Mechanism for limited 55 C storage performance of Li{sub 1.05}Mn{sub 1.95}O{sub 4} electrodes

Journal Article · Mon Feb 01 04:00:00 EST 1999 · Journal of the Electrochemical Society

DOI:https://doi.org/10.1149/1.1391625· OSTI ID:328197

Du Pasquier, A; Blyr, A; Courjal, P; Larcher, D; Gerand, B ^[1]; Amatucci, G; Tarascon, J M ^[2]

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1. UPRES, Amiens (France). Lab. de Reactivite et de Chimie des Solides
2. Bellcore, Red Bank, NJ (United States)

A survey of the chemical stability of high-surface area LiMn{sub 2}O{sub 4} in various Li-based electrolytes was performed as a function of temperature. The evidence for an acidic-induced Mn dissolution was confirmed, but more importantly the authors identified, by means of combined infrared spectroscopy, thermogravimetric analysis, and X-ray diffraction measurements, the growth, upon storage of LiMn{sub 2}O{sub 4} in the electrolyte at 100 C, of a protonated {lambda}-MnO{sub 2} phase partially inactive with respect to lithium intercalation. This results sheds light on how the mechanism of high temperature irreversible capacity loss proceeds. Mn dissolution first occurs, leading to a deficient spinel having all the Mn in the +4 oxidation state. Once this composition is reached, Mn cannot be oxidized further, and a protonic ion-exchange reaction takes place at the expense of the delithiation reaction. The resulting protonated {lambda}-Mn{sub 2{minus}y}O{sub 4} phase has a reduced capacity with respect to lithium, thereby accounting for some of the irreversible capacity loss experienced at 55 C for such a material.

• OSTI ID: 328197
• Journal Information: Journal of the Electrochemical Society, Journal Name: Journal of the Electrochemical Society Journal Issue: 2 Vol. 146; ISSN JESOAN; ISSN 0013-4651
• Country of Publication: United States
• Language: English

Related Subjects

25 ENERGY STORAGE
36 MATERIALS SCIENCE
DISSOLUTION
ELECTRICAL PROPERTIES
ELECTRODES
LITHIUM OXIDES
MANGANESE OXIDES
METAL-NONMETAL BATTERIES
STABILITY