A neutron powder diffraction study of. cap alpha. - and. beta. -PbO/sub 2/ in the positive electrode material of lead-acid batteries

Journal Article · Fri Jul 01 04:00:00 EDT 1983 · J. Electrochem. Soc.; (United States)

DOI:https://doi.org/10.1149/1.2120008· OSTI ID:5366500

Santoro, A; Caulder, S M; D'Antonio, P

A neutron powder diffraction study of ..cap alpha..- and ..beta..-PbO/sub 2/, both chemically prepared and electrochemically formed in cycled battery plates, was carried out to correlate the electrochemical activity of the lead-acid battery with the atomic arrangement of the electrode constituents. Our results are consistent with the presence of hydrogen in the structure of ..beta..-PbO/sub 2/, but the departure of the occupancy factors from stoichiometric values are not large enough to unambiguously establish whether there are lead or oxygen deficiencies. If the Pb:O ratio corresponds to exact stoichiometry, any hydrogen which is present must be accompanied by a reduction of Pb/sup +4/. There is a significant increase in the lattice parameter ..cap alpha.. of ..beta..-PbO/sub 2/ in cycled battery electrodes relative to the value found in chemically prepared ..beta..-PbO/sub 2/. No change in the c parameter, however, was detected. These dimensional changes are consistent with a configuration for hydrogen similar to that observed in the rutile type structure of SnO/sub 2/, in which there are OH-ions oriented perpendicular to the c axis. The profile parameters obtained in this analysis show that the crystallites of ..beta..-PbO/sub 2/ in the positive plate material of a battery cycled three times (Y3) are smaller than those in the chemically prepared compound (about 450A vs. 800A), while there are no significant differences between the latter and ..beta..-PbO/sub 2/ in the positive plate material of a battery cycled 36 times (Y36). The average structure of ..cap alpha..-PbO/sub 2/ cannot be accurately determined by profile analysis, at the present time. The difficulties encountered in the refinement may be due to extensive defects, nonspherical crystallites of small size, and/or small departures of the structure from orthorhombic symmetry.

• Research Organization: National Bureau of Standards, Washington, DC
• OSTI ID: 5366500
• Journal Information: J. Electrochem. Soc.; (United States), Journal Name: J. Electrochem. Soc.; (United States) Vol. 130:7; ISSN JESOA
• Country of Publication: United States
• Language: English

Related Subjects

25 ENERGY STORAGE
250903 -- Energy Storage-- Batteries-- Materials
Components
& Auxiliaries
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400400* -- Electrochemistry
CATHODES
CHALCOGENIDES
CHEMICAL PREPARATION
CHEMICAL REACTIONS
CHEMISTRY
COHERENT SCATTERING
CONFIGURATION
CRYSTAL DEFECTS
CRYSTAL STRUCTURE
CRYSTALS
DIFFRACTION
DIMENSIONS
ELECTRIC BATTERIES
ELECTROCHEMICAL CELLS
ELECTROCHEMISTRY
ELECTRODES
ELEMENTS
HYDROGEN
HYDROGEN COMPOUNDS
HYDROXIDES
LATTICE PARAMETERS
LEAD COMPOUNDS
LEAD OXIDES
LEAD-ACID BATTERIES
MATERIALS
MINERALS
NEUTRON DIFFRACTION
NONMETALS
OXIDE MINERALS
OXIDES
OXYGEN
OXYGEN COMPOUNDS
PLATES
QUANTITY RATIO
RADIOACTIVE MATERIALS
RADIOACTIVE MINERALS
REDUCTION
RUTILE
SCATTERING
SIZE
STOICHIOMETRY
SYMMETRY
SYNTHESIS
TIN COMPOUNDS
TIN OXIDES
TITANIUM COMPOUNDS
TITANIUM OXIDES
TRANSITION ELEMENT COMPOUNDS