Structural disorder along the lithium diffusion pathway in cubically stabilized lithium manganese spinel II. Molecular dynamics calculation

Kenji Tateishi, Douglas Du Boulay, Nobuo Ishizawa, Katsuyuki Kawamura

Research output: Contribution to journalArticle

24 Citations (Scopus)

Abstract

Molecular dynamics (MD) simulations were carried out to investigate the local structural disorder in LiMn2O4 spinel. Small but significant shifts of lithium and oxygen atom positions from the high symmetry sites of the Fd3̄m lattice were observed. The lithium atoms are displaced approximately 0.16Å away from 8a site of the Fd3̄m lattice and are shifted along the diffusion pathway towards the face midpoints of the coordinating LiO4 tetrahedra. A diffuse population of Li atoms was also detected centered about 0.38Å away from the 16c octahedral vacancy, suggesting a portion of the Li atoms are free from their tetrahedral cages at room temperature. The tetrahedrally coordinated O atoms are displaced by as much as 0.12Å when bonded to one Li and three Mn atoms in identical oxidation states. On the other hand, if the coordinating Mn atoms are in mixed oxidation states, much larger O atom shifts of 0.22Å are observed. Structural features obtained in this MD simulation, especially the off-center displacements of Li and O atoms, are in accord with the electron density distribution study of cubically stabilized Mg-doped LiMn2O4 spinel reported in Part I.

Original languageEnglish
Pages (from-to)175-181
Number of pages7
JournalJournal of Solid State Chemistry
Volume174
Issue number1
DOIs
Publication statusPublished - Aug 2003
Externally publishedYes

Fingerprint

Manganese
Lithium
spinel
Molecular dynamics
manganese
lithium
disorders
molecular dynamics
Atoms
atoms
spinell
Oxidation
oxidation
Electronic density of states
shift
Computer simulation
tetrahedrons
Vacancies
density distribution
oxygen atoms

Keywords

  • LiMnO
  • Lithium diffusion pathway
  • Lithium manganese spinel
  • Molecular dynamics simulations
  • Structural disorder

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Physical and Theoretical Chemistry
  • Materials Chemistry

Cite this

Structural disorder along the lithium diffusion pathway in cubically stabilized lithium manganese spinel II. Molecular dynamics calculation. / Tateishi, Kenji; Du Boulay, Douglas; Ishizawa, Nobuo; Kawamura, Katsuyuki.

In: Journal of Solid State Chemistry, Vol. 174, No. 1, 08.2003, p. 175-181.

Research output: Contribution to journalArticle

Tateishi, Kenji ; Du Boulay, Douglas ; Ishizawa, Nobuo ; Kawamura, Katsuyuki. / Structural disorder along the lithium diffusion pathway in cubically stabilized lithium manganese spinel II. Molecular dynamics calculation. In: Journal of Solid State Chemistry. 2003 ; Vol. 174, No. 1. pp. 175-181.
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abstract = "Molecular dynamics (MD) simulations were carried out to investigate the local structural disorder in LiMn2O4 spinel. Small but significant shifts of lithium and oxygen atom positions from the high symmetry sites of the Fd3̄m lattice were observed. The lithium atoms are displaced approximately 0.16{\AA} away from 8a site of the Fd3̄m lattice and are shifted along the diffusion pathway towards the face midpoints of the coordinating LiO4 tetrahedra. A diffuse population of Li atoms was also detected centered about 0.38{\AA} away from the 16c octahedral vacancy, suggesting a portion of the Li atoms are free from their tetrahedral cages at room temperature. The tetrahedrally coordinated O atoms are displaced by as much as 0.12{\AA} when bonded to one Li and three Mn atoms in identical oxidation states. On the other hand, if the coordinating Mn atoms are in mixed oxidation states, much larger O atom shifts of 0.22{\AA} are observed. Structural features obtained in this MD simulation, especially the off-center displacements of Li and O atoms, are in accord with the electron density distribution study of cubically stabilized Mg-doped LiMn2O4 spinel reported in Part I.",
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AB - Molecular dynamics (MD) simulations were carried out to investigate the local structural disorder in LiMn2O4 spinel. Small but significant shifts of lithium and oxygen atom positions from the high symmetry sites of the Fd3̄m lattice were observed. The lithium atoms are displaced approximately 0.16Å away from 8a site of the Fd3̄m lattice and are shifted along the diffusion pathway towards the face midpoints of the coordinating LiO4 tetrahedra. A diffuse population of Li atoms was also detected centered about 0.38Å away from the 16c octahedral vacancy, suggesting a portion of the Li atoms are free from their tetrahedral cages at room temperature. The tetrahedrally coordinated O atoms are displaced by as much as 0.12Å when bonded to one Li and three Mn atoms in identical oxidation states. On the other hand, if the coordinating Mn atoms are in mixed oxidation states, much larger O atom shifts of 0.22Å are observed. Structural features obtained in this MD simulation, especially the off-center displacements of Li and O atoms, are in accord with the electron density distribution study of cubically stabilized Mg-doped LiMn2O4 spinel reported in Part I.

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