Chlorine Gas Generation in Mixed-Acid Vanadium Redox

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Chlorine Gas Generation in Mixed-Acid Vanadium Redox ( chlorine-gas-generation-mixed-acid-vanadium-redox )

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4. Cl2 Consumption The Cl2 removal process likely takes place through the dissolving of chlorine gas into the electrolyte, as governed by equation S1: 𝑒𝑞 𝑆1. log(𝐶𝑙 ) = −1.21 + log(𝑃 ) 14 " ()# Cl2 gas generated electrochemically is re-absorbed into the electrolyte as the system tries to maintain equilibrium between its gas and liquid phases. When voltage is removed, the gas concentration in all cases drops rapidly to near or below 1% as there is no driving force to generate more Cl2. Cl2 is not stable in solution and will readily form Cl-.14 The formation of Cl- reduces the dissolved Cl2 concentration which allows more Cl2 to dissolve into the electrolyte. Another mechanism for additional consumption of Cl2 could be the reverse of equation 2, shown in equation S2: 𝑒𝑞𝑆2. 𝑉𝑂"$ + 𝐻 𝑂+ 1𝐶𝑙 ®𝑉𝑂$ +2𝐻$ +𝐶𝑙! "2"" Kim et al. determined this reaction is thermodynamically favorable in the conditions present in the mixed acid system.11 This process may help compensate for coulombic losses from the Cl2 generating side reaction as it moves a vanadium ion from the V4+ state to the V5+ state, thus charging the battery. 26

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