteries. We systematically investigate the electrochemical properties as well as the structure–property relationship of this class of compounds. The unmodified dihydroxyphthalazine exhibits a favorably high redox potential of 796 mV vs SHE in acidic solution that is competitive with benzoquinone compounds. Moreover, the introduced dihydroxyphthalazines feature a high electron transfer rate surpassing benzoquinone species by almost one order of magnitude. With regard to stable cycling performance, we further achieved a high resilience against detrimental side reactions such as Michael addition by adding methyl substituents to the base structure. Our experimental findings are supported and extended by theoretical considerations in terms of density functional theory calculations. With this combined approach we outline further promising dihydroxyphthalazine-based materials with regard to performance-relevant quantities like redox potential, cycling stability, and water solubility. This study aims to propel further research in the field of quinone-based active materials for the catholyte of future aqueous redox flow batteries.