Abstract Aqueous redox flow batteries (ARFBs) are a promising technology for grid‐scale energy storage, however, their commercial success relies on redox‐active materials (RAM) with high electron storage capacity and cost competitiveness. Herein, a redox‐active material lithium ferrocyanide (Li4Fe(CN)6) is designed. Li+ ions not only greatly boost the solubility of Fe(CN)64− to 2.32 M at room temperature due to weak intermolecular interactions, but also improves the electrochemical performance of Fe(CN)64−/3−. By coupling with Zn, ZIRFBs were built, and the capacity of the batteries was as high as 61.64 Ah L−1 (pH‐neutral) and 56.28 Ah L−1 (alkaline) at a Fe(CN)64− concentration of 2.30 M and 2.10 M. These represent unprecedentedly high Fe(CN)64− concentrations and battery energy densities reported to date. Moreover, benefiting from the low cost of Li4Fe(CN)6, the overall chemical cost of alkaline ZIRFB is as low as $11 per kWh, which is one‐twentieth that of the state‐of‐the‐art VFB ($211.54 per kWh). This work breaks through the limitations of traditional electrolyte composition optimization and will strongly promote the development of economical Fe(CN)64−/3−‐based RFBs in the future.
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