Redox flow batteries (RFBs) have been investigated as a promising energy storage system (ESS) for grid applications over the past several decades due to their unique features, which include the separation of energy and power output, high safety, and long cycle life. It is therefore vital but still in severe deficiency to understand the reliability of RFBs, and the mechanisms that cause degradation with time. One of the primary challenges involves the unseparated contributions from individual electrodes due to the absence of a stable reference electrode (RE), particularly for long-term cycle testing in a scaled cell. Herein, we first develop an ultra-stable RE for scaled all-vanadium RFBs. The newly developed RE, based on a dynamic hydrogen electrode (DHE) with a novel design on the area (size) and surface roughness of platinum electrodes, demonstrates high accuracy and long-term stability that enables in situ monitoring of individual electrode potentials throughout 500 cycles. By introducing the RE approach to decouple the cathode and anode in conjunction with the measurement of voltage profiles, overpotentials and polarization curves, the reliability and degradation mechanism of a scaled all-vanadium RFB are further explored, revealing the diverse behaviors of individual electrodes. This exploratory work will benefit the future design and development of a stable RE for a scaled ESS, as well as the fundamental understanding of the RFB's reliability and degradation mechanism.
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