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Title: Crystal structure of tetrabasic lead sulfate (4PbO {center_dot} PbSO{sub 4}): An intermediate phase in the production of lead-acid batteries

Journal Article · · Journal of the Electrochemical Society
DOI:https://doi.org/10.1149/1.1838298· OSTI ID:599910
;  [1]
  1. Univ. of Chicago, IL (United States)

Demand for improved battery systems for electric vehicles and power sources in general suggests the need for more accurate descriptions of the solid-state and electrochemical reactions which may affect active-material usage. Tetrabasic lead sulfate (4PbO {center_dot} PbSO{sub 4}) is an intermediate phase commonly formed during production of lead-acid batteries and, with tribasic lead sulfate, determines some battery characteristics. Single-crystal X-ray data have been used to determine its structure to a final weighted R of 0.024 (a = 7.297, b = 11.698, and c = 11.498 {angstrom}, {beta} = 90.93{degree}, P2{sub 1}/c). Its structure is closely related to that of tetragonal PbO, except that one of six Pb sites is occupied by SO{sub 4}. This sulfate group shows either dynamic (librations) or static disorder, but there is no evidence in the crystal for Pb-S disorder as proposed by other X-ray studies. This determination and that for tribasic lead sulfate complete structural determinations of the major phases formed during production of lead-acid batteries. These structural models allow Rietveld studies using either X-ray or neutron-diffraction data to evaluate properties such as crystallinity, atomic ordering, and reactions during curing and cycling. The structures of tetrabasic and tribasic lead sulfate, as well as tetragonal and orthorhombic PbO, have basic features in common. These similarities suggest that there may be structural control during some reactions whereby heterogeneous nucleation influences the products in concert with external variables such as temperature, humidity, and pH.

Research Organization:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Organization:
USDOE, Washington, DC (United States); National Aeronautics and Space Administration, Washington, DC (United States); National Science Foundation, Washington, DC (United States)
DOE Contract Number:
W-31109-ENG-38; FG02-94ER14466
OSTI ID:
599910
Journal Information:
Journal of the Electrochemical Society, Vol. 145, Issue 2; Other Information: PBD: Feb 1998
Country of Publication:
United States
Language:
English