Corrosion management of PbCaSn alloys in lead-acid batteries: Effect of composition, metallographic state and voltage conditions

Since several years, lead calcium-based alloys have supplanted lead antimony alloys as structural materials for positive grids of lead-acid batteries in many applications, especially for VRLA batteries. Nevertheless, the positive grid corrosion probably remains one of the causes of rapid and premature failure of lead-acid batteries. The objective of the present study is to present a comprehensive study of the PbCaSn alloy corrosion in function of their composition, metallographic state and voltage conditions (discharge, overcharge, floating and cycling conditions). For that, four alloys PbCaSn x wt.% (x = 0, 0.6, 1.2, 2) were synthesized in two extreme metallurgical conditions and tested by four electrochemical lab-tests. Weight loss measurements and analyses by SEM, EPMA and XRD allowed to monitor the oxidation tests and to characterize the corrosion layers after the oxidation tests.The results show that the tin level in PbCaSn alloys should be adapted on the calcium concentration and the rate of overageing process, to maintain the beneficial effect of tin in service during the battery lifetime. According to our results, a Sn/Ca ratio of 2.5 gives good corrosion resistance in all potential conditions. Nevertheless, when tin level is too high, the corrosion layers can peel off from the metal, which involves a lack of cohesion between the collector and the paste, in cycling conditions.The anodic potential undergone by the metal is a second main factor determining the corrosion, especially the floating conditions and the frequency of deep discharge and overcharge. Thus the adjustment of the charge controller parameters of a battery system is a necessity to increase the lifetime of the grids and maintain a good rechargeability.