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Solid-state redox reactions of LiCoO[sub 2] (R[bar 3]m) for 4 volt secondary lithium cells

Journal Article · · Journal of the Electrochemical Society; (United States)
DOI:https://doi.org/10.1149/1.2059267· OSTI ID:6667060

LiCoO[sub 2] (R[bar 3]m; a = 2.82 [angstrom], c = 14.1 [angstrom] in hexagonal setting) was prepared and examined in nonaqueous lithium cells using 1M LiClO[sub 4] propylene carbonate solution at 30 C. The oxidation of LiCoO[sub 2] and the reduction of Li[sub 1[minus]x]CoO[sub 2] proceeded reversibly in the voltage region above 3.9 V. X-ray diffraction (XRD) examinations indicated the reaction proceeded in a topotactic manner, i.e., two-phase reactions (0 < x < 1/4 and 3/4 < x < 1 in Li[sub 1[minus]x]CoO[sub 2]) and a single-phase reaction (1/4 < x < 3/4). A monoclinic phase was observed in 3/4 < x < 1 in addition to that at about x = 0.45. Detailed open-circuit voltage measurements were carried out. The open-circuit voltage are invariable at 3.92 V for 0 < x < 1/4 and at 4.50 V for 3/4 < x < 1. The two straight lines are connected smoothly by a composition-dependent curve for 1/4 < x < 3/4, which was consistent with the XRD observations. The differences and similarities between the solid-state redox reactions of LiCoO[sub 2] and LiNiO[sub 2] were discussed by comparing the structural and electrochemical data. Possible lithium ordering at x = 1/4 and 3/4 for this type of material is described in terms of a [2 x 2] superlattice in a triangular lattice of sites.

OSTI ID:
6667060
Journal Information:
Journal of the Electrochemical Society; (United States), Journal Name: Journal of the Electrochemical Society; (United States) Vol. 141:11; ISSN JESOAN; ISSN 0013-4651
Country of Publication:
United States
Language:
English