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To confirm Cl2 is the product of an electrochemical side reaction rather than a chemical one, we completed a potential stepping experiment wherein the cell was held at a series of different voltages for two hours each (Fig. 3). After each step the cell rested for 30 min at open circuit voltage (OCV). Cl2 generation starts when the cell is held at 1.5 V (Fig. 3c), a slightly lower voltage than observed in the cycling experiments (1.52 V). The lower voltage is likely from a lag between when gas is generated in the cell and when it is transported to the vial and detected by the UGA. The voltage in the cycling experiments is steadily increasing during charging, so the perceived voltage of Cl2 generation would be slightly higher by the time the Cl2 reached the UGA. The potential hold experiments thus offer a more accurate onset potential for gas generation. At cell voltage holds of 1.55, 1.6 and 1.65 V, the Cl2 concentration reaches peaks of about 1.2%, 3.0%, and 4.9%, respectively. When the potential is removed, the Cl2 Figure 3: Potential stepping experiment. Cell was discharged and then charged at 10 mA/cm2 in 50 mV of cell voltage increments. Each potential was held for 2 h with a 30 min rest afterwards. Note that the 0.05 V steps (1.15 V, 1.25 V, etc.) are unlabeled. a) Cell voltage during potential steps. b) PE voltage vs Pt pseudo reference electrode. c) Cl2 gas concentration in the posolyte vial headspace. d) 2Cl-/Cl2 formal potential calculated using equation 4. 8PDF Image | Chlorine Gas Generation in Mixed-Acid Vanadium Redox
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