The SEM Observation of the Potentiostatic Oxidation of Lead Sulfate on a Gold Plate in Sulfuric Acid Solution

Takehara, Zen‐ichiro; Kanamura, Kiyoshi

doi:10.1149/1.2100394

Cited by 23 publications

(19 citation statements)

References 3 publications

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“…The dissociation of lead sulfate followed by the electron transfer takes place at the microscopic level. A similar situation is reported in the case of the oxidation of lead sulfate to lead dioxide (8).…”

supporting

confidence: 79%

“…Such a rapidly rising initial current may be due to the fast kinetics of the electrodeposition of lead. In the case of the oxidation of lead sulfate such a rapid increase in current was not observed (8). This reaction may involve a slow electron transfer.…”

Section: Resultsmentioning

confidence: 97%

“…i Present address: Genera] Electric Corporate Research & Development, Schenectady, NY 12301.oxygen and that the open-circuit potential (OCP) of the nickel hydroxide electrode depends on KOH concentrations(6,7). Also, Barnard et al(8) have studied the oxidation state of the nickel hydroxide electrode as a function of OCP.…”

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confidence: 99%

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Microscopic Reaction Site Model for Cathodic Reduction of Lead Sulfate to Lead

Kanamura

Takehara

1992

J. Electrochem. Soc.

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The cathodic reduction of lead sulfate to lead was investigated by using the potential sweep method. A microscopic reaction site model was proposed in order to discuss the current-potential curves of the cathodic reduction of lead sulfate to lead. In this study it was assumed that the reaction occurred at the interface between the lead and the lead sulfate crystals. The electrochemical kinetics of the cathodic reduction of the lead sulfate at the reaction site was assumed to be controlled by the diffusion of lead ion. The current-potential curve was explained by the change of the reaction site area and the diffusion of lead ion. The electrochemical behavior of a lead/lead sulfate electrode is in good agreement with the model proposed in this study. The effects of crystal size, solubility, diffusion coefficient, and length of diffusion path on the reduction of lead sulfate to lead were examined.

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supporting

confidence: 79%

Section: Resultsmentioning

confidence: 97%

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Microscopic Reaction Site Model for Cathodic Reduction of Lead Sulfate to Lead

Kanamura

Takehara

1992

J. Electrochem. Soc.

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“…[16][17][18][19][20][21][22] However, from the data in Fig. 2, we believe that PbO 2 electrocrystallization is not a slow step in the pulse charge.…”

Section: Mass Transfer Of O Atoms In Pulse Charge-many Authors Havementioning

confidence: 84%

Rate‐Determining Step Investigations of Oxidation Processes at the Positive Plate during Pulse Charge of Valve‐Regulated Lead‐Acid Batteries

Guo

Groiss

Döring

et al. 1999

J. Electrochem. Soc.

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In order to develop electric vehicles (EVs), electrochemical scientists and engineers have paid great attention to the study of batteries in recent years. Now, while new types of batteries are still in development, the valve-regulated lead-acid (VRLA) battery is a near-term candidate for EV applications in mass markets. 1 A key usage issue is the possibility of fast recharge. More recently, much work has been carried out on pulse charging of lead-acid batteries. 2-7 The recharge time for valve-regulated lead-acid batteries has been reduced and is now less than 5, 15, and 240 min for 50, 80, and 100% charge. However, many other problems arise from pulse charging such as reduced cycle life of the battery, corrosion of the positive-electrode grid, loss of electrolyte, and thermal management. To enhance the pulse charging of a VRLA battery, it is important to understand the detailed processes during the charge. Therefore, attention has to be paid to the kinetics of important processes during pulse charging. Although many papers have reported on the mechanism of the oxidation processes at the PbSO 4 /PbO 2 electrode and the positive plate, 8-29 this remains a subject of research. It is necessary to study further the electrode kinetics of the positive plate in VRLA batteries under pulse charging conditions. Experimental The tested battery was a 2 V 4.2 Ah VRLA battery with gel electrolyte, produced by Sonnenschein Lead-Acid Battery Company. The pulse charge system, controlled by a computer, is a self-made system. The maximum output current and voltage are 100 A and 10 V, respectively. The rise time of the analog circuit is less than 1 s/A. The control period of the digital circuit is 2 ms. The internal pressures of the gas in the battery were measured by a pressure sensor. The relative pressures of oxygen and hydrogen were measured with a micropipette of 0.5 mm internal diam and 8 cm length, which linked the battery to a quadripole mass spectrometer (Balzers QMS 402). All potentials were measured vs. a Hg/Hg 2 SO 4 /H 2 SO 4 (sp gr 1.28) reference electrode, which was linked to the battery by a proton-conducting polymer bridge. The infrared (IR)-corrected potentials were measured by imposing an instantaneous open circuit. Different interactive pulse charging and discharge/constant-voltage procedures were used, and the current profiles are shown in Fig. 1. Their average current was 15.5 A. The maximum limit voltage with IR compensation was 2.45 V at 25ЊC and it is also compensated by a temperature coefficient with Ϫ4.5 mV/ЊC, to avoid thermal runaway of the VRLA battery. To simulate the situation of a large battery, the test battery was thermally isolated. Literature StudyDuring recent decades, both oxygen evolution and the oxidation of PbSO 4 to PbO 2 have been studied extensively on solid Pb electrodes and on the positive plates of lead-acid batteries. Different models for the kinetics of both reactions have been put forward.A model with hydration structure carried out much work on the kinetic processes of the PbSO 4...

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“…Takehara and Kanamura have investigated the influence of H 2 SO 4 concentration on the processes of PbSO 4 oxidation to PbO 2 [12,13]. They have established that the highest rate of PbSO 4 oxidation is in 0.5 M H 2 SO 4 solutions (1.048 s.g.).…”

Section: Introductionmentioning

confidence: 99%