High‐Stable All‐Iron Redox Flow Battery with Innovative Anolyte based on Steric Hindrance Regulation

All-soluble all-iron redox flow batteries (AIRFBs) are an innovative energy storage technology that offer significant financial benefits. Stable and affordable redox-active materials are essential for the commercialization of AIRFBs, yet the battery stability must be significantly improved to achieve practical value. Herein, ferrous complexes combined with the triisopropanolamine (TIPA) ligand are identified as promising anolytes to extend battery life by reducing cross-contamination due to a pronounced steric hindrance effect. The coordination structure and failure mechanism of our Fe-TIPA complexes were determined by molecular dynamics simulation and spectroscopic experiments. By coupling with [Fe(CN)₆]^4-/3-, Fe-TIPA/Fe-CN AIRFBs retained excellent stability exceeding 1831 cycles at 80 mA ⋅ cm^-2, yielding an energy efficiency of ~80 % and maintaining a steady discharge capacity. Moreover, the all-soluble electrolyte was tested in an industrial-scale Fe-TIPA/Fe-CN AIRFB prototype energy storage system, where an energy efficiency of 81.3 % was attained. Given the abundance of iron resources, we model the TIPA AIRFB electrolyte cost to be as low as 32.37 $/kWh, which is significantly cheaper than the current commercial level. This work demonstrates that steric hindrance is an effective measure to extended battery life, facilitating the commercial development of affordable flow batteries.