Aqueous Organic Redox Flow Batteries (AORFBs) have emerged as promising and potentially disruptive technologies for the storage of energy from intermittent renewable sources. With the goal of cost-effective, safe, and scalable stationary electricity storage systems, AORFBs could eclipse Li-ion batteries due to their inherent non-flammability, lack of materials scarcity fluctuations, and intrinsic decoupling of energy and power capacities. Recent work has demonstrated that calendar life, rather than cycle life, limits molecular lifetimes in AORFBs due to various molecular instabilities that lead to side reactions, thus inhibiting performance. For accurately determining molecular fade rates, the importance has been demonstrated of potentiostatic holds in order to avoid artifacts caused by drifts in internal resistance; additionally the utility of volumetrically unbalanced, compositionally-symmetric cell configurations to distinguish molecular fade from membrane crossover has been demonstrated [1]. However, some reports continue to use purely galvanostatic cycling to characterize molecular stability, leading to unreliable reports of molecular fade rates.An in-depth study comparing previously published redox-active organic molecules [2-8] has been performed using the symmetric cell protocol. True capacity fade rates as functions of concentration and pH are evaluated in a high-throughput setup using high-precision coulometry. Collectively, these results highlight the relevance of electrochemical techniques to understand molecular degradation in AORFBs. By accelerating the screening process of candidate molecules for AORFBs and ensuring rigorous assessment of battery performance, these techniques are expected to more rapidly advance good candidates for long lifetime RFB designs, capable of enabling massive grid penetration of intermittent renewable energy.[1] M.-A. Goulet and M. J. Aziz, “Flow Battery Molecular Reactant Stability Determined by Symmetric Cell Cycling Methods,” Journal of the Electrochemical Society , 165, A1466 (2018).[2] D. G. Kwabi, K. Lin, Y. Ji, E. F. Kerr, M.-A. Goulet, D. De Porcellinis, D. P. Tabor, D. A. Pollack, A. Aspuru-Guzik, R. G. Gordon, and M. J. Aziz, “Alkaline Quinone Flow Battery with Long Lifetime at pH 12,” Joule, 2, 1894 (2018).[3] Y. Ji, M.-A. Goulet, D. A. Pollack, D. G. Kwabi, S. Jin, D. De Porcellinis, E. F. Kerr, R. G. Gordon, and M. J. Aziz, “A Phosphonate-Functionalized Quinone Redox Flow Battery at Near-Neutral pH with Record Capacity Retention Rate,” Advanced Energy Materials, 9, 1900039 (2019).[4] M.-A. Goulet, L. Tong, D. A. Pollack, D. P. Tabor, S. A. Odom, A. Aspuru-Guzik, E. E. Kwan, R. G. Gordon, and M. J. Aziz, “Extending the Lifetime of Organic Flow Batteries via Redox State Management,” Journal of the American Chemical Society, 141, 8014 (2019).[5] E. Drazevic, C. Szabo, D. Konya, T. Lund, K. Wedege, and A. Bentien, “Investigation of Tetramorpholinohydroquinone as a Potential Catholyte in a Flow Battery,” ACS Applied Energy Materials, 2, 4745 (2019).[6] Y. Liu, M.-A. Goulet, L. Tong, Y. Liu, Y. Ji, L. Wu, R. G. Gordon, M. J. Aziz, Z. Yang, and T. Xu, “A Long Lifetime All-Organic Aqueous Flow Battery Utilizing TMAP-TEMPO Radical,” Chem, 5, 1 (2019).[7] J. Luo, W. Wu, C. Debruler, B. Hu, M. Hu, and T. L. Liu, “A 1.51 V pH Neutral Redox Flow Battery towards Scalable Energy Storage,” Journal of Materials Chemistry A, 7, 9130 (2019).[8] J. Luo, B. Hu, M. Hu, Y. Zhao, and T. L. Liu, “Status and Prospects of Organic Redox Flow Batteries toward Sustainable Energy Storage,” ACS Energy Letters, 4, 2220 (2019).
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