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

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21 Citations (Scopus)


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
Issue number2
Publication statusPublished - 2006 Sept 22

Bibliographical note

Funding Information:
This work was performed by the financial support of National R&D programs’ of the Ministry of Science and Technology (MOST), Republic of Korea, and supported partly by the SRC/ERC program of MOST/KOSEF (grant: R11-2005-008-00000-0). The experiments at PLS were supported in part by MOST and POSTECH.

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


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