Lead alloys for maintenance-free and sealed lead/acid batteries

doi:10.1016/0378-7753(93)90029-Z

Journal of Power Sources

Volume 46, Issues 2–3, October–December 1993, Pages 327-333

https://doi.org/10.1016/0378-7753(93)90029-Z Get rights and content

Abstract

The preparation of low-antimony and leadcalcium multi-element alloys for battery grids are studied. The effects of various minor constituents (tin, aluminium, copper, selenium, cerium, thallium, sulfur, etc.) on the performance and methods for preparing copperantimony, arsenicantimony and calciumaluminium master alloys are described in detail. The reaction mechanism of tin in the alloys and the casting conditions of the alloys are examined.

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In the manufacture of components for Pb-acid batteries (positive and negative grids, connectors, etc), the producers commonly use Pb–Sb, Pb–Sn and Pb–Sn–Ca alloys [1–4].
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Influence of temperature on corrosion behavior of PbCaSnCe alloy in 4.5 M H<inf>2</inf>SO<inf>4</inf> solution
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The temperature effect on corrosion behaviors of PbCaSnCe alloy in 4.5 M H₂SO₄ solution was investigated by using potentiodynamic curve, electrochemical impedance spectra (EIS), Mott–Schottky plot and photocurrent response methods. It was found that PbCaSnCe alloy was in passive state in sulfuric acid solution, a passive film can be formed on alloy surface. The compositions of passive films formed at 0.9 V for 2 h under different temperatures were detected by X-ray photoelectron spectroscopy (XPS). The results showed that the film resistance and the transfer resistance decreased with the increment of the solution temperature. Mott–Schottky analysis and the photocurrent response revealed that the passive film exhibited n-type semi-conductive character, the donor density of the passive film decreased with increasing the solution temperature. Photocurrent response revealed that the photocurrent increased with increasing temperature. XPS results indicated that the PbO₂ content in passive films may increase with increasing the solution temperature.
Investigation on characteristics of anodic film formed on PbCaSnCe alloy in sulfuric acid solution
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The electrochemical properties of the anodic films formed on PbCaSnCe and PbCaSn alloys at 0.9 V (versus Hg/Hg₂SO₄ electrode) in 4.5 mol/L sulfuric acid solution were investigated by linear sweeping voltammetry (LSV), ac voltammetry (ACV), electrochemical spectroscopy impedance (EIS), capacitance measurement and X-ray photoelectron spectroscopy (XPS) technology. Based on Mott–Schottky analysis, the effect of cerium on the semiconductor properties of anodic film is discussed as well in this paper. The experimental data shows that cerium can significantly decrease the impedance of the anodic film on PbCaSn alloy, and can improve the corrosion resistance of the alloy. It can be inferred from the capacitance measurement result that the passive film should be an n-type semiconductor. The addition of cerium can decrease the slope of M–S plot, which indicates the increasing of defect density in the film, and this can contribute to improve the conductivity of the anodic film on PbCaSn alloy. XPS results shows that the anodic film formed on PbCaSnCe alloy is consisted of PbO_1+x (0 < x < 1) and PbSO₄, while for the anodic film formed on PbCaSn alloy, PbO and PbSO₄ are the major component. Considering the better conductivity of PbO_1+x (0 < x < 1) than that of PbO, it is concluded that PbCaSnCe may serve as the candidate of the new grid material for maintenance-free lead acid battery.
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2004, Journal of Alloys and Compounds
The anodic behavior of Pb–0.73 wt.% Sm–0.63 wt.% Sn and Pb–0.088 wt.% Ca–0.63 wt.% Sn alloys in sulfuric acid solution has been studied using linear sweep voltammetry, impedance–time curves and cyclic voltammetry. The experimental results show that the samarium in the Pb–Sm–Sn alloy can inhibit the growth of the anodic corrosion layer (PbO₂) formed on the alloy. Moreover, the rate of the oxygen evolution at the Pb–Sm–Sn alloy electrode is lower than that at the Pb–Ca–Sn alloy electrode. 2V-200Ah VRLA batteries were separately manufactured using the Pb–Sm–Sn and Pb–Ca–Sn positive grids. The results of the test show that the capacity loss of the battery with the Pb–Sm–Sn positive grids is significantly less than that of the battery with the Pb–Ca–Sn positive grids.
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The anodic corrosion of Pb–0.10 wt.% Ca–0.88 wt.% Sn alloy and Pb–0.10 wt.% Ca–0.88 wt.% Sn–0.048 wt.% Ce alloy in 4.5 M H₂SO₄ at 20°C was studied using cyclic voltammetry, linear sweep voltammetry, ac voltammetry, chronoamperometry, and scanning electron microscopy. The experimental results show that the cerium added to Pb–Ca–Sn alloy inhibits the growth of the anodic corrosion layer and reduces the resistivity of the anodic Pb(II) film.
Laser Ablation Inductive Coupled Plasma Mass Spectroscopy (LA-ICP-MS) Analysis on Lead-Acid Battery System: Development of Evaluation Method of Sub-ppm Metal Impurity Elements
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Lead alloys for maintenance-free and sealed lead/acid batteries

Abstract

J. Power Sources

Chin. J. Power Sources

Metalloberflaeche