Recharge Kinetics of the Porous Lead Dioxide Electrode: I . The Effect of Structural Changes

Ekdunge, P.; Simonsson, Daniel

doi:10.1149/1.2113616

Cited by 20 publications

(42 citation statements)

References 15 publications

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“…8. ͑The solid circles give the temperature during the constant-voltage portion of charge for cycle 231.͒ PbO 2 electrode-solid-state mechanism.-As we mentioned earlier, Eckdunge and Simonsson 18,19 suggested that a solid-state mechanism occurs during PbO 2 charging because they did not observe limiting-current behavior ͑as observed for Pb electrodes.͒ Since they observed two Tafel slopes in their polarization curves, they also suggested that two, consecutive, single-electron transfer reactions were occurring. Eckdunge and Simonsson found that the general equation for this case, Eq.…”

Section: An Increase In D Pb 2ϩmentioning

confidence: 83%

“…17 With this information, one may suggest that the conclusions drawn from experiments involving coherent PbSO 4 layers may not apply in actual cells and that a PbO 2 charging mechanism involving solid-state transport would be plausible if there were experimental evidence to support it. Such evidence exists in 1985 papers by Eckdunge and Simonsson et al; 18,19 these researchers obtained anodic polarization curves of PbO 2 porous electrodes in a controlled acid-concentration and temperature environment. They investigated various states-of-charge ͑SOC͒ and found no evidence of diffusion-limiting currents to support the dissolutiontransport mechanism.…”

mentioning

confidence: 79%

“…39 for j PbO 2 . Since Eckdunge and Simonsson 18,19 did not discuss reacting species, transport, or reactions in a mechanism that would be consistent with the behavior described by Eq. 39, we attempt to do this in the following paragraphs.…”

Section: An Increase In D Pb 2ϩmentioning

confidence: 99%

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Study of Charge Kinetics in Valve-Regulated Lead-Acid Cells

Bernardi

Ying

Watson

2004

J. Electrochem. Soc.

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Model predictions of half-cell voltages, current, and gassing behavior are compared to experimental results of valve-regulated lead-acid ͑VRLA͒ cells to elucidate the charge mechanisms. Good comparisons of experimental Pb half-cell voltages with model predictions confirm the importance of liquid-phase Pb 2ϩ transport early during charge. In the latter stages of Pb-electrode charge, limitations in the PbSO 4 dissolution rate are more important than those of Pb 2ϩ transport and control charge behavior. Model predictions with an analogous mechanism for the PbO 2 electrode ͑i.e., involving dissolution and Pb 2ϩ transport͒ were not consistent with the charge polarization behavior, since comparisons of experimental half-cell voltages with model results were poor. Satisfactory comparisons with a model that incorporates a solid-state PbO 2 charge mechanism confirmed the insignificance of dissolution and transport in PbO 2 charging. The good agreement between model and experimental current behavior during the constant-voltage portion of charge support our conclusions regarding the electrode charging mechanisms. Conditions under which to expect charging difficulties as well as improved charge regimes are also discussed. The model also predicted the characteristic double-peak gas-flow behavior seen when charging VRLA cells with constant current to a specific voltage lid. The first peak is due to the onset of significant amounts of O 2 generation even though the internal residual gas is dominantly H 2 . The second peak is due to the onset of H 2 evolution.

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Section: An Increase In D Pb 2ϩmentioning

confidence: 83%

mentioning

confidence: 79%

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Study of Charge Kinetics in Valve-Regulated Lead-Acid Cells

Bernardi

Ying

Watson

2004

J. Electrochem. Soc.

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“…Valeriote, Ekdunge, Casson, and others have carried out much work on the kinetic processes occurring in this transient. [15][16][17][18][19][20][21] They concluded that the nucleation and growth of the PbO 2 crystals is a rate-determining step in the oxidation of PbSO 4 and that this process is diffusion limited. The dimension of the nucleation and growth of PbO 2 crystals changes under different conditions such as potential, concentration of sulfuric acid, etc.…”

Section: Literature Studymentioning

confidence: 99%

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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“…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.). Hattori et al [14], Mathews et al [15], Tsubota and co-workers [16] and Eckdunge and Simonsson [17] have found that the concentration of H 2 SO 4 affects not only the kinetics of the electrochemical reactions in PAM, but also the utilization of the active materials in the lead-acid battery.…”

Section: Introductionmentioning

confidence: 99%