Versatile electronic behavior of the LixMn3−x−yFeyO4 spinels

• Published in: Journal of alloys and compounds 2013-11, Vol.577, p.269-277
• Main Authors: Alonso-Domínguez, D., Álvarez-Serrano, I., López, M.L., Veiga, M.L., Pico, C., Mompeán, F., García-Hernández, M., Cuello, G.J.
• Format: Article
• Language: English
• Subjects: Alloys; Condensed matter: electronic structure, electrical, magnetic, and optical properties; Condensed matter: structure, mechanical and thermal properties; Dielectric behavior; Domain effects, magnetization curves, and hysteresis; Electron and ion emission by liquids and solids; impact phenomena; Electron energy loss spectra; Electronics; Exact sciences and technology; Ferrimagnetics; Ferrites; Impact phenomena (including electron spectra and sputtering); Li cathodes; Magnetic properties and materials; Magnetization; Magnetization curves, magnetization reversal, hysteresis, barkhausen and related effects; Magnetocaloric effect; Neutron diffraction; Physics; Spinel; Structure of solids and liquids; crystallography; Structure of specific crystalline solids; Studies of specific magnetic materials; Thermogravimetric analysis; Transformations; X-rays
• ISSN: 0925-8388; 1873-4669
• DOI: 10.1016/j.jallcom.2013.05.043

•The LixMn3−x−yFeyO4 spinels show a versatile electronic behavior.•Optimal compositional ranges for different application fields are proposed.•Frustrated ferromagnetic response is compositionally driven.•High ε′ values are obtained when B sites are occupied by both Mn and Fe cations.•High lithium contents are linked to the electrochemical behavior. The detailed structural and electronic characterization of microcrystalline powders of new spinels LixMn3−x−yFeyO4 (0.4⩽x⩽1.33; 0⩽y⩽1.30), obtained by the “liquid mix” method, is reported. Compositional characterization was carried out by means of thermogravimetric analysis, energy-dispersive X-ray spectroscopy and electron energy loss spectroscopy, and their structure was refined from neutron and X-ray diffraction showing a cubic symmetry between 5 and 550K, Space Group Fd3¯m. However, at temperatures above ca. 950K, a reversible transformation, probably implying the formation of an ordered vacant phase, has been detected. The magnetic behavior, analyzed from neutron diffraction data and magnetization measurements, is interpreted considering an “incomplete” ferrimagnetic response, due to magnetic frustration in the B sites. Potential applications have been evaluated from the magnetocaloric, electrochemical and dielectric behavior in selected compositional ranges.