A Universal Additive Design Strategy to Modulate Solvation Structure and Hydrogen Bond Network toward Highly...

Aqueous all-iron redox flow batteries (RFBs) are promising competitors for next-generation grid-scale energy storage applications. However, the high-performance operation of all-iron RFBs in a wider temperature range is greatly hindered by inferior iron plating/stripping reaction and low solid-liquid transition temperature at Fe anode. Herein, a universal electrolyte additive design strategy for all-iron RFBs is reported, which realizes a highly reversible and dendrite-free Fe anode at low temperatures. Quantum chemistry calculations first screen several organic molecules with oxygen-containing functional groups and identify N,N-Dimethylacetmide (DMAc) as a potential candidate with low cost, high solubility, and strong interactions with Fe²⁺ and H₂ O. Combined experimental characterizations and theoretical calculations subsequently demonstrate that adding DMAc into the FeCl₂ solution effectively reshapes the primary solvation shell of Fe²⁺ via the Fe²⁺ -O (DMAc) bond and breaks hydrogen-bonding network of water through intensified H-bond interaction between DMAc and H₂ O, thereby affording the Fe anode with enhanced Fe/Fe²⁺ reversibility and lower freezing point. Consequently, the assembled all-iron RFB achieves an excellent combination of high power density (25 mW cm^-2 ), long charge-discharge cycling stability (95.59% capacity retention in 103 h), and preeminent battery efficiency at -20 °C (95% coulombic efficiency), which promise a future for wider temperature range operation of all-iron RFBs.