Person:

Goulet, Marc-Antoni

Redox flow batteries based on quinone-bearing aqueous electrolytes have emerged as promising systems for energy storage from intermittent renewable sources. The lifetime of these batteries is limited by quinone stability. Here, we confirm that 2,6-dihydroxyanthrahydroquinone tends to form an anthrone intermediate that is vulnerable to subsequent irreversible dimerization. We demonstrate quantitatively that this decomposition pathway is responsible for the loss of battery capacity. Computational studies indicate that the driving force for anthrone formation is greater for anthraquinones with lower reduction potentials. We show that the decomposition can be substantially mitigated. We demonstrate that conditions minimizing anthrone formation and avoiding anthrone dimerization slow the capacity loss rate by over an order of magnitude. We anticipate that this mitigation strategy readily extends to other anthraquinone-based flow batteries and is thus an important step toward realizing renewable electricity storage through long-lived organic flow batteries.

The massive-scale integration of renewable electricity into the power grid is impeded by its intrinsic intermittency. The aqueous organic redox flow battery (AORFB) rises as a potential storage solution; however, the choice of positive electrolytes is limited, and the aqueous-soluble organic positive redox-active species reported to date have short lifetimes. Here we report a stable organic molecule for the positive terminal, 4-[3-(trimethylammonio)propoxy]-2,2,6,6- tetramethylpiperidine-1-oxyl (TMAP-TEMPO) chloride, exhibiting high (4.62 M) aqueous solubility. When operated in a practical AORFB against a negative electrolyte comprising BTMAP-viologen at neutral pH, the flow cell displayed an open-circuit voltage of 1.1 Volts and a coulombic efficiency of >99.73%. The capacity retention rate is among the highest of all-organic AORFBs reported to date, at 99.993% per cycle over 1000 consecutive cycles; the temporal capacity fade rate of 0.026% per hour is independent of concentration.