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when the cell potential was near 1.5 V the PE experienced over 100 mV of polarization. This is likely caused by poor mass transport of V4+ in the form of VO2+ to the electrode. The observed polarization would provide enough overpotential to enable the Cl2 gas evolution reaction to occur. In a full-scale system with a larger stack and total volume of electrolyte, the generated amounts of Cl2 could pose a significant safety risk. The size of the system may even increase the amount of gas evolution as inefficiencies from mass transport are likely to increase as systems scale. A hypothetical 1 MW/4 MWh system held at 1.55 or 1.65 V would generate 140 or 564 L of Cl2, respectively, based on the potential step data shown in Figure 3 (see calculations and assumptions in the SI). If this gas leaked, it would pose a significant risk to those around the system. The gas could also directly as Cl2 or indirectly as HCl corrode the battery components, particularly any electrical components or pumps, leading to reduced performance and even failure of the system.17 Full reaction of all the Cl2 generated at cell potentials of 1.55 and 1.65 V with H2 (produced at the negative electrode) would generate 1.1 and 4.6 MJ of heat, respectively. The speed of this reaction would limit heat absorption by the bulk electrolyte and be sufficient to cause loss of primary and possibly secondary containment.18-21 Based on our initial experiments, the following practices may limit Cl2 gas generation. First, limiting the max SOC to 70% or less may prevent the system from being driven by a mass transport limited PE. In general, mass transport should be optimized, particularly for operation at higher SOCs. For example, the pumping rate could be varied based on system SOC. Second, limiting the head space may reduce the total amount of Cl2 generated. Third, selectively balancing the electrolyte so that the posolyte volume is greater than the negolyte would reduce the PE potential and reduce the likelihood of Cl2 generation (but at the cost of increasing H2 11PDF Image | Chlorine Gas Generation in Mixed-Acid Vanadium Redox
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