PbO_2/Pb~(2+) cycling in methanesulfonic acid and mechanisms associated for soluble lead-acid flow battery applications

摘要

Is this paper, the electrodeposition/electrodissolution cycling of lead dioxide (PbO_2) is studied on vitreous carbon electrodes in lead methanesulfonate/methanesulfonic acid medium for a soluble lead acid flow battery application. The influence of the active species concentrations (Pb~(2+), H~+) on the cyclability of lead dioxide (charge efficiency, lifetime of cycling, etc.) is assessed. The proton has a very adverse effect when its concentration is above 1 M. Electrochemical impedance spectroscopy (EIS) shows that the lead dioxide layer can be passivated at the end of reduction when the electrolyte is strongly acidic. Mass changes investigations carried out during PbO_2 cycling with a quartz crystal microbalance (QCM) confirm the presence of the solid-state reaction predicted in the literature. This side reaction suggests the formation of a non-stoichiometric PbO_x compound with a poor solubility and a high electric resistance. The effect of the acid concentration as well as the current density on the formation of PbO_x is assessed. The poor cyclability of PbO_2 in high acidic media can be related to the accumulation of this resistive compound within the layer. Finally, considerations for an optimal operation of the battery are presented.