Mechanism for Limited 55°C Storage Performance of Li1.05 Mn1.95 O4 Electrodes

A. Du Pasquier, A. Blyr, P. Courjal, D. Larcher, Glenn Amatucci, B. Gérand, J. M. Tarascon

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Abstract

A survey of the chemical stability of high-surface area LiMn2O4 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 we identified, by means of combined infrared spectroscopy, thermogravimetric analysis, and X-ray diffraction measurements, the growth, upon storage of LiMn2O4 in the electrolyte at 100°C, of a protonated λ-MnO2 phase partially in active with respect to lithiumintercalation.This result 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 Mninthe+4oxidationstate. Once this composition is reached, Mn cannot be oxidized further, and aprotonic ion-exchange reaction takes place at the expense of the delithiation reaction.The resulting protonated λ-Mn2-yO4 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.

Original languageEnglish (US)
Pages (from-to)428-436
Number of pages9
JournalJournal of the Electrochemical Society
Volume146
Issue number2
DOIs
StatePublished - Jan 1 1999

All Science Journal Classification (ASJC) codes

  • Electronic, Optical and Magnetic Materials
  • Renewable Energy, Sustainability and the Environment
  • Surfaces, Coatings and Films
  • Electrochemistry
  • Materials Chemistry

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    Du Pasquier, A., Blyr, A., Courjal, P., Larcher, D., Amatucci, G., Gérand, B., & Tarascon, J. M. (1999). Mechanism for Limited 55°C Storage Performance of Li1.05 Mn1.95 O4 Electrodes. Journal of the Electrochemical Society, 146(2), 428-436. https://doi.org/10.1149/1.1391625