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concluded that the Cl2 generation risk was low. However, Cl2 generation has proven an issue in scaled, deployed systems. A public presentation described an MA VRFB system โburpingโ electrolyte beyond containment and rapid component corrosion that resulted in leaks.12 In private communications with our group, additional operators of fielded MA VRFBs have reported high levels of Cl2 generation. This gas generation resulted in several incidents with energetic reactions that led to loss of electrolyte containment. These developments highlight the importance of revisiting the question of Cl2 evolution in MA electrolytes, especially as investment and interest in MA VRFBs continues to grow.13 In the present study, we used a Universal Gas Analyzer (UGA) to directly detect Cl2 in the headspace of a single flow cell system (Fig. S1) to quantify Cl2 generation from the electrolyte and identify the underlying mechanism. We considered gas evolution pathways through electrochemical and chemical means as described by equations 1 and 2, respectively: ๐๐1. 2๐ถ๐!ยฎ๐ถ๐" + 2๐! , ๐ธ# =1.359๐๐ฃ๐ ๐๐ป๐ธ๐๐ก๐๐๐,1๐๐ป๐ถ๐ 14 ๐๐2. ๐๐$ +2๐ป$ +๐ถ๐! ยฎ๐๐"$ + ๐ป ๐+ %๐ถ๐ 11 " """ The electrochemical pathway could occur as a side reaction during charging of the posolyte (equation 3) and the chemical pathway as a self-discharge reaction at high states of charge. ๐๐3. ๐๐$ +2๐ป$ + ๐! ยฎ๐๐"$ + ๐ป ๐,๐ธ# = 1.00๐๐ฃ๐ ๐๐ป๐ธ 15 "" We found that electrochemical generation at the positive electrode (PE) during charging is the most likely pathway for generation of Cl2 gas, despite the formal potential for Cl2 evolution being ~360 mV higher than the V4+/V5+ formal potential (1.359 V versus 1.00 V, respectively). 4PDF Image | Chlorine Gas Generation in Mixed-Acid Vanadium Redox
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