A Viologen-Based Anolyte with a Very Negative Redox Potential for Neutral Aqueous Redox Flow Batteries

Abstract

Redox flow batteries have been recognized as a promising option for energy-storage purposes, mitigating the intermittency of renewable sources of energy such as solar, wind, and hydroelectric power. In particular, aqueous redox flow batteries (ARFBs) are very attractive owing to high conductivity, relatively low cost, and safe nature of aqueous electrolytes. Performance of ARFBs can be further improved with developing new electroactive species. Viologens are a group of organic compounds with great tunability, making them appealing for flow battery applications. In this study, a viologen-based electroactive compound called MMV is proposed with the potential of improving performance of aqueous flow batteries.The potential of MMV as an anolyte was investigated for developing a neutral aqueous flow battery. MMV required a simple synthesis procedure with inexpensive starting materials, resulting in a low cost. MMV showed solubility of almost 3 M that is relatively high compared to other organic electroactive compounds, such as quinones, especially in neutral electrolytes. The electrochemical reaction of MMV involved the transfer of one electron at fast kinetics. Additionally, MMV demonstrated a redox potential of -1.05 V vs. SCE that is one of the most negative redox potentials reported for organic electroactive species under neutral conditions. These characteristics indicated that MMV is a promising anolyte candidate. Such a very negative redox potential and high solubility provide MMV the potential to significantly improve performance of a flow battery in terms of capacity, energy density, and cell potential. Despite these interesting properties, MMV exhibited a poor cycling performance. MMV underwent irreversible reactions at elevated concentrations. Signs of dimerization and also precipitation were observed during cycling. The irreversible reactions led to a high capacity fade rate (2.1%/cycle). Approaches to improve the cycling performance include synthesizing MMV-derivatives that possess a higher charge compared to that of MMV to possibly limit the extent of both dimerization and precipitation.