Abstract
Abstract Magnetic susceptibility measurements and electron paramagnetic resonance spectra of samples prepared from the reactive system MnO/Li2CO3 with different starting Li cationic fraction x are analyzed, taking into account the structural and compositional information provided by x-ray diffraction. Parent phases, as Mn2O3 , Mn3O4 and Li2 MnO3 , arise together with the lithium-manganese spinel as a result of Li-deficiency or Li-excess with respect to the x = 0.33 composition pertinent to the stoichiometric LiMn2O4 spinel. The data show that the spinel phase can sustain a partial Li-Mn substitution in the cation sites, according to compositional models described, for x > 0.33, by Li1+y Mn3+ 1-3y Mn4+ 1+2y O4 (Li-rich spinel) and, for x< 0.33, by Li1-|y| Mn2+ |y| Mn3+ 1+|y| Mn4+ 1-|y| O4 (Li-poor spinel). Paramagnetic resonance data of the Li-poor spinel phase are analyzed to discuss the possible oxidation state of Mn in the tetrahedral site.
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