Abstract
Electrochemical impedance spectroscopy, scanning electron microscopy, X-ray diffraction and secondary ionisation mass spectroscopy (SIMS) have been utilized to investigate the mechanism of reactions taking place on Pb and Pb-Ag alloy anodes in acidic zinc sulphate electrolytes, in the potential domain above 1.16 V sse. At these polarizations, the main reaction is oxygen evolution on a porous deposit of PbO 2, or PbO 2 + MnO 2 in Mn 2+-containing electrolytes. In all cases, the electrode impedance reveals a slow electrode activation with increasing polarization, probably related to the deposit conductivity. With lead-silver anodes it also appears an inhibition process of the main reaction, which becomes more important and turns into passivation, when the electrolyte contains Mn 2+ ions. This process has been assigned to the formation of inhibiting adsorbates on the oxide layers.
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