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concentration decreases, indicating that it was the application of voltage and the drawing of current that drove the reaction. If the reaction was a chemical process as described in equation two, we would expect the Cl2 concentration to remain stable after potential was removed. The conclusion is further supported by Kim et al. who show that the chemical reaction in Equation 2 thermodynamically favors consumption of Cl2 rather than production.11 Gas consumption is discussed more in section 4 of the SI. Figure 4: Process whereby Cl2 gas generation may become favorable in the mixed-acid vanadium flow battery. The changes to both reactions’ potentials are relative as further work is needed to determine the precise contribution of each factor. Based on all the collected data, Figure 4 describes a possible pathway for electrochemical Cl2 generation to become favorable despite the Cl-/Cl2 standard reaction potential being 360 mV higher than the V4+/V5+ potential. We start with the ideal case where the two reactions are 360 mV apart. Then we factor in the effects of addition of HCl, low Cl2 partial pressure, and mass transport losses at high SOCs. The electrolyte chemistry may increase the voltage of the V4+/V5+ reaction. Two separate studies have observed that the V4+/V5+ reaction is shifted to 1.2 V vs SHE in a MA system of 2.5 M H2SO4 and 6 M HCl, 200 mV higher than in just sulfuric acid.6, 10 If we assume that this 9PDF Image | Chlorine Gas Generation in Mixed-Acid Vanadium Redox
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