Evaluation of lead-calcium-tin-aluminium grid alloys for valve-regulated lead/acid batteries

Cast lead-calcium alloys have been generally employed in valve-regulated lead/acid (VRLA) batteries since they appeared in the early 1970s. Some minor elements such as aluminium, silver, bismuth and some alkaline earth metals are also added to lead-calcium alloys to improve the alloy properties and the battery performance. A convenient method for the addition of aluminium into the alloy, compared with other methods reported, is presented. On addition to lead-calcium alloys, bismuth can form a Bi-Ca compound according to the de-bismuthizing equation: 3Pb(3)Ca + 2Bi --> Bi2Ca3 + 9Pb. There is a slight solubility of Bi2Ca3 in the lead at its melting point (327 degrees C) with an amount of 0.048 wt.% resident bismuth. It is confirmed that the creep strength and the corrosion resistance is distinctly increased by the addition of silver into the grid alloy, but the associated gassing problem should be considered when such alloys are employed in VRLA batteries. Addition of sodium can refine grain sizes and increase the mechanical properties of the grid alloy, but the corrosion resistance of sodium-contained grids is inferior. A general description of experiments and application of tin, aluminium, bismuth, silver and sodium as additives in lead-calcium alloys is given.