Electrochemical behavior of lead alloys in sulfuric and phosphoric acid solutions

Paleska, Iwona; Pruszkowska-Drachal, R.; Kotowski, Jakub; Dziudzi, A.; Milewski, Jarosław; Kopczyk, M.; Czerwiński, A.

doi:10.1016/s0378-7753(02)00530-x

Cited by 29 publications

(14 citation statements)

References 34 publications

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“…It is assumed that the formation of PbHPO 4 is the reason behind the significant changes, especially the diffusion characteristics of the passive layer. Previous reports on oxidation of Pb alloys in H 3 PO 4 have indicated that the passive layer containing PbHPO 4 is porous 20,21) and this may explain the lower W values in the H 3 PO 4 -containing solution recorded in the present study. Since the Warburg parameter is inversely proportional to the square root of the diffusion coefficient(s) of the soluble species involved in the redox process, 42) one can deduce that the effective diffusion coefficient(s) of soluble species through the passive layer containing PbHPO 4 is (are) higher than those in the H 3 PO 4 -free solution.…”

Section: )supporting

confidence: 47%

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Effect of Phosphoric Acid on the Electronic and Diffusion Properties of the Anodic Passive Layer Formed on Pb-1.7%Sb Grid of Lead-acid Batteries

El-Rahman¹,

Salih²,

Elwahab³

2011

Journal of Electrochemical Science and Technology

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:Potentiostatic oxidation of Pb-1.7%Sb alloy used in the manufacture of grids of lead-acid batteries over the potential range from −1.0 V to 2.3 V in 5 M H 2 SO 4 in the absence and the presence of 0.4 M H 3 PO 4 and the self-discharge characteristics of the oxide layer formed is studied by electrochemical impedance spectroscopy (EIS). Depending on the potential value, sharp variations in resistance and capacitance of the alloy are recorded during the oxidation and they can be used for identification of the various substances involved in passive layer. Addition of H 3 PO 4 is found to deteriorate the insulating properties of the passive layer by the retardation of the formation of PbSO 4 . H 3 PO 4 completely inhibits the current and impedance fluctuations recorded in H 3 PO 4 -free solutions in the potential range 0.5 V-1.7 V. These fluctuations are attributed to the occurrence of competitive redox processes that involve the formation of PbSO 4 , PbOSO 4 , PbO and PbO 2 and the repeated formation and breakdown of the passive layer. Self-discharge experiments indicate that the amount of PbO 2 formed in the presence of H 3 PO 4 is lesser than in the H 3 PO 4 -free solutions. The start of transformation of PbSO 4 into PbO 2 is greatly shortened. H 3 PO 4 facilitates the diffusion process of soluble species through the passive layer (PbSO 4 and basic PbSO 4 ) but impedes the diffusion process through PbO 2 .

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Section: )supporting

confidence: 47%

“…The behavior may be attributed to the nucleation and 3-dimensional growth of some PbHPO 4 grains together with the deposition of the insulating PbSO 4 , possible at 0.5 V and higher. 20,21) The presence of PbHPO 4 seems to be the reason of disappearance of the fluctuations. Fig.…”

Section: 40)mentioning

confidence: 96%

Effect of Phosphoric Acid on the Electronic and Diffusion Properties of the Anodic Passive Layer Formed on Pb-1.7%Sb Grid of Lead-acid Batteries

El-Rahman¹,

Salih²,

Elwahab³

2011

Journal of Electrochemical Science and Technology

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“…To prove that H 3 PO 4 has no effect on the nature of the self-discharging processes but it only affect the amount of PbO 2 formed during the charging, a modified Q SD is calculated according to the following. [20,21] or Pb 3 (PO 4 ) 2 [6] instead.…”

Section: Effect Of Charging Currentmentioning

confidence: 99%

“…In the presence of H 3 PO 4 , However, the extent of surface penetration and the transformation of Pb into PbO 2 seem to be inhibited by the retardation of PbO 2 formation. This can be achieved via the adsorption of phosphate species on PbSO 4 particles [13,15] and/or the formation of PbHPO 4 or Pb 3 (PO 4 ) 2 on the expense of PbSO 4 [6,20,21].…”

Section: Effect Of Cycle Numbermentioning

confidence: 99%

“…The diffusion parameter W is high in the H 3 PO 4 -free solution than in its presence. Since W is inversely proportional to the square root of the diffusion coefficient of the species involved in the corrosion of the alloy through the passive film [54], one can inferred that the passive film in the H 3 PO 4 -free solution retards the diffusion more than in the presence of H 3 PO 4 , probably via increasing the film porosity by the deposition of the porous PbHPO 4 or Pb 3 (PO 4 ) 2 [6,20,21].…”

Section: Effect Of Cycle Numbermentioning

confidence: 99%

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Effect of phosphoric acid on the performance of low antimony grid of Pb‐acid cell under constant current charging and discharging

El-Rahman¹,

Salih²,

Elwahab³

2011

Materialwissenschaft Werkst

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Effect of phosphoric acid on the performance of Pb-1.7%Sb grid of lead-acid cell is studied in 5 M H 2 SO 4 by cyclic galvanostatic polarization and impedance spectroscopy. An increase in capacitance to a maximum is recorded during the initial stages of the electro-reduction of PbO 2 into Pb(II) compounds and attributed to concurrent compositional and dimensional changes. These changes include removal of O 2 bubbles, insertion of large amounts of H 2 SO 4 and H 2 O. Efficiency of PbO 2 formation decreases, while its rate of self-discharge increases with increasing the charging current and in the presence of H 3 PO 4 . The charge capacity increases with increasing the discharging current due to the decrease in the self-discharge. The charge capacity is lower in the presence of H 3 PO 4 . On increasing the cycle number, the corrodibility of the grid increases, because more layers of the surface Pb are involved in the self-discharge. H 3 PO 4 significantly retards the effect of cycle number.

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Electrochemistry of Lead

Stroka

Maksymiuk

Galus

2006

Encyclopedia of Electrochemistry

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The sections in this article are Double‐layer Properties of Pb Electrodes Properties of Solid Electrodes Properties of Liquid Electrodes Adsorption on Solid Electrodes Electrochemical Properties and Kinetics of Lead and Lead Compounds Pb ( II )/ Pb ( Hg ) System Studies in the Presence of Inhibitors and Organic Solvents Other Phenomena Complexes of Pb ( II ) and Related Phenomena Electrochemical Processes of Liquid Lead in Molten Salts Voltammetric Behavior of Lead Sulfuric Acid Solutions Nitric Acid Solutions Phosphoric Acid Solutions Sodium Hydroxide Solutions Different Salt Solutions Voltammetric Behavior of Several Lead Compounds Pb O Pb O 2 Pb chalcogenides Electrodeposition and Underpotential Deposition of Lead on Solid Substrates Platinum Gold Silver Copper Carbon Silicon Germanium Other Materials Corrosion and Passivation Applied Electrochemistry Lead‐acid Batteries Electrocatalytic Properties Pb Pb O 2 Electrochemical Sensors Potentiometric Sensors Amperometric/Voltammetric Sensors

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Electrochemical behavior of lead alloys in sulfuric and phosphoric acid solutions

Cited by 29 publications

References 34 publications

Effect of Phosphoric Acid on the Electronic and Diffusion Properties of the Anodic Passive Layer Formed on Pb-1.7%Sb Grid of Lead-acid Batteries

Effect of Phosphoric Acid on the Electronic and Diffusion Properties of the Anodic Passive Layer Formed on Pb-1.7%Sb Grid of Lead-acid Batteries

Effect of phosphoric acid on the performance of low antimony grid of Pb‐acid cell under constant current charging and discharging

Electrochemistry of Lead

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