An Electrolyte with Elevated Average Valence for Suppressing the Capacity Decay of Vanadium Redox Flow Batteries

Nafion series membranes are widely used in vanadium redox flow batteries (VRFBs). However, the poor ion selectivity of the membranes to vanadium ions, especially for V²⁺, results in a rapid capacity decay during cycling. Although tremendous efforts have been made to improve the membrane's ion selectivity, increasing the ion selectivity without sacrificing the proton conductivity is still a challenging issue. In this work, instead of focusing on enhancing the membranes' ion selectivity, we develop an efficient valence regulation strategy to suppress the capacity decay caused by the crossover of V²⁺ in VRFBs. Despite the discharge capacity of the VRFB with the elevated average valence electrolytes (V^3.68+) being slightly lower than that with commercial electrolytes (V^3.50+) in the first 35 cycles, the accumulated discharge capacity in 400 cycles is improved by 52.33%. Moreover, this method is efficient, is easy to scale up, and provides deep insights into the capacity decay mechanism of VRFBs.