Electrolyte Imbalance Determination of a Vanadium Redox Flow Battery by Potential‐Step Analysis of the Initial Charging

Vanadium redox flow batteries (VRFB) suffer from capacity fades owing to side reactions and crossover effects through the membrane. These processes lead to a deviation of the optimal initial average oxidation state (AOS=+3.5) of vanadium species in both half‐cell electrolytes. To rebalance the electrolyte solutions, it is first necessary to determine the current AOS. In this study, a new method was developed that enables an accurate determination of the AOS. A potential‐step analysis was performed with mixed electrolyte solutions of both half‐cells during the initial charging. The potential was recorded with a simple open‐circuit voltage (OCV) cell, and the potential‐steps were analyzed. A correlation between the duration of the potential plateaus in the OCV and the amount of vanadium ions of a certain oxidation state in the half‐cell electrolytes was found and used to precisely determine the AOS with a maximum error of 3.6 %.