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Formation of Fe and Ni substituted LiMn2–XMXO4 nanopowders and their crystal and electronic structure and magnetic properties

E. Talik
E. Talik
, 
L. Lipińska
L. Lipińska
, 
A. Guzik
A. Guzik
, 
P. Zajdel
P. Zajdel
, 
M. Michalska
M. Michalska
, 
M. Szubka
M. Szubka
, 
M. Kądziołka-Gaweł
M. Kądziołka-Gaweł
 et 
R.L. Paul
R.L. Paul
   | 02 avr. 2017
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Publié en ligne: 02 avr. 2017
Pages: 159 - 172
Reçu: 08 févr. 2016
Accepté: 12 déc. 2016
DOI: https://doi.org/10.1515/msp-2017-0014
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© 2017 E. Talik, L. Lipińska, A. Guzik, P. Zajdel, M. Michalska, M. Szubka, M. Kądziołka-Gaweł, R.L. Paul
This article is distributed under the terms of the Creative Commons Attribution Non-Commercial License, which permits unrestricted non-commercial use, distribution, and reproduction in any medium, provided the original work is properly cited.

Example XRD patterns for LiMn1.7Ni0.3O4 and LiMn1.7Fe0.3O4.
Example XRD patterns for LiMn1.7Ni0.3O4 and LiMn1.7Fe0.3O4.

Lattice parameter dependence (a) on nickel concentration for LiMn2–xNixO4 (the real concentrations were obtained by XPS and PGAA methods); (b) on iron concentration for LiMn2–xFexO4 (the real concentrations were obtained by XPS method).
Lattice parameter dependence (a) on nickel concentration for LiMn2–xNixO4 (the real concentrations were obtained by XPS and PGAA methods); (b) on iron concentration for LiMn2–xFexO4 (the real concentrations were obtained by XPS method).

SEM micrographs of the Ni series: (a) LiMn1.9Ni0.1O4, (b) LiMn1.8Ni0.2O4, (c) LiMn1.7Ni0.3O4, (d) LiMn1.6Ni0.4O4, (e) LiMn1.5Ni0.5O4, and Fe series: (f) LiMn1.9Fe0.1O4, (g) LiMn1.8Fe0.2O4, (h) LiMn1.7Fe0.3O4, (i) LiMn1.6Fe0.4O4, (j) LiMn1.5Fe0.5O4. Magnification 50000×, except (i) where it is 20000×.
SEM micrographs of the Ni series: (a) LiMn1.9Ni0.1O4, (b) LiMn1.8Ni0.2O4, (c) LiMn1.7Ni0.3O4, (d) LiMn1.6Ni0.4O4, (e) LiMn1.5Ni0.5O4, and Fe series: (f) LiMn1.9Fe0.1O4, (g) LiMn1.8Fe0.2O4, (h) LiMn1.7Fe0.3O4, (i) LiMn1.6Fe0.4O4, (j) LiMn1.5Fe0.5O4. Magnification 50000×, except (i) where it is 20000×.

57Fe Mössbauer hyperfine parameters of LiMn1.5Fe0.5O4. The fitted subspectra are presented on the spectrum.
57Fe Mössbauer hyperfine parameters of LiMn1.5Fe0.5O4. The fitted subspectra are presented on the spectrum.

XPS overview spectra of the samples with x = 0.5 for the Ni and Fe series.
XPS overview spectra of the samples with x = 0.5 for the Ni and Fe series.

XPS Mn3p and their deconvolution into synthetic lines of Mn3+, Mn4+ and Li1s for (a) the Ni series and (b) the Fe series.
XPS Mn3p and their deconvolution into synthetic lines of Mn3+, Mn4+ and Li1s for (a) the Ni series and (b) the Fe series.

XPS O1s of (a) the Ni and (b) Fe series. 1 marks oxygen in the compound, 2 to 5 enumerate additional lines.
XPS O1s of (a) the Ni and (b) Fe series. 1 marks oxygen in the compound, 2 to 5 enumerate additional lines.

XPS of the Ni2p (a) and Fe2p (b) lines.
XPS of the Ni2p (a) and Fe2p (b) lines.

The XPS spectrum of valence bands.
The XPS spectrum of valence bands.

Magnetic susceptibility of (a) the Ni series and (b) the Fe series measured under 1 T.
Magnetic susceptibility of (a) the Ni series and (b) the Fe series measured under 1 T.

Profile parameters obtained from the Rietveld refinement of the Ni doped series (CDS is Coherent Domain Size; estimated shape anisotropy is reported in curly brackets).

Nominal compositiona [Å]V [Å3]CDS [nm]Strain [%]SGComment
LiMn1.9Ni0.1O48.222(1)555.9(2)91{1}0.25(5)Fd3mpure
LiMn1.8Ni0.2O48.203(2)552.0(2)36{7}0.25(2)Fd3mpure
LiMn1.7Ni0.3O48.190(1)549.4(2)58{32}0.40(6)Fd3m+2nd phase
LiMn1.6Ni0.4O48.190(1)549.3(2)107{78}0.52(5)Fd3m+2nd phase
LiMn1.5Ni0.5O48.172(2)545.8(2)43{1}0.12(2)Fd3m+2nd phase
LiMn1.5Ni0.5O48.167(1)544.7(2)51{10}0.0800(1)Fd3m[43]
LiMn2O48.207(1)552.8(1)80{7}0.3101(1)Fd3m[43]
Li1.12Mn1.88O48.2232(4)556.1Fd3m[64]
Undoped8.2228(4)Fd3m[52] NPD
Ni(II) 0.078.2156(1)Fd3m[52] NPD
LiMn1.5Ni0.5O48.16594(3)[53] XRD
LiMn1.5Ni0.5O48.169036.9Fd3m/P4332[31] XRD

57Fe Mössbauer hyperfine parameters of LiMn1.5Fe0.5O4 where A is abundance, IS – isomer shift, QS – quadrupole splitting.

ComponentIS [mm/s]QS [mm/s]A [%]
D10.347±0.0030.643±0.04065.17
D20.354±0.0030.846±0.03234.83

Structural parameters for the LiMn2–xFexO4 series.

xAnion parameterSize K00Size K41Strain S400Strain S220ADP [Å2]
LiMn/FeO
0.10.2704(3)1.55(2)–0.23(1)–6.3(9)4.68(8)5.5(2)
0.20.2695(3)2.3(3)–0.19(2)–2.8(7)3.82(8)4.7(2)
0.30.2697(3)2.00(3)–0.25(2)–3.7(8)4.2(1)5.1(1)
0.40.2663(2)0.40(1)–0.48(1)–1.0(4)3.22(5)4.2(1)
0.50.2646(2)0.88(2)–0.60(1)––0.1(3)2.66(5)3.8(1)

Profile parameters obtained from the Rietveld refinement of the Fe doped series (CDS is Coherent Domain Size; estimated shape anisotropy is reported in curly brackets).

Nominal compositiona [Å]V [Å3]CDS [nm]Strain [%]SGComment
LiMn1.9Fe0.1O48.241(1)559.7(1)64{1}0.15(3)Fd3mpure
LiMn1.8Fe0.2O48.241(1)559.7(1)43{1}0.14(2)Fd3mpure
LiMn1.7Fe0.3O48.2454(8)560.54(9)50{1}0.15(2)Fd3mpure
LiMn1.6Fe0.4O48.2546(6)562.46(7)250{1}0.22(4)Fd3mpure
LiMn1.5Fe0.5O48.2547(6)562.47(7)113{1}0.24(4)Fd3mpure
LiMn2O48.207(1)552.8(1)80{7}0.3101(1)Fd3m[43]
Li1.12Mn1.88O48.2232(4)556.1Fd3m[64]
Undoped8.2228(4)Fd3m[52] NPD
LiMn1.5Fe0.5O48.258(1)563.1(2)51{3}0.2444(1)Fd3m[43]

Structural parameters for the LiMn2–xNixO4 series.

xAnion parameterSize K00Size K41Strain S400Strain S220ADP [Å2]
LiMn/NiO
0.10.2697(3)1.10(2)–0.62(2)–3.3(7)3.87(7)3.7(1)
0.20.2686(4)3.00(9)1.3(2)0.22(5)1.0(2)12(1)3.67(9)3.3(1)
0.30.2587(3)2.56(7)2.6(2)0.36(6)3.3(2)3.0(fix)2.04(6)2.8(1)
0.40.2594(3)1.60(7)1.8(1)0.98(7)4.7(2)3.0(fix)1.70(5)2.7(1)
0.50.2710(3)2.34(4)–0.15(2)–9.0(1.0)4.4(1)3.3(2)

Chemical compositions and magnetic properties of the Ni series.

XPScompositionLi/(Mn+Ni)0.5: nominalPGAAcompositionMn3+/Mn4+Theta[K]µeff (µB)exp.µeff (µB)calc.
Li1.16Mn1.82Ni0.13O3.890.60LiMn1.64Ni0.09 Oy0.61166.15.9 Mn3+(HS), Mn4+, Ni2+
Li1.36Mn1.93Ni0.2703.460.62LiMn1.44Ni0.16 Oy0.59405.96.1 Mn3+(HS), Mn4+, Ni2+
*Li1.16Mn1.65Ni0.2803.920.60LiMn1.54Ni0.28 Oy0.67514.34.6 Mn3+(LS), Mn4+, Ni2+
*Li1.01Mn1.73Ni0.41O3.820.47LiMn1.33Ni0.34 Oy0.641103.75.0 Mn3+(LS), Mn4+, Ni2+
*Li1.17Mn1.59Ni0.67O3.580.52LiMn1.29Ni0.44 Oy0.951692.54.9 Mn3+(LS), Mn4+, Ni2+

Chemical compositions and magnetic properties of the Fe series.

XPScompositionLi/(Mn+Fe)0.5: nominalMn3+/Mn4+Theta[K] 1 Tµeff (µB)exp.µeff (µB)calc.
Li1.18Mn1.78Fe0.12O3.920.621.541284.884.88 0.75Mn3+(LS) + 0.25Mn3+(HS), Mn4+, Fe3+(LS)
Li1.17Mn1.80Fe0.17O3.870.591.171004.864.85 0.82Mn3+(LS) + 0.18Mn3+(HS), Mn4+, Fe3+(LS)
Li1.37Mn1.70Fe0.21O3.700.711.09895.655.62 0.4Mn3+(LS) + 0.6Mn3+(HS), Mn4+, Fe3+(HS)
Li1.23Mn1.82Fe0.27O3.670.591.332885.205.21 0.8Mn3+(LS) + 0.2Mn3+(HS), Mn4+, 2/3Fe3+(LS) + 1/3Fe3+(HS)
Li0.91Mn1.66Fe0.31O4.120.461.76–––
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