A survey of the chemical stability of high-surface area LiMn2O4 in various
Li-based electrolytes was performed as a function of temperature. The evide
nce for an acidic-indued Mn dissolution was confirmed, hut more importantly
we identified, by means of combined infrared spectroscopy, thermogravimetr
ic analysis, and X-ray diffraction measurements, the growth, upon storage o
f LiMn2O4 in the electrolyte at 100 degrees C, of a protonated lambda-MnO2
phase partially inactive with respect to Lithium intercalation. This result
sheds light on bow 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 reach
ed, Mn cannot he oxidized further, and a protonic ion-exchange reaction tak
es place at the expense of the delithiation reaction. The resulting protona
ted lambda-Mn2-yO4 phase has a reduced capacity with respect to lithium, th
ereby accounting for some of the irreversible capacity loss experienced at
55 degrees C for such a material (C) 1999 The Electrochemical Society. S001
3-4651(98)01-081-7. All rights reserved.