Thermally Tuned Redox Matching in Redox-Mediated Flow Batteries

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The intermittency of renewable energy sources remains a central challenge for grid-scale energy storage. Redox flow batteries (RFBs) offer a promising solution by decoupling power and energy; however, their deployment is hindered by low energy density imposed by the solubility of redox-active species. 1 Redox-mediated flow batteries (RMFBs) address this limitation by incorporating solid charge boosters, but their performance critically depends on the thermodynamic redox matching and kinetic synchronization between the soluble mediator and solid booster. 2,3 This study introduces temperature as a dynamic and reversible control parameter for tuning redox thermodynamics and reaction kinetics in RMFBs, offering a versatile alternative to conventional electrolyte engineering strategies. Using a ferri/ferrocyanide mediator and a Prussian blue booster as a model system, we demonstrate that the redox potentials of the mediator and booster exhibit divergent temperature dependencies. 4 This divergence enables thermally driven redox matching, creating an operational window to enhance solid booster utilization and offering a pathway for harvesting low-grade thermal energy. Electrochemical characterization, including cyclic voltammetry and state-of-charge-dependent open-circuit voltage measurements, is used to quantify temperature-induced shifts in redox potentials. Symmetric flow cell experiments utilizing an in-line reference electrode further isolate mediator-booster kinetic interactions under controlled thermal conditions. Together, these results establishe temperature as a versatile control knob for optimizing redox matching and reaction kinetics in RMFBs, providing a framework for coupling electrochemical energy storage with thermal resources. References J. Egitto et al., Journal of Electrochemical Energy Conversion and Storage , 19 (2022) https://doi.org/10.1115/1.4054697. N. J. Matteucci, C. T. Mallia, B. J. Neyhouse, and F. R. Brushett, J. Electrochem. Soc. , 172 , 070539 (2025). M. Moghaddam et al., Molecules , 26 , 2111 (2021). Y. Yang et al., Proceedings of the National Academy of Sciences , 111 , 17011–17016 (2014).

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