Evolution of local structure around manganese in layered LiMnO2 upon chemical and electrochemical delithiation/relithiation

Seong Ju Hwang, Hyo Suk Park, Jin Ho Choy, Guy Campet

Research output: Contribution to journalArticle

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Abstract

Mn K-edge X-ray absorption spectroscopic (XAS) analyses have been performed to probe the evolution of electronic and crystal structures of layered LiMnO2 upon chemical and electrochemical delithiation/relithiation. According to the X-ray absorption near-edge structure studies, it becomes clear that the trivalent manganese ion in LiMnO2 is significantly oxidized by acid treatment and is not fully recovered by subsequent lithiation reaction with n-BuLi. The extended X-ray absorption fine structure results presented here demonstrate that the local structure around manganese in LiMnO2 is changed from a layered α-NaFeO2-type structure to a spinel-like one upon chemical delithiation reaction. It is also found from the XAS analyses for the cycled LiMnO2 that the electrochemical charge - discharge process gives rise not only to the partial oxidation of manganese ion but also to the migration of Mn into the interlayer lithium site, resulting in the coexistence of the layered structure and the spinel one. Such results highlight the lattice instability of layered manganese oxide for the chemical and electrochemical extraction of lithium, which is responsible for the remarkable capacity fading and the formation of two plateaus at around the 3 and 4 V regions after the first electrochemical cycle. On the basis of the present experimental findings, we are now able to suggest that the electrochemical performance of layered LiMnO2 can be improved by blocking the Mn migration path through cationic substitution.

Original languageEnglish
Pages (from-to)1818-1826
Number of pages9
JournalChemistry of Materials
Volume12
Issue number7
DOIs
Publication statusPublished - 2000 Jan 1

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X ray absorption
Manganese
Lithium
Ions
Manganese oxide
Electronic structure
Chemical reactions
Substitution reactions
Crystal structure
Oxidation
Acids
spinell

All Science Journal Classification (ASJC) codes

  • Chemistry(all)
  • Chemical Engineering(all)
  • Materials Chemistry

Cite this

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title = "Evolution of local structure around manganese in layered LiMnO2 upon chemical and electrochemical delithiation/relithiation",
abstract = "Mn K-edge X-ray absorption spectroscopic (XAS) analyses have been performed to probe the evolution of electronic and crystal structures of layered LiMnO2 upon chemical and electrochemical delithiation/relithiation. According to the X-ray absorption near-edge structure studies, it becomes clear that the trivalent manganese ion in LiMnO2 is significantly oxidized by acid treatment and is not fully recovered by subsequent lithiation reaction with n-BuLi. The extended X-ray absorption fine structure results presented here demonstrate that the local structure around manganese in LiMnO2 is changed from a layered α-NaFeO2-type structure to a spinel-like one upon chemical delithiation reaction. It is also found from the XAS analyses for the cycled LiMnO2 that the electrochemical charge - discharge process gives rise not only to the partial oxidation of manganese ion but also to the migration of Mn into the interlayer lithium site, resulting in the coexistence of the layered structure and the spinel one. Such results highlight the lattice instability of layered manganese oxide for the chemical and electrochemical extraction of lithium, which is responsible for the remarkable capacity fading and the formation of two plateaus at around the 3 and 4 V regions after the first electrochemical cycle. On the basis of the present experimental findings, we are now able to suggest that the electrochemical performance of layered LiMnO2 can be improved by blocking the Mn migration path through cationic substitution.",
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Evolution of local structure around manganese in layered LiMnO2 upon chemical and electrochemical delithiation/relithiation. / Hwang, Seong Ju; Park, Hyo Suk; Choy, Jin Ho; Campet, Guy.

In: Chemistry of Materials, Vol. 12, No. 7, 01.01.2000, p. 1818-1826.

Research output: Contribution to journalArticle

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