In Situ Characterization of Metastable Pb3O5 and Pb2O3 Phases During Thermal Decomposition of PbO2 to PbO.
Inorg Chem
; 63(31): 14313-14324, 2024 Aug 05.
Article
em En
| MEDLINE
| ID: mdl-39052493
ABSTRACT
Nonstoichiometric lead oxides play a key role in the formation and cycling of the positive electrodes in a lead acid battery. These phases have been linked to the underutilization of the positive active material but also play a key role in the battery's cycle life, providing interparticle adhesion and the connection to the underlying lead grid. Similar phases have previously been identified by mass loss or color change during thermal annealing of PbO2 to PbO, suggesting that at least two intermediate PbOx phases exist. Using multiple, in situ analysis techniques (powder diffraction, X-ray absorption, X-ray photoelectron spectroscopy) and ex situ nuclear magnetic resonance measurements, the structural conversion and changes in the lead oxidation state were identified during this process. Isolation of the PbOx phases enabled confirmation of Pb3O5 and Pb2O3 by diffraction and the first 207Pb NMR measurement of these intermediates. The thermodynamic and kinetic stability of these intermediates and other reported polymorphs were determined by density functional theory, providing key insight into their origins and variation of PbOx structures found in previous studies.
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Base de dados:
MEDLINE
Idioma:
En
Revista:
Inorg Chem
Ano de publicação:
2024
Tipo de documento:
Article
País de afiliação:
Estados Unidos