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Analysis of the temperature dependence of the high-frequency EMR spectra of Mn ions in the lithium-ion battery material LiMn2O4

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This paper deals with the analysis of the temperature dependence of high-frequency EMR (HF-EMR) spectra due to Mn3+ and Mn4+ ions in the lithium manganese spinel LiMn2O4. A range of powder samples obtained by the sol–gel method with calcinations in several temperature ranges were prepared for this study. Based on the initial characterization carried out by a number of techniques, the physicochemical and structural properties of the samples were earlier determined. Independently, temperature magnetization and HF-EMR measurements were carried out. The EMR spectra vary strongly between samples, indicating possible structural or chemical changes. Quantitative analysis of the temperature dependence of the HF-EMR spectra due to Mn3+ and Mn4+ ions in LiMn2O4 is presented in this paper. The spectral analysis concerns the line shape, linewidth, intensity and g-factors. Fittings using the Lorentzian spectral shape and, to a certain extent, the Gaussian spectral shape have been carried out in order to parameterize the temperature dependence of the HF-EMR spectra. This parameterization of the HF-EMR experimental data enables a deeper characterization of the samples. Subsequently, a better insight into the role of the Mn3+ and Mn4+ ions in accounting for the characteristics most suitable for application of LiMn2O4 as a cathode material may be gained.

Affiliations: 1: Institute of Physics, Szczecin University of Technology, Al. Piastów 17, 70-310 Szczecin, Poland; 2: Institute of Physics, University of Rzeszow, Rejtana 16a, 35-310 Rzeszow, Poland; 3: Faculty of Chemistry, Jagiellonian University, Ingardena 3 Str., 30-060 Cracow, Poland; 4: Molecular Photoscience Research Center, Kobe University, 1-1 Rokkodai, Nada, Kobe 657-8501, Japan


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