Magnetic properties of the chemically delithiated Li{sub x}Mn{sub 2}O{sub 4} with 0.07{<=}x{<=}1

Journal Article · Sun May 15 00:00:00 EDT 2011 · Journal of Solid State Chemistry

DOI:https://doi.org/10.1016/j.jssc.2011.03.019· OSTI ID:21494266

Mukai, Kazuhiko ^[1]; Sugiyama, Jun; Kamazawa, Kazuya; Ikedo, Yutaka ^[1]; Andreica, Daniel ^[2]; Amato, Alex ^[2]

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1. Toyota Central Research and Development Laboratories, Inc., 41-1 Yokomichi, Nagakute, Aichi 480-1192 (Japan)
2. Laboratory for Muon-Spin Spectroscopy, Paul Scherrer Institut, PSI Villigen CH-5232 (Switzerland)

Magnetism for the Li{sub x}Mn{sub 2}O{sub 4} samples with 0.07{<=}x{<=}1, which are prepared by a chemical reaction in HNO{sub 3} solution, is investigated by direct current susceptibility ({chi}) and muon-spin rotation/relaxation ({mu}SR) measurements. The effective magnetic moment ({mu}{sub eff}) of Mn ions decreases monotonically with decreasing x, indicating that Mn{sup 3+} ions with S=2 (t{sub 2g}{sup 3}e{sub g}{sup 1}) are oxidized to Mn{sup 4+} ions with S=3/2 (t{sub 2g}{sup 3}) with decreasing x. On the other hand, as x decreases from 1 to 0.6, the Curie-Weiss temperature ({Theta}{sub p}) increases monotonically from {approx}-260 to -100 K, and then levels off to -100 K with further decreasing x. This indicates that the antiferromagnetic interaction is dominant in the whole x range. For the x=0.48 sample, the temperature dependence of {chi} in field-cooling mode clearly deviates from that in zero-field-cooling mode below {approx}63 K (=T{sub m}). Furthermore, the hysteresis loop is observed in the magnetization vs. field curve at 5 K. Since the zero-field {mu}SR spectrum is well fitted by a strongly damped oscillation function, the Mn moments for the x=0.48 sample are in a highly disordered fashion down to the lowest temperature measured. -- Graphical abstract: Magnetic phase diagram of the chemically delithiated spinel Li{sub x}Mn{sub 2}O{sub 4} determined by magnetic susceptibility ({chi}) and muon spin rotation/relaxation ({mu}SR) measurements. Display Omitted Highlights: {yields} Magnetic properties of the chemically delithiated Li{sub x}Mn{sub 2}O{sub 4} samples are investigated. {yields} The antiferromagnetic interaction is dominant in the whole x range. {yields} All the Li{sub x}Mn{sub 2}O{sub 4} samples show a magnetic transition below T{sub m}. {yields} The remanent magnetization vs. x curve exhibits a maximum at x=0.48. {yields} The x=0.48 sample is in a highly disordered magnetic state even at 1.8 K.

• OSTI ID: 21494266
• Journal Information: Journal of Solid State Chemistry, Vol. 184, Issue 5; Other Information: DOI: 10.1016/j.jssc.2011.03.019; PII: S0022-4596(11)00116-2; Copyright (c) 2011 Elsevier Science B.V., Amsterdam, The Netherlands, All rights reserved.; ISSN 0022-4596
• Country of Publication: United States
• Language: English

Related Subjects

36 MATERIALS SCIENCE
ANTIFERROMAGNETISM
CHEMICAL REACTIONS
COOLING
ELECTRIC BATTERIES
HYSTERESIS
INTERACTIONS
LITHIUM COMPOUNDS
LITHIUM IONS
MAGNETIC MOMENTS
MAGNETIC SUSCEPTIBILITY
MAGNETIZATION
MANGANESE COMPOUNDS
MANGANESE IONS
MUON SPIN RELAXATION
NITRIC ACID
OXIDES
PHASE DIAGRAMS
SPINELS
TEMPERATURE DEPENDENCE
TEMPERATURE RANGE 0000-0013 K
TEMPERATURE RANGE 0013-0065 K
TEMPERATURE RANGE 0065-0273 K
ALKALI METAL COMPOUNDS
CHALCOGENIDES
CHARGED PARTICLES
DIAGRAMS
ELECTROCHEMICAL CELLS
ENERGY STORAGE SYSTEMS
ENERGY SYSTEMS
HYDROGEN COMPOUNDS
INFORMATION
INORGANIC ACIDS
INORGANIC COMPOUNDS
IONS
MAGNETIC PROPERTIES
MAGNETISM
MINERALS
NITROGEN COMPOUNDS
OXIDE MINERALS
OXYGEN COMPOUNDS
PHYSICAL PROPERTIES
RELAXATION
TEMPERATURE RANGE
TRANSITION ELEMENT COMPOUNDS