Spectroscopic evidence of the Mn3+-Fe2+ octahedral pair in lithium-manganese ferrites near the order-disorder transition

Petit, F.; Lenglet, M.

doi:10.1016/0038-1098(93)90923-b

Cited by 25 publications

(4 citation statements)

References 30 publications

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“…This cation distribution is based on the premise that 80% of Mn ions occupy the tetrahedral position (i.e., the A-site), while the remaining 20% occupy the octahedral position (i.e., the B-site) [18]. Although iron and manganese ions exist at both A-and B-sites, they have preference for the B-and the A-sites, respectively.…”

Section: Structural Propertiesmentioning

confidence: 99%

Doping effect of Mn2+ on the magnetic behavior in Ni–Zn ferrite nanoparticles prepared by sol–gel auto-combustion

Shirsath

Toksha

Kadam

et al. 2010

Journal of Physics and Chemistry of Solids

189

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Section: Structural Propertiesmentioning

confidence: 99%

Doping effect of Mn2+ on the magnetic behavior in Ni–Zn ferrite nanoparticles prepared by sol–gel auto-combustion

Shirsath

Toksha

Kadam

et al. 2010

Journal of Physics and Chemistry of Solids

189

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“…͒ can exhibit 3/1 transition metal ordering on the 4b and 12d octahedral sites of space group P4 3 32 vs the random octahedral 16d sites of Fd3m. [3][4][5][6][7][8] Despite numerous papers on LiMn 1.5 Ni 0.5 O 4 , [9][10][11][12][13] to our knowledge there is no single study covering the order-disorder transition, providing a comparison and basis of the electrochemical performance difference of phases on both sides of the transition temperature. Some exceptions are those by Dahn et al 14 and Kumagai et al 15 who provided ͑without naming the transition͒ the dependence of lattice parameter of spinel phase on synthesis temperature, an indication of this phenomenon.…”

mentioning

confidence: 99%

Synthesis and Characterization of Nanostructured 4.7 V Li[sub x]Mn[sub 1.5]Ni[sub 0.5]O[sub 4] Spinels for High-Power Lithium-Ion Batteries

Kunduraci

Amatucci

2006

J. Electrochem. Soc.

396

408

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͑x = 0.95,1.0,1.05͒ spinel powders were synthesized by a modified Pechini method. The powders were annealed at different temperatures between 500 and 800°C for 15 h. Depending on the ordering/disordering of transition metal ions on octahedral sites, spinels were assigned to either ordered P4 3 32 ͑P͒ or disordered Fd3m ͑F͒ space groups. The spinels of the two symmetry groups differed significantly in fast discharge rate capability. Extensive characterization was employed to identify the source of the difference. Vibrational spectroscopy techniques ͑FTIR and Raman͒, in situ and ex situ XRD and impedance spectroscopy did not reveal any sign of structural degradation for electrochemically inferior P4 3 32 spinels even after rigorous cycling. The poor performance was assigned to an intrinsic property, the lower electrical conductivity of the cation ordered samples. Arrhenius plots of sintered pellets revealed that the ordered spinels were shown to have two orders of magnitude lower electronic conductivity than disordered samples. The difference in electronic conductivity was assigned to the presence of a small amount of Mn 3+ in disordered samples.

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“…Further information arises from synthesis conditions known for other spinel oxides of the system LiO 0,5 -MnO x -FeO x . Spinel ferrites Li 0.5-0.5x Fe 2.5-0.5x Mn x O 4 (0 ≤ x ≤ 1 [ii]) with only Mn(II) were prepared by the reaction of lithium ferrite / manganese ferrite mixtures at 850°C in a vacuum ampoule [10]. On the other hand, compounds of the solid solution series Li 1-0.5x Fe 2.5x Mn 2-2x O 4 [iv] and Li 1-0.5x Fe 1.5x+1 Mn 1-x O 4 [v] each with 0 ≤ x ≤ 1, whose contain manganese in the oxidations state III and/or IV, were synthesized at 600°C to 750°C in air [11] and/or at 800°C in oxygen atmosphere [12].…”

mentioning

confidence: 99%

Synthesis and characterization of compounds Li_xMn_1+xFe_2–2xO₄ with spinel structure in the quasiternary system “LiO_0,5 – MnO_x – FeO_x“

Wende

Langbein²

2005

Cryst. Res. Technol.

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Key words thermal analysis, spinel phases Li x Mn 1+x Fe 2-2x O 4 , freeze drying, XRD. PACS 61.10.Nz, 61.66.Fn, 75.50.Gg The thermal decomposition of freeze-dried Li-Mn(II)-Fe(III)-formate precursors was investigated by means of DTA, TG and mass spectroscopy. By the thermal treatment of the prefired precursors between 400 and 1000°C, single phase solid solutions Li x Mn 1+x Fe 2-2x O 4 (0 ≤ x ≤ 1) with cubic spinel structure were obtained. To get single phase spinels, special conditions concerning the temperature T and the oxygen partial pressure p(O 2 ) during the synthesis are required. Because of the high reactivity of the freeze-dried precursors, in comparison with the conventional solid state reaction, the reaction temperature can be lowered by 200°C. The cation distribution and the properties of the Li-Mn-ferrites were studied by chemical analysis, X-ray powder diffraction and magnetization measurements. It was found that for high substitution rates, almost all lithium occupies the tetrahedral coordinated A-sites of the spinel lattice AB 2 O 4 , while at small x-values, lithium ions are distributed over the tetrahedral and octahedral sites.

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Spectroscopic evidence of the Mn3+-Fe2+ octahedral pair in lithium-manganese ferrites near the order-disorder transition

Cited by 25 publications

References 30 publications

Doping effect of Mn2+ on the magnetic behavior in Ni–Zn ferrite nanoparticles prepared by sol–gel auto-combustion

Doping effect of Mn2+ on the magnetic behavior in Ni–Zn ferrite nanoparticles prepared by sol–gel auto-combustion

Synthesis and Characterization of Nanostructured 4.7 V Li[sub x]Mn[sub 1.5]Ni[sub 0.5]O[sub 4] Spinels for High-Power Lithium-Ion Batteries

Synthesis and characterization of compounds Li_xMn_1+xFe_2–2xO₄ with spinel structure in the quasiternary system “LiO_0,5 – MnO_x – FeO_x“

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Spectroscopic evidence of the Mn3+-Fe2+ octahedral pair in lithium-manganese ferrites near the order-disorder transition

Cited by 25 publications

References 30 publications

Doping effect of Mn2+ on the magnetic behavior in Ni–Zn ferrite nanoparticles prepared by sol–gel auto-combustion

Doping effect of Mn2+ on the magnetic behavior in Ni–Zn ferrite nanoparticles prepared by sol–gel auto-combustion

Synthesis and Characterization of Nanostructured 4.7 V Li[sub x]Mn[sub 1.5]Ni[sub 0.5]O[sub 4] Spinels for High-Power Lithium-Ion Batteries

Synthesis and characterization of compounds LixMn1+xFe2–2xO4 with spinel structure in the quasiternary system “LiO0,5 – MnOx – FeOx“

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Synthesis and characterization of compounds Li_xMn_1+xFe_2–2xO₄ with spinel structure in the quasiternary system “LiO_0,5 – MnO_x – FeO_x“