Zinc–iron redox flow batteries (ZIRFBs) possess intrinsic safety and stability and have been the research focus of electrochemical energy storage technology due to their low electrolyte cost. This review introduces the characteristics of ZIRFBs which can be operated within a wide pH range, including the acidic ZIRFB taking advantage of Fen+ with high solubility, the alkaline ZIRFB operating at a relatively high open-circuit potential and current densities, and the neutral ZIRFB providing a non-toxic, harmless, and mild environment. No matter what kind of ZIRFB, there are always zinc dendrites limiting areal capacity on the anode, which has become an obstacle that must be considered in zinc-based RFBs. Therefore, we focus on the current research progress, especially the summarizing and analysis of zinc dendrites, Fe(III) hydrolysis, and electrolytes. Given these challenges, this review reports the optimization of the electrolyte, electrode, membrane/separator, battery structure, and numerical simulations, aiming to promote the performance and development of ZIRFBs as a practical application technology. Based on these investigations, we also provide the prospects and development direction of ZIRFBs.
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