A guide to the influence of bismuth on lead/acid battery performance

• Published in: Journal of power sources 1993, Vol.45 (3), p.365-377
• Main Authors: Koop, M.J., Rand, D.A.J., Culpin, B.
• Format: Article
• Language: English
• Subjects: Applied sciences; Direct energy conversion and energy accumulation; Electrical engineering. Electrical power engineering; Electrical power engineering; Electrochemical conversion: primary and secondary batteries, fuel cells; Exact sciences and technology
• ISSN: 0378-7753; 1873-2755
• DOI: 10.1016/0378-7753(93)80025-K

A review is given of the literature that deals with the influence of bismuth on the microstructure, oxygen/hydrogen evolution kinetics and anodic corrosion of lead and lead alloys with regard to their performance in lead/acid batteries. Analysis shows that there is considerable disagreement as to the effect of bismuth on lead microstructure. For example, the various investigators report an increase, a decrease, or negligible change in grain size. In general, it is concluded that the oxygen overpotential on PbO 2 is lowered in the presence of bismuth. The effect is enhanced as the bismuth content is increased. It is postulated that the behaviour results from the formation of a mixed oxide, PbO 2·BiO x . By contrast, cathodic hydrogen evolution is reported widely to be largely unaffected by bismuth. Nevertheless, there is evidence that the reaction is particularly sensitive to the surface characteristics of electrodes and that these features can induce either a suppression or an enhancement of the hydrogen-gassing rate. Many studies have shown that bismuth accelerates the anodic corrosion of lead alloys, especially at high concentrations of bismuth. At 0.1 wt.% bismuth and below, the effect on the corrosion rate is negligible. The authors of this discussion are of the opinion that much of the conflicting evidence in the areas reported is caused by spurious differences in grain structure that are introduced by variations in sample preparation, rather than by the action of bismuth itself. In battery-related tests, bismuth has usually been found to exert little influence on performance, but there is some suggestion that cycle life is increased. The present body of knowledge is insufficient to confirm the correctness of any currently specified maximum level for bismuth with respect to a given battery design.