Electrochemical Performance of Grids of Lead-acid Batteries made from Pb-0.8%Ca-1.1%Sn Alloys Containing Cu, As and Sb Impurities in the presence of phosphoric acid

摘要

Electrochemical performance of grids of lead-acid Batteries manufactured from Pb-0.8%Ca-1.1%Sn alloys containing Cu, As and Sb impurities at 0.1 wt% level were studied in 4.0 M H2SO4 without and with 0.4 M H3PO4. The presence of impurities in the alloy or addition of H3PO4was found to suppress the corrosion rate. H3PO4 increased the rates of both hydrogen and oxygen evolution reactions at high overpotentials for all alloys. Except for Cu-containing alloy, H3PO4 had a slight positive effect on PbO2 formation. The self-discharge of PbO2 under polarization or open-circuit conditions increased in the presence of H3PO4 but the positive grid corrosion decreased, except for the As-containing alloy. Impurity-containing alloys showed significantly lower self-discharge rate in the presence of H3PO4 than in its absence. Impedance measurement was able to detect and quantify the formation of the highly insulating inner PbO layer beneath the outer PbSO4 layer and its transformation to the conducting PbO2, during the oxidation of alloys under constant current conditions. H3PO4 significantly enhanced the formation of PbO in the presence of impurities, especially Sb.