Structual parameters of. beta. -PbO/sub 2/ and their relationship to the hydrogen-loss concept of lead-acid battery failure

Journal Article · Sun Jul 01 04:00:00 EDT 1984 · J. Electrochem. Soc.; (United States)

DOI:https://doi.org/10.1149/1.2115878· OSTI ID:6229208

Hill, R J; Madsen, I C

Full-profile, Rietveld-type, x-ray powder diffraction studies have been performed on ..beta..-PbO/sub 2/ samples either prepared chemically or obtained from batteries operated under simulated electric vehicle service at 25/sup 0/ and 50/sup 0/C. After a sharp initial decrease, the unit cell volume and cell edge ratio of battery ..beta..-PbO/sub 2/ assume relatively stable values which are both independent of the battery capacity and indistinguishable from those of chemically prepared material. A comparison of the observed unit cell volumes with values calculated for given levels of O/sup 2 -//(OH)/sup -/, Pb/sup 4 +//Pb/sup 2 +/ coupled substitution in the ..beta..-PbO/sub 2/ structure indicates that the maximum amount of this substitution is about 0.01 atoms of hydrogen per formula unit. These results suggest that the decline in battery capacity is not a function of the loss of a hydrogen species from the crystal structure of electrochemically active ..beta..-PbO/sub 2/. Estimates of the changes in PbO/sub 2/ crystallite size as a function of battery cycling history show that batteries began service with ..beta..-PbO/sub 2/ crystallite sizes of around 250A, irrespective of the temperature of operation, but increased to values of about 700 and 900A at 25/sup 0/ and 50/sup 0/C, respectively. Since this increase in crystallite size occurred well before battery failure, the loss in battery capacity with cycling cannot be correlated with the changes in crystallite size and, therefore, with changes in the degree of structural order of the active material.

• Research Organization: CSIRO Division of Mineral Chemistry, Port Melbourne, Victoria
• OSTI ID: 6229208
• Journal Information: J. Electrochem. Soc.; (United States), Journal Name: J. Electrochem. Soc.; (United States) Vol. 131:7; ISSN JESOA
• Country of Publication: United States
• Language: English

Related Subjects

25 ENERGY STORAGE
250902* -- Energy Storage-- Batteries-- Performance & Testing
CAPACITY
CHALCOGENIDES
COHERENT SCATTERING
CRYSTAL STRUCTURE
DIFFRACTION
ELECTRIC BATTERIES
ELECTROCHEMICAL CELLS
ELEMENTS
FAILURES
HYDROGEN
LEAD COMPOUNDS
LEAD OXIDES
LEAD-ACID BATTERIES
MEDIUM TEMPERATURE
NONMETALS
OXIDES
OXYGEN COMPOUNDS
SCATTERING
STRUCTURE FACTORS
X-RAY DIFFRACTION