An attempt was made to build up a thick and compact oxide layer rapidly by pre-treating the Pb-Ag-Nd anode in fluoride-containing H2SO4 solution. The passivation reaction of Pb-Ag-Nd anode during pre-treatment process was investigated using cyclic voltammetry, linear scanning voltammetry, environmental scanning electron microscopy and X-ray diffraction analysis. The results show that Pb F2 and PbSO4 are formed near the potential of Pb/PbSO4 couple. The pre-treatment in fluoride-containing H2SO4 solution contributes to the formation of a thick, compact and adherent passive film. Furthermore, pre-treatment in fluoride-containing H2SO4 solution also facilitates the formation of PbO2 on the anodic layer, and the reason could be attributed to the formation of more PbF2 and PbSO4 during the pre-treatment which tend to transform to PbO2 during the following electrowinning process. In addition, the anodic layer on anode with pre-treatment in fluoride-containing H2SO4 solution is thick and compact, and its predominant composition is β-PbO2. In summary, the pre-treatment in fluoride-containing H2SO4 solution benefits the formation of a desirable protective layer in a short time.
The anodic layer and oxygen evolution behavior of Pb-Ag-Nd alloy during pulse current polarization and constant current polarization in 160 g/L H2SO4 solution was comparatively investigated by chronopotentiometry, SEM, XRD, EIS and Tafel techniques. The results show that the anodic layer on Pb-Ag-Nd alloy formed through pulse current polarization is more intact and presents fewer micro-holes than that formed through constant current polarization. This could be attributed to the low current density period, which works as a ‘recovery period＇. During this period, the oxygen evolution reaction is less intense, which benefits the recovery of porous anodic layer. Pb-Ag-Nd anode also shows a lower anodic potential during pulse current polarization, which is in accordance with its smaller charge transfer resistance and smaller Tafel slope coefficient at high over-potential region. The lower anodic potential could be ascribed to the higher concentration of Pb O2 in the anodic layer, which promotes the formation of more reactive sites for the oxygen evolution reaction.
