Spectroscopic studies of the structural properties of Ni substituted spinel LiMn2O4

Yingjin Wei; Kyung Wan Nam; Kwang Bum Kim; Gang Chen

doi:10.1016/j.ssi.2005.10.015

Spectroscopic studies of the structural properties of Ni substituted spinel LiMn₂O₄

Yingjin Wei, Kyung Wan Nam, Kwang Bum Kim, Gang Chen

Department of Materials Science and Engineering

Research output: Contribution to journal › Article › peer-review

61 Citations (Scopus)

Abstract

Microstructure and local structure of spinel LiNi_xMn _{2 - x}O₄ (x = 0, 0.1 and 0.2) were studied using X-ray diffraction (XRD) and a combination of X-ray photoelectron spectroscopy (XPS), X-ray absorption near edge spectroscopy (XANES) and Raman scattering with the aim of getting a clear picture of the local structure of the materials responsible for the structural stability of LiNi_xMn _{2 - x}O₄. XRD study showed that Ni substitution caused the changes of the materials' microstructure from the view of the lattice parameter, mean crystallite size, and microstrain. XPS and XANES studies showed the Ni oxidation state in LiNi_xMn_{2 - x}O₄ was larger than + 2, and the Mn oxidation state increased with Ni substitution. The decrease of the intensity of the 1s → 4p_z shakedown transition on the XANES spectra indicated that Ni substitution suppressed the tetragonal distortion of the [MnO₆] octahedron. The Mn(Ni)-O bond in LiNi _xMn_{2 - x}O₄, which is stronger than the Mn-O bond in LiMn₂O₄ was responsible for the blue shift of the A_1g Raman mode and could enhance the structural stability of the [Mn(Ni)O₆] octahedron.

Original language	English
Pages (from-to)	29-35
Number of pages	7
Journal	Solid State Ionics
Volume	177
Issue number	1-2
DOIs	https://doi.org/10.1016/j.ssi.2005.10.015
Publication status	Published - 2006 Jan 16

Bibliographical note

Funding Information:
This work was supported by the Key Project (No. 10411) sponsored by the Ministry of Education of China and the special funds for major state basic research project of China under the Grant 2002CB211802. The work was also partially supported by the Ministry of Information and Communication of Korea [“Support Project of University Information Technology Research Center” supervised by the Korea IT Promotion Agency]. One of the authors, Yingjin Wei, is grateful to Yonsei University and ERC program of MOST/KOSEF (Grant No. R11-2002-102-00000-0) for financial assistance. ITRC supported the XAS work at PAL.

All Science Journal Classification (ASJC) codes

Chemistry(all)
Materials Science(all)
Condensed Matter Physics

Access to Document

10.1016/j.ssi.2005.10.015

Cite this

@article{08fdefd00fd64e0ea81411b9e8b13742,

title = "Spectroscopic studies of the structural properties of Ni substituted spinel LiMn2O4 ",

abstract = "Microstructure and local structure of spinel LiNixMn 2 - xO4 (x = 0, 0.1 and 0.2) were studied using X-ray diffraction (XRD) and a combination of X-ray photoelectron spectroscopy (XPS), X-ray absorption near edge spectroscopy (XANES) and Raman scattering with the aim of getting a clear picture of the local structure of the materials responsible for the structural stability of LiNixMn 2 - xO4. XRD study showed that Ni substitution caused the changes of the materials' microstructure from the view of the lattice parameter, mean crystallite size, and microstrain. XPS and XANES studies showed the Ni oxidation state in LiNixMn2 - xO4 was larger than + 2, and the Mn oxidation state increased with Ni substitution. The decrease of the intensity of the 1s → 4pz shakedown transition on the XANES spectra indicated that Ni substitution suppressed the tetragonal distortion of the [MnO6] octahedron. The Mn(Ni)-O bond in LiNi xMn2 - xO4, which is stronger than the Mn-O bond in LiMn2O4 was responsible for the blue shift of the A1g Raman mode and could enhance the structural stability of the [Mn(Ni)O6] octahedron.",

author = "Yingjin Wei and Nam, {Kyung Wan} and Kim, {Kwang Bum} and Gang Chen",

note = "Funding Information: This work was supported by the Key Project (No. 10411) sponsored by the Ministry of Education of China and the special funds for major state basic research project of China under the Grant 2002CB211802. The work was also partially supported by the Ministry of Information and Communication of Korea [“Support Project of University Information Technology Research Center” supervised by the Korea IT Promotion Agency]. One of the authors, Yingjin Wei, is grateful to Yonsei University and ERC program of MOST/KOSEF (Grant No. R11-2002-102-00000-0) for financial assistance. ITRC supported the XAS work at PAL.",

year = "2006",

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AU - Wei, Yingjin

AU - Nam, Kyung Wan

AU - Kim, Kwang Bum

AU - Chen, Gang

N1 - Funding Information: This work was supported by the Key Project (No. 10411) sponsored by the Ministry of Education of China and the special funds for major state basic research project of China under the Grant 2002CB211802. The work was also partially supported by the Ministry of Information and Communication of Korea [“Support Project of University Information Technology Research Center” supervised by the Korea IT Promotion Agency]. One of the authors, Yingjin Wei, is grateful to Yonsei University and ERC program of MOST/KOSEF (Grant No. R11-2002-102-00000-0) for financial assistance. ITRC supported the XAS work at PAL.

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Y1 - 2006/1/16

N2 - Microstructure and local structure of spinel LiNixMn 2 - xO4 (x = 0, 0.1 and 0.2) were studied using X-ray diffraction (XRD) and a combination of X-ray photoelectron spectroscopy (XPS), X-ray absorption near edge spectroscopy (XANES) and Raman scattering with the aim of getting a clear picture of the local structure of the materials responsible for the structural stability of LiNixMn 2 - xO4. XRD study showed that Ni substitution caused the changes of the materials' microstructure from the view of the lattice parameter, mean crystallite size, and microstrain. XPS and XANES studies showed the Ni oxidation state in LiNixMn2 - xO4 was larger than + 2, and the Mn oxidation state increased with Ni substitution. The decrease of the intensity of the 1s → 4pz shakedown transition on the XANES spectra indicated that Ni substitution suppressed the tetragonal distortion of the [MnO6] octahedron. The Mn(Ni)-O bond in LiNi xMn2 - xO4, which is stronger than the Mn-O bond in LiMn2O4 was responsible for the blue shift of the A1g Raman mode and could enhance the structural stability of the [Mn(Ni)O6] octahedron.

AB - Microstructure and local structure of spinel LiNixMn 2 - xO4 (x = 0, 0.1 and 0.2) were studied using X-ray diffraction (XRD) and a combination of X-ray photoelectron spectroscopy (XPS), X-ray absorption near edge spectroscopy (XANES) and Raman scattering with the aim of getting a clear picture of the local structure of the materials responsible for the structural stability of LiNixMn 2 - xO4. XRD study showed that Ni substitution caused the changes of the materials' microstructure from the view of the lattice parameter, mean crystallite size, and microstrain. XPS and XANES studies showed the Ni oxidation state in LiNixMn2 - xO4 was larger than + 2, and the Mn oxidation state increased with Ni substitution. The decrease of the intensity of the 1s → 4pz shakedown transition on the XANES spectra indicated that Ni substitution suppressed the tetragonal distortion of the [MnO6] octahedron. The Mn(Ni)-O bond in LiNi xMn2 - xO4, which is stronger than the Mn-O bond in LiMn2O4 was responsible for the blue shift of the A1g Raman mode and could enhance the structural stability of the [Mn(Ni)O6] octahedron.

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