The Hydrogen-Loss Concept of Battery Failure: The PbO[sub 2] Electrode

Caulder, S. M.; Murday, J. S.; Simon, Adam C.

doi:10.1149/1.2403293

Cited by 73 publications

(35 citation statements)

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“…Similar behavior for Fe in air at 300~ was reported by Lustman and Mehl (4),-in air up to 200~ by Vernon et al (5), in air up to 300~ by Davies et al (6), and in 1.3 X 10 -2 Torr 02 up to 200~ by Graham et al (7). Similar behavior for Fe in air at 300~ was reported by Lustman and Mehl (4),-in air up to 200~ by Vernon et al (5), in air up to 300~ by Davies et al (6), and in 1.3 X 10 -2 Torr 02 up to 200~ by Graham et al (7).…”

Section: Discussionsupporting

confidence: 87%

Thermal Decomposition Mechanism of Formed and Cycled Lead Dioxide Electrodes and Its Relationship to Capacity Loss and Battery Failure

Guilder¹,

Simon²

1974

J. Electrochem. Soc.

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The structural changes accompanying capacity loss in the PbO2/PbSO4 electrode were followed using differential thermal analysis. The thermal decomposition mechanism of formed plates was found to differ, depending on the method of manufacture. All cycled plates, however, gave the same decomposition mechanism after a few cycles. The major changes in the DTA curves, as the positive electrode was cycled to failure, was the gradual disappearance of the exothermic peak at 200*C and the endothermic peak at 358~ It is believed that these peaks are associated with an electrochemically active amorphous form of PbO2. As the electrochemically active PbOs is cycled to failure it is converted to an electrochemically inactive form of PbO2. This latter form of PbO2 gives DTA results similar to those obtained on reagent PbOz. The continual conversion of electrochemically active PbO2 to the electrochemically inactive PbO2 is one of the major factors that accounts for the loss in battery capacity and ultimate failure. ElectrochemicalSociety Active Member.

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Section: Discussionsupporting

confidence: 87%

Thermal Decomposition Mechanism of Formed and Cycled Lead Dioxide Electrodes and Its Relationship to Capacity Loss and Battery Failure

Guilder¹,

Simon²

1974

J. Electrochem. Soc.

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“…The results also corroborate both the earlier NMR observations of Caulder et al (3), and the photoelectron spectroscopic studies ofKim et al (11), in demonstrating that there are two kinds of hydrogen species in battery PbO2. However, the NMR spectrum obtained from outgassed, extensively cycled, battery PbO~ (sample 3) is not greatly different from that obtained from outgassed, fresh PbO2 (sample 2.2), i.e., both spectra contain a single, broad, low intensity peak, P~ at 6 --* 7.5 ppm (Table I).…”

Section: Resultssupporting

confidence: 90%

“…The resulting composite film such as Prussian blue (PB) containing Nation (Nf) denoted by PB-Nf has been found to have a great utility for applications to a solid-state rechargeable battery or an electrochromic display device (2,3). An electrochemical cell made of the composite PB-Nf film sandwiched with supporting electrodes was examined on i-V curves in solid state and for characteristics as a rechargeable battery.…”

Section: Prussian Blue Containing Nation Composite Film As Rechargeabmentioning

confidence: 99%

“…In spite of the above interest, the pioneering NMR study of hydrogen in PbO2 undertaken nearly 15 years ago by Caulder et al (3) has not been repeated or extended. In the present work, one of the new generation of high resolution, solid-state, NMR instruments, incorporating the technique of "magic-angle" sample spinning, has been applied to the study of protons in a variety of samples of~-PbO2 and ~-PbO2 prepared by both chemical and electrolytic methods.…”

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confidence: 99%

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The Electrochemical Activity of PbO2 : A Nuclear Magnetic Resonance Study of Hydrogen in Battery and Chemically Prepared Material

Hill

Jessel

1987

J. Electrochem. Soc.

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Solid-state magic-angle-spinning nuclear magnetic resonance studies have been undertaken on positive plate material from lead-acid batteries and on samples of both pure ~-PbO2 and pure ~-PbO~ prepared by nonelectrochemical methods. Battery positive plate samples contain protons in two different surface and near surface configurations. One of these proton species is associated with mobile, isolated, adsorbed hydroxyl groups, and/or water molecules that can be removed by outgassing. The other proton species is not removed by outgassing; it probably corresponds to water molecules and/or closely spaced hydroxyl groups trapped on internal crystal surfaces. The proton species present in fresh (uncycled) positive plate material are not significantly different in either configuration or abundance from those in extensively cycled samples. Thus, it is unlikely that decline in battery capacity with cycling service is associated with a change in the hydrogen content of PbO2. Chemically prepared varieties of ~-PbO2 and ~-PbO2 are each different from their electrolytically formed counterparts in terms of both the abundance and the nature of the proton species on or near their surfaces; these differences can be related to differences in the manner of their preparation. With the possible exception of chemical ~-PbO2, none of the samples of PbO2 contain protons in configurations attributable to strongly bound, structural hydroxyl groups, as occur in the stoichiometric phase Pb302(OH)2.The role of hydrogen.--The lead-acid battery derives ) unless CC License in place (see abstract). ecsdl.org/site/terms_use address. Redistribution subject to ECS terms of use (see 129.173.72.87

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“…The model accounts for the fact that experimental studies report evidence for the presence of Pb(II) [45] and structural water (e.g. [46][47][48][49]) in the PbO 2 lattice. Substitution of part of the hydroxyl groups by F À , having a similar ionic radius, was shown by radiotracer experiments [50] and by SIMS data [51], and can explain the XPS data reported in [17,18].…”

Section: Pb 4þmentioning

confidence: 99%