Alloys antimony-free

The basis for the performance of the alloy in VRLA batteries is corrosion of the lead-cadmium-antimony alloy to produce antimony in the corrosion layer of the positive grid, which thus eliminates the antimony-free eifect of pure lead or lead-calcium alloys. During corrosion, small amounts of antimony and cadmium present in the lead matrix are introduced into the corrosion product and thereby dope it with antimony and cadmium oxides. The antimony and cadmium give excellent conductivity through the corrosion product. The major component of the alloy, the CdSb intermetallic alloy, is not significantly oxidized upon float service, but may become oxidized in cycling service. 

Highly corrosion-resistant, antimony-free, lead alloys have been used successfully in the positive electrode grids of both single-plate and spiral-wound cells. Spiral-wound cells almost exclusively feature binary lead-tin alloys [36,41] whereas flat-plate electrodes use either lead-calcium alloys, with or without silver additive [26], or lead-tin alloys [48]. Binary lead-tin is known to be highly corrosion-resistant, but rather soft, which is a handicap for plate stacking in prismatic cells. 

At the end of the twentieth century, maintenance-free VRLA batteries were invented. The first VRLA batteries employed lead—calcium grids. The antimony-free effect exhibited fully, which forced metallurgists to switch back to Pb—Sb alloys for the positive grids, minimising... 

The properties of the corrosion layer, and of its interfaces, depend strongly on the additives to the grid alloy (in this case, antimony). Antimony affects the corrosion layer in such a way that it does not limit the discharge of the active mass, so the latter exhibits its full capacity. This phenomenon is known as antimony-free effect . 

Figure 7.20 shows that normal lead-acid batteries with antimony-free alloys (e.g. Gro E cells have a cycle life of less than 200 cycles (DIN/IEC cycles)). 

Important for the maintenance-free properties of these batteries was the possibility to use antimony-free grid alloys instead of the conventional lead-antimony alloys, which were used only at this time. Because antimony in the grid alloys provides a high cycle life for the battery, it was necessary to develop more sophisticated methods in battery manufacturing in order to achieve the required product properties. 

Besides the usage of clean materials and antimony-free lead alloys for the construction of batteries, the so-called oxygen recombination is the basis for the function of valve-regulated maintenance-free lead-acid batteries. Because of the thermodynamic locations of hydrogen and lead, a complete prevention of decomposition of small amounts of water generally is not possible. But the oxygen... 

First, by increasing the overvoltage of H2 and O2 evolution by choosing an antimony-free grid alloy. 

Silver reduces the oxygen evolution potential at the anode, which reduces the rate of corrosion and decreases lead contamination of the cathode. Lead—antimony—silver alloy anodes are used for the production of thin copper foil for use in electronics. Lead—silver (2 wt %), lead—silver (1 wt %)—tin (1 wt %), and lead—antimony (6 wt %)—silver (1—2 wt %) alloys ate used as anodes in cathodic protection of steel pipes and stmctures in fresh, brackish, or seawater. The lead dioxide layer is not only conductive, but also resists decomposition in chloride environments. Silver-free alloys rapidly become passivated and scale badly in seawater. Silver is also added to the positive grids of lead—acid batteries in small amounts (0.005—0.05 wt %) to reduce the rate of corrosion. 

Selenium acts as a grain refiner in lead antimony alloys (114,115). The addition of 0.02% Se to a 2.5% antimonial lead alloy yields a sound casting having a fine-grain stmcture. Battery grids produced from this alloy permit the manufacture of low maintenance and maintenance-free lead—acid batteries with an insignificant loss of electrolyte and good performance stability. 

Where free machining characteristics are required, this may be achieved by additions of cadmium, antimony, tin or lead (e.g. BS 4300/5). Materials for electrical use are of special composition (BS 2627, 3988), while bearings are manufactured from Al-Sn alloys. 

Of the elements commonly found in lead alloys, zinc and bismuth aggravate corrosion in most circumstances, while additions of copper, tellurium, antimony, nickel, silver, tin, arsenic and calcium may reduce corrosion resistance only slightly, or even improve it depending on the service conditions. Alloying elements that are of increasing importance are calcium especially in maintenance-free battery alloys and selenium, or sulphur combined with copper as nucleants in low antimony battery alloys. Other elements of interest are indium in anodesaluminium in batteries and selenium in chemical lead as a grain refiner ". 

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