(Invited) Understanding Capacity Fade Behavior in Aqueous Organic Redox Flow Batteries Via Zero-Dimensional Models and High-Throughput Cell Cycling
Authors: Fell Eric M. , Aziz Michael J. 
Published: February 2024

Aqueous Organic Redox Flow Batteries (AORFBs) have emerged as promising and potentially disruptive technologies for the storage of electrical energy from intermittent renewable sources for use over long discharge durations when the sun isn’t shining and the wind isn’t blowing. AORFBs could become preferred over Li-ion batteries for grid-scale stationary storage due to their potentially low-cost active materials made of Earth-abundant elements, their inherent non-flammability, and the intrinsic decoupling of energy and power capacities in the flow battery design. Our group 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 [1]. To accurately determine molecular fade rates, we utilize potentiostatic cycling to avoid artifacts caused by drifts in internal resistance and employ volumetrically unbalanced compositionally symmetric cell configurations to distinguish molecular fade from membrane crossover or the two sides drifting out of balance.
We have developed a high-throughput setup for AORFBs, capable of cycling cells at elevated temperatures, providing a new dimension in the flow battery characterization space to explore multiple cell parameters simultaneously. The recent incorporation of the decay of active material into zero-dimensional cell-cycling models for AORFBs [2,3] allows for exploration of the causes of various trends seen in flow cell temporal capacity behavior. Complemented by zero-dimensional modelling, we explore temporal capacity evolution in symmetric cells driven by different capacity fade mechanisms such as active species degradation [4], self-discharge [5], and membrane crossover. Collectively, these results highlight the relevance of electrochemical techniques to understand molecular degradation in AORFBs and expedite the screening process of candidate molecules for long lifetime AORFBs, which may enable 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] S. Modak and D. G. Kwabi, “A Zero-Dimensional Model for Electrochemical Behavior and Capacity Retention in Organic Flow Cells,” Journal of the Electrochemical Society, 168, 080528 (2021).
[3] B. J. Neyhouse, J. Lee, F. R. Brushett, “Connecting Material Properties and Redox Flow Cell Cycling Performance through Zero-Dimensional Models” Journal of The Electrochemical Society, 169, 090503 (2022).
[4] D. G. Kwabi, Y. Ji, M. J. Aziz, “Electrolyte Lifetime in Aqueous Organic Redox Flow Batteries: A Critical Review,” Chemical Reviews, 120, 6467 (2020).
[5] E. M. Fell, D. De Porcellinis, Y. Jing, V. Gutierrez-Venegas, R. G. Gordon, S. Granados-Focil, M. J. Aziz, “Long-term stability of ferri-/ferrocyanide as an electroactive component for redox flow battery applications: On the origin of apparent capacity fade,” ChemRxiv (2022). https://chemrxiv.org/engage/chemrxiv/article-details/62913087f89e5d4e6ee8828d