Restoring capacity and efficiency of vanadium redox flow battery via controlled adjustment of electrolyte composition by electrolysis cell

Abstract

One of the major challenges in vanadium redox flow batteries (VRFB) is a gradual decrease of available capacity over operation time. The VRFB capacity fade is a complex issue that affects volume, total content, and average valence of vanadium ions in posolyte and negolyte. Imbalances that occur due to crossover of vanadium ions, osmosis and electroosmosis of water can be dealt with by intermittent mixing of posolyte and negolyte, thereby prolonging VRFB operation at high capacity rates. However, the change in the average oxidation state (AOS) should be considered for stable VRFB operation. The imbalance of vanadium valence arises due to side reactions during charge–discharge processes. This work proposes a novel operando method for restoration of the initial VRFB capacity. Partial posolyte reduction on the cathode and oxygen evolution reaction on the RuO2/Ti electrode of the electrolysis cell, following which electrolytes mix and recharge, allow to recover initial performance parameters. Optimizing electrolysis conditions ensures high energy efficiency of the rebalancing procedure. Coulometric sensors data provide the charge required for posolyte reduction. The proposed approach for VRFB capacity recovery allows for complete restoration of performance parameters regardless of the magnitude of a capacity drop.