Alkaline zinc-iron flow batteries (AZIFBs) are well suited for energy storage because of their good safety, high cell voltage, and low cost. However, the occurrence of irreversible anodic parasitic reactions results in a diminished coulombic efficiency (CE), unbalanced charge state of catholyte/anolyte and subsequently, a poor cycling performance. Here, a universal CE compensation strategy centered around the oxygen evolution reaction (OER) on the cathodic side, is reported. This strategy aims to equalize the charge state of the [Fe(CN)6]3-/4--based catholyte and counteract pH fluctuations. The OER process can be implemented either directly on the electrode through electrochemical reaction or in an external catalytic reactor column via a redox-mediated process. This innovative approach effectively mitigates the gradual accumulation of [Fe(CN)6]3- in discharged catholyte and [Zn(OH)4]2- in charged anolyte by consuming the extra OH- during a continuous cycling process. As a result, AZIFBs demonstrate exceptional cycling performance with an extremely low capacity fading rate of 0.0128%/day (or 0.0005%/cycle) over 600 cycles at 80% state of charge (SOC). The proposed CE compensation strategy not only provides an effective way to address the CE loss issue for AZIFBs, but also can be applied to diverse battery technologies encountering CE loss caused by water/oxygen-induced parasitic reactions.
Keywords: alkaline Zn‐Fe flow batteries; coulombic efficiency compensation; oxygen evolution reaction; redox mediated chemistry.
© 2024 The Author(s). Advanced Materials published by Wiley‐VCH GmbH.