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Vanadium redox-flow batteries are a promising energy storage technology due to their safety, long-term stability, and independent adjustability of power and capacity. However, the vanadium crossover through the membrane causes a self-discharge, which results in a capacity shift towards one half cell. This leads to a gradual decrease in its efficiency over time. Capacity balancing methods for compensation of this effect require a reliable online state of charge (SoC) monitoring. Most common methods cannot provide exact values of the individual concentration of each species in both electrolytes. In particular, the state of the positive electrolyte cannot yet be precisely determined. In this work, an amperometric SoC monitoring is proposed as a new approach. First, the suitability of the principle is investigated with a rotating disc electrode (RDE). Then, a sensor based on a gas diffusion layer (GDL) is developed and tested in the positive electrolyte. The dependencies between oxidative current and V(IV)-concentration are examined as well as those between reduction current and V(V)-concentration. Using both relationships, a reliable measurement of all relevant concentrations is possible.

Monitoring the State of Charge of the Positive Electrolyte in a Vanadium Redox-Flow Battery with a Novel Amperometric Sensor