Influence of nickel content on the chemical bonding character of LiMn2-xNixO4 spinel oxides

Dae Hoon Park, Seung Tae Lim, Seong Ju Hwang, Jin Ho Choy, Jung Hyun Choi, Jaebum Choo

Research output: Contribution to journalArticle

16 Citations (Scopus)

Abstract

A relationship between the chemical bonding nature of LiMn2-xNixO4 and the Ni content has been systematically investigated. According to X-ray diffraction analysis, nickel-substituted lithium manganates crystallize with a cubic spinel structure without the formation of any impurity phase such as NiO in the present substitution range of 0 ≤ x ≤ 0.4. Micro-Raman analysis showed that Ni substitution gave rise to an increase in the intensities and energies of the two main phonon lines at ∼580 and ∼620 cm-1, indicating enhancement of the average Mn oxidation states and reinforcement of the Mn{single bond}O bonds. This was confirmed by Mn K-edge X-ray absorption spectroscopic (XAS) analysis. Also, a new phonon line appeared at ∼495 cm-1 after the Ni substitution, which can be assigned as an Ni-O vibration mode rather than as a T2g(2) mode of LiMn2O4. Ni K-edge XAS and micro-Raman analyses clearly demonstrate that divalent nickel ions existed in the octahedral sites of the cubic spinel lattice without a significant change in the chemical environment with the Ni content. In this regard, the poor electrochemical performance of heavily Ni-substituted compounds for the 3 V region is not attributable to the variation in the local environment of Ni ions with the Ni content, but to the low structural stability of the substituted NiO6 octahedra.

Original languageEnglish
Pages (from-to)1346-1352
Number of pages7
JournalJournal of Power Sources
Volume159
Issue number2
DOIs
Publication statusPublished - 2006 Sep 22

Fingerprint

Nickel
Oxides
spinel
Substitution reactions
X ray absorption
nickel
substitutes
oxides
Ions
x rays
Spectroscopic analysis
spectroscopic analysis
structural stability
reinforcement
Lithium
X ray diffraction analysis
vibration mode
Reinforcement
ions
lithium

All Science Journal Classification (ASJC) codes

  • Renewable Energy, Sustainability and the Environment
  • Energy Engineering and Power Technology
  • Physical and Theoretical Chemistry
  • Electrical and Electronic Engineering

Cite this

Park, Dae Hoon ; Lim, Seung Tae ; Hwang, Seong Ju ; Choy, Jin Ho ; Choi, Jung Hyun ; Choo, Jaebum. / Influence of nickel content on the chemical bonding character of LiMn2-xNixO4 spinel oxides. In: Journal of Power Sources. 2006 ; Vol. 159, No. 2. pp. 1346-1352.
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abstract = "A relationship between the chemical bonding nature of LiMn2-xNixO4 and the Ni content has been systematically investigated. According to X-ray diffraction analysis, nickel-substituted lithium manganates crystallize with a cubic spinel structure without the formation of any impurity phase such as NiO in the present substitution range of 0 ≤ x ≤ 0.4. Micro-Raman analysis showed that Ni substitution gave rise to an increase in the intensities and energies of the two main phonon lines at ∼580 and ∼620 cm-1, indicating enhancement of the average Mn oxidation states and reinforcement of the Mn{single bond}O bonds. This was confirmed by Mn K-edge X-ray absorption spectroscopic (XAS) analysis. Also, a new phonon line appeared at ∼495 cm-1 after the Ni substitution, which can be assigned as an Ni-O vibration mode rather than as a T2g(2) mode of LiMn2O4. Ni K-edge XAS and micro-Raman analyses clearly demonstrate that divalent nickel ions existed in the octahedral sites of the cubic spinel lattice without a significant change in the chemical environment with the Ni content. In this regard, the poor electrochemical performance of heavily Ni-substituted compounds for the 3 V region is not attributable to the variation in the local environment of Ni ions with the Ni content, but to the low structural stability of the substituted NiO6 octahedra.",
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Influence of nickel content on the chemical bonding character of LiMn2-xNixO4 spinel oxides. / Park, Dae Hoon; Lim, Seung Tae; Hwang, Seong Ju; Choy, Jin Ho; Choi, Jung Hyun; Choo, Jaebum.

In: Journal of Power Sources, Vol. 159, No. 2, 22.09.2006, p. 1346-1352.

Research output: Contribution to journalArticle

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N2 - A relationship between the chemical bonding nature of LiMn2-xNixO4 and the Ni content has been systematically investigated. According to X-ray diffraction analysis, nickel-substituted lithium manganates crystallize with a cubic spinel structure without the formation of any impurity phase such as NiO in the present substitution range of 0 ≤ x ≤ 0.4. Micro-Raman analysis showed that Ni substitution gave rise to an increase in the intensities and energies of the two main phonon lines at ∼580 and ∼620 cm-1, indicating enhancement of the average Mn oxidation states and reinforcement of the Mn{single bond}O bonds. This was confirmed by Mn K-edge X-ray absorption spectroscopic (XAS) analysis. Also, a new phonon line appeared at ∼495 cm-1 after the Ni substitution, which can be assigned as an Ni-O vibration mode rather than as a T2g(2) mode of LiMn2O4. Ni K-edge XAS and micro-Raman analyses clearly demonstrate that divalent nickel ions existed in the octahedral sites of the cubic spinel lattice without a significant change in the chemical environment with the Ni content. In this regard, the poor electrochemical performance of heavily Ni-substituted compounds for the 3 V region is not attributable to the variation in the local environment of Ni ions with the Ni content, but to the low structural stability of the substituted NiO6 octahedra.

AB - A relationship between the chemical bonding nature of LiMn2-xNixO4 and the Ni content has been systematically investigated. According to X-ray diffraction analysis, nickel-substituted lithium manganates crystallize with a cubic spinel structure without the formation of any impurity phase such as NiO in the present substitution range of 0 ≤ x ≤ 0.4. Micro-Raman analysis showed that Ni substitution gave rise to an increase in the intensities and energies of the two main phonon lines at ∼580 and ∼620 cm-1, indicating enhancement of the average Mn oxidation states and reinforcement of the Mn{single bond}O bonds. This was confirmed by Mn K-edge X-ray absorption spectroscopic (XAS) analysis. Also, a new phonon line appeared at ∼495 cm-1 after the Ni substitution, which can be assigned as an Ni-O vibration mode rather than as a T2g(2) mode of LiMn2O4. Ni K-edge XAS and micro-Raman analyses clearly demonstrate that divalent nickel ions existed in the octahedral sites of the cubic spinel lattice without a significant change in the chemical environment with the Ni content. In this regard, the poor electrochemical performance of heavily Ni-substituted compounds for the 3 V region is not attributable to the variation in the local environment of Ni ions with the Ni content, but to the low structural stability of the substituted NiO6 octahedra.

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