Magnetic characterization of orthorhombic LiMnO2 and electrochemically transformed spinel LixMnO2 (x <
Journal
Journal of Physics and Chemistry of Solids
Journal Volume
64
Journal Issue
12
Pages
2525-2533
Date Issued
2003
Author(s)
Abstract
Orthorhombic LiMnO2 exhibits complex magnetic behavior. In addition to short- and long-range antiferromagnetic ordering, we observed spin-glass behavior in the reported temperature regime of long-range antiferromagnetic ordering. Lithium extraction from LiMnO2 further complicates its magnetic behavior. A broad maximum of susceptibility at ≈360 K, characteristic of well-ordered LiMnO2, disappears upon electrochemical delithiation to Li0.39MnO2, indicating that two-dimensional ordering on the folded triangular Mn lattice in LiMnO 2 is destroyed as the cation sublattice begins to transform to a spinel. Spin-glass behavior is, however, observed in Li0.39MnO 2 as well. Compared to conventionally prepared spinel LiMn 2O4, a lower degree of frustration is deduced, which is attributed to incomplete spinel ordering in the early stages of the cycling-induced transformation. In addition, the fraction of Mn ions occupying tetrahedral sites during the spinel transformation has been quantitatively determined for the first time, using magnetic susceptibility data. The results, surprisingly, support the existence of low-spin Mn ions on tetrahedral sites in the electrochemically transformed spinel. © 2003 Elsevier Ltd. All rights reserved.
Type
journal article