Influence of the iodide/iodine redox system on the self-discharge of AC/AC electrochemical capacitors in salt aqueous electrolyte

Self-discharge (SD) of AC/AC (AC=activated carbon) electrochemical capacitors in aqueous solutions of lithium sulfate (Li2SO4) and lithium sulfate+iodide salts (Li2SO4+KI or Li2SO4+LiI) was investigated at 24 °C and −40 °C after cell potential hold at values from 1 V to 1.6 V. At 24 °C, the cells exhibit lower SD in Li2SO4+KI than in Li2SO4, owing to the redox activity of the 2I−/I2 system which drives the positive AC electrode to operate in narrow potential range and display lower potential drop than in Li2SO4. At −40°C, the capacitors exhibit comparable and reduced SD both in Li2SO4+LiI and Li2SO4, whatever the holding cell potential. Three-electrode cell experiments demonstrate that, at −40 °C, hydrogen chemisorption is thermodynamically unfavored under negative polarization, while the activity of the 2I−/I2 redox system under positive polarization is only slightly reduced. As a consequence, the AC/AC cells in Li2SO4 exhibit a typical electrical double-layer performance at −40°C, whereas they still behave as hybrid ones in Li2SO4+LiI, with twice higher capacitance than in Li2SO4. The (Ui-Ut) vs t1/2 plots demonstrate that SD is essentially controlled by diffusion at −40°C, suggesting that it originates from bulkier hydrated ions. Overall, in the investigated temperature range, the AC/AC capacitors in Li2SO4+LiI demonstrate low self-discharge and high capacitance, while being able to operate up to 1.6 V.