The structural stability of LiCoO{sub 2} at 400{degrees}C.

Journal Article · Tue Oct 01 04:00:00 EDT 2002 · J. Solid State Chem.

DOI:https://doi.org/10.1006/jssc.2002.9679· OSTI ID:961224

Shao-Horn, Y; Hackney, S A; Kahaian, A J; Thackeray, M M

The relative stability of the lithiated-spinel structure, Li{sub 2}[Co{sub 2}]O{sub 4}, at 400{sup o}C to the layered LiCoO{sub 2} structure has been investigated. 'Low-temperature' LT-LiCoO{sub 2} samples were synthesized at 400{sup o}C by the solid-state reaction of Li{sub 2}CO{sub 3} with CoCO{sub 3} (or Co{sub 3}O{sub 4}) for various times between 10 min and 232 days. Least-squares refinements of X-ray powder diffraction patterns were used to determine the fractions of lithiated-spinel Li{sub 2}[Co{sub 2}]O{sub 4} and layered LiCoO{sub 2} in the samples. X-ray powder diffraction and transmission electron microscope data show that Li{sub 2}[Co{sub 2}]O{sub 4} nucleates from an intermediate Li{sub x}Co{sub 1-x}[Co{sub 2}]O{sub 4} spinel product before transforming very slowly to layered LiCoO{sub 2}. The experimental data confirm the theoretical prediction that layered LiCoO{sub 2} is thermodynamically more stable than the lithiated-spinel structure at 400{sup o}C and support the arguments that a non-ideal cation distribution in Li{sub 2}[Co{sub 2}]O{sub 4}, non-stoichiometry and kinetic factors restrict the transformation of the lithiated-spinel structure to layered LiCoO{sub 2} at this temperature.

• Research Organization: Argonne National Laboratory (ANL)
• Sponsoring Organization: SC
• DOE Contract Number: AC02-06CH11357
• OSTI ID: 961224
• Report Number(s): ANL/CMT/JA-45542
• Journal Information: J. Solid State Chem., Journal Name: J. Solid State Chem. Journal Issue: 1 ; Oct. 2002 Vol. 168; ISSN 0022-4596; ISSN JSSCBI
• Country of Publication: United States
• Language: ENGLISH

Related Subjects

25 ENERGY STORAGE
CATIONS
COBALT OXIDES
DATA
DIFFRACTION
DISTRIBUTION
ELECTRIC BATTERIES
ELECTRON DIFFRACTION
ELECTRON MICROSCOPES
KINETICS
LITHIUM OXIDES
PHASE TRANSFORMATIONS
POWDERS
SPINELS
STABILITY
TEMPERATURE RANGE 0065-0273 K
TRANSFORMATIONS
TRANSMISSION
TRANSMISSION ELECTRON MICROSCOPY
X-RAY DIFFRACTION