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Title: Structural and magnetic characterization of LiMn{sub 1.825}Cr{sub 0.175}O{sub 4} spinel obtained by ultrasonic spray pyrolysis

Abstract

Quaternary spinel oxide LiMn{sub 1.825}Cr{sub 0.175}O{sub 4} powder was synthesized by using an ultrasonic spray pyrolysis method, without additional annealing. The crystal structure of the as-prepared powder was revealed by X-ray powder diffraction and identified as a single spinel phase with Fd3m space group. The powders had a spherical morphology with extremely smooth surface appearance and densely congested interior structure. Transmission electron microscopy confirmed that the particle consisted by the cohesion of the primary particles. Magnetic measurements performed in DC field in both zero-field-cooled and field-cooled regimes, as well as AC susceptibility experiments, show that system undergoes spin-glass transition at the freezing temperature T {sub f} = 20 K. The value of the effective magnetic moment {mu} {sub eff} = 4.34 {mu} {sub B} obtained from the Curie-Weiss fit in the high temperature region confirms the substitution of Mn{sup 3+} ions with Cr{sup 3+} ions.

Authors:
 [1];  [2];  [3];  [3];  [4];  [5];  [1]
  1. Institute of Technical Sciences of the Serbian Academy of Sciences and Arts, Knez Mihailova 35/IV, 11 000 Belgrade (Serbia)
  2. Faculty of Physical Chemistry, University of Belgrade, Studentski trg 12-16, P.O. Box 137, Belgrade (Serbia)
  3. Vinca Institute of Nuclear Sciences, Laboratory for Theoretical and Condensed Matter Physics, P.O. Box 522, 11001 Belgrade (Serbia)
  4. Faculty of Medicine, University of Nis (Serbia)
  5. Jozef Stefan Institute, Ljubljana (Slovenia)
Publication Date:
OSTI Identifier:
21000607
Resource Type:
Journal Article
Resource Relation:
Journal Name: Materials Research Bulletin; Journal Volume: 42; Journal Issue: 3; Other Information: DOI: 10.1016/j.materresbull.2006.06.018; PII: S0025-5408(06)00260-1; Copyright (c) 2006 Elsevier Science B.V., Amsterdam, The Netherlands, All rights reserved; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; ANNEALING; CHROMIUM IONS; CUBIC LATTICES; FREEZING; MAGNETIC MOMENTS; MAGNETIC PROPERTIES; MANGANESE IONS; MORPHOLOGY; OXIDES; PYROLYSIS; SPACE GROUPS; SPHERICAL CONFIGURATION; SPIN GLASS STATE; SPINELS; SPRAYS; TRANSMISSION ELECTRON MICROSCOPY; X-RAY DIFFRACTION

Citation Formats

Jugovic, D., Cvjeticanin, N., Kusigerski, V., Mitric, M., Miljkovic, M., Makovec, D., and Uskokovic, D.. Structural and magnetic characterization of LiMn{sub 1.825}Cr{sub 0.175}O{sub 4} spinel obtained by ultrasonic spray pyrolysis. United States: N. p., 2007. Web. doi:10.1016/j.materresbull.2006.06.018.
Jugovic, D., Cvjeticanin, N., Kusigerski, V., Mitric, M., Miljkovic, M., Makovec, D., & Uskokovic, D.. Structural and magnetic characterization of LiMn{sub 1.825}Cr{sub 0.175}O{sub 4} spinel obtained by ultrasonic spray pyrolysis. United States. doi:10.1016/j.materresbull.2006.06.018.
Jugovic, D., Cvjeticanin, N., Kusigerski, V., Mitric, M., Miljkovic, M., Makovec, D., and Uskokovic, D.. Thu . "Structural and magnetic characterization of LiMn{sub 1.825}Cr{sub 0.175}O{sub 4} spinel obtained by ultrasonic spray pyrolysis". United States. doi:10.1016/j.materresbull.2006.06.018.
@article{osti_21000607,
title = {Structural and magnetic characterization of LiMn{sub 1.825}Cr{sub 0.175}O{sub 4} spinel obtained by ultrasonic spray pyrolysis},
author = {Jugovic, D. and Cvjeticanin, N. and Kusigerski, V. and Mitric, M. and Miljkovic, M. and Makovec, D. and Uskokovic, D.},
abstractNote = {Quaternary spinel oxide LiMn{sub 1.825}Cr{sub 0.175}O{sub 4} powder was synthesized by using an ultrasonic spray pyrolysis method, without additional annealing. The crystal structure of the as-prepared powder was revealed by X-ray powder diffraction and identified as a single spinel phase with Fd3m space group. The powders had a spherical morphology with extremely smooth surface appearance and densely congested interior structure. Transmission electron microscopy confirmed that the particle consisted by the cohesion of the primary particles. Magnetic measurements performed in DC field in both zero-field-cooled and field-cooled regimes, as well as AC susceptibility experiments, show that system undergoes spin-glass transition at the freezing temperature T {sub f} = 20 K. The value of the effective magnetic moment {mu} {sub eff} = 4.34 {mu} {sub B} obtained from the Curie-Weiss fit in the high temperature region confirms the substitution of Mn{sup 3+} ions with Cr{sup 3+} ions.},
doi = {10.1016/j.materresbull.2006.06.018},
journal = {Materials Research Bulletin},
number = 3,
volume = 42,
place = {United States},
year = {Thu Mar 22 00:00:00 EDT 2007},
month = {Thu Mar 22 00:00:00 EDT 2007}
}
  • The spinel oxides Zn{sub x}Mg{sub 1.5-x}Mn{sub 0.5}FeO{sub 4} (x = 0.0 to 0.6) and MgAl{sub x}Cr{sub x}Fe{sub 2-2x}O{sub 4} (x = 0.0 to 0.6) abbreviated as ZMMFO and MACFO respectively, were synthesized by standard ceramic processing. The compositional purity of all the specimens was checked by EDAX technique. The X-ray diffractometry was employed to determine the lattice constants and distribution of cations in the interstitial voids. The initial decrease of cell edge parameter (a) for ZMMFO up to x = 0.2 and thereafter expected rise in the ‘a’ and the initial slower rate of reduction in the lattice constant formore » MACFO are explained as basic of cation occupancy. The magnetic ordering in both systems is explained by invoking statistical canting models. The compositional variation of magneton number (n{sub B}) for ZMMFO could be very well explained by Localized canting of spin (LCS) model while Random canting of spin (RCS) model was used for MACFO system.« less
  • The 4 V rechargeable capacity of the spinel LiMn{sub 2}O{sub 4} was stabilized by substituting less than 1 mole percent (m/o) Mn{sup 3+} with Cr{sup 3+}. The optimum composition was determined as LiCr{sub 0.012}Mn{sub 1.988}O{sub 4}, which had a discharge capacity exceeding 110 mAh/g even after 100 cycles, although improved stabilities were attained for all Cr-modified compositions studied (0.1 to 7.0 m/o Cr{sup 3+} substitution). The effects of varying electrolyte salt, temperature, and current density were also investigated. Capacity losses in 4 V LiMn{sub 2}O{sub 4}-based spinel systems were attributed to Mn dissolution into the electrolyte causing structural degradation ofmore » the cathode and an increase in cell polarization from deposited Mn interfering with Li{sup +} transport through the anodic solid-electrolyte interphase. Substitution of even a small amount of Mn{sup 3+} by trivalent Cr{sup 3+} minimized this dissolution and resulted in enhanced cathodic electrochemical stability.« less
  • To improve the cycle performance of eco-friendly and cost-effective spinel LiMn{sub 2}O{sub 4} as the cathode of 4 V class Li secondary batteries, the spinel phase LiCr{sub x}Mn{sub 2-x}O{sub 4} (x = 0.01-0.20) was synthesized by soft chemistry method using oxalic acid as chelating agent. The present technique results in better homogeneity, good surface morphology, shorter heat treatment time, sub-micron sized particles, good agglomeration and better crystallinity. Electrochemical studies were monitored in the potential range of 3-4.5 V. The present paper reveals that chromium substituted manganese spinel improves the structural stability of the parent material.
  • Structural changes of LiMn{sub 2}O{sub 4} spinel electrodes have been investigated in 4 V Li/Li{sub x}Mn{sub 2}O{sub 4} cells by X-ray diffraction during prolonged electrochemical cycling between 4.5 and 3.4 V at room temperature. The capacity fade that is observed during cycling is attributed, at least partly, to disproportionation reactions at the particle surface of discharged Li{sub x}Mn{sub 2}O{sub 4} electrodes, resulting in a soluble MnO component. The disproportionation reactions are described with respect to the Li-Mn-O phase diagram. The data support recent reports that Li{sub 2}Mn{sub 2}O{sub 4} can be formed at the electrode surface slightly above 3 Vmore » when cells are discharged and charged at high rates.« less
  • The preparation and characterization of spinel LiMn{sub 2}O{sub 4} having small average particle sizes (<4.0 {micro}m) and narrow particle size distribution are reported. They were obtained by heating a 1:4 Li{sub 2}CO{sub 3}/MnCO{sub 3} mixture at 650 to 850 C in oxygen. Particle size control of the product was achieved by controlling the particle sizes of the precursor materials and the heating conditions. Heating the Li{sub 2}CO{sub 3}/4MnCO{sub 3} mixture results in the formation of Mn{sub 2}O{sub 3} initially, which then reacts with Li{sub 2}CO{sub 3} to form spinel LiMn{sub 2}O{sub 4} according to: 2Li{sub 2}CO{sub 3} + 4 Mn{submore » 2}O{sub 3} + O{sub 2} {yields} 2CO{sub 2}. The LiMn{sub 2}O{sub 4} cathodes have shown excellent rechargeability as well as superior rate capability in Li/polymer electrolyte/LiMn{sub 2}O{sub 4} cells cycled between 3.0 and 4.3 V. Specific capacities between 0.75 and 0.83 /Li per LiMn{sub 2}O{sub 4} were obtained for more than fifty cycles. The LiMn{sub 2}O{sub 4} cathodes can be reversibly cycled between 2.4 and 3.5 V but with declining capacity. For the LiMn{sub 2}O{sub 4} prepared at 650 C, cycling in the 3 V region has little effect on its subsequent performance in the 4 V region, while for the LiMn{sub 2}O{sub 4} prepared at higher temperatures, such cycling causes the 4 V capacity to decline.« less