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Lattice dynamics and vibrational spectra of lithium manganese oxides: A computer simulation and spectroscopic study

Journal Article · · Journal of Physical Chemistry B: Materials, Surfaces, Interfaces, amp Biophysical
DOI:https://doi.org/10.1021/jp984398l· OSTI ID:682094
 [1];  [2];  [3];  [4];  [5]
  1. Univ. Montpellier 2 (France). Lab. des Agregats Moleculaires et Materiaux Inorganiques
  2. Victoria Univ. of Wellington (New Zealand). School of Chemical and Physical Sciences
  3. Univ. of Surrey, Guildford (United Kingdom). Dept. of Chemistry
  4. Shikoku National Industrial Research Inst., Takamatsu (Japan)
  5. Univ. Montpellier 2 (France). Lab des Agregats Moleculaires et Materiaux Inorganiques

The lattice vibrational modes of spinel-structured lithium manganese oxides have been calculated using atomistic modeling methods. The simulations allow the Raman and infrared spectra of lithiated, fully delithiated, and partially delithiated phases to be assigned for the first time. Calculations for the spinels LiMn{sub 2}O{sub 4}, {lambda}-MnO{sub 2}, and Li{sub 0.5}Mn{sub 2}O{sub 4} are compared with experimental Raman data measured for thin films of the oxides coated on a platinum electrode. The appearance of a number of new bands in the Raman spectrum of LiMn{sub 2}O{sub 4} following partial extraction of lithium is shown to result from local lowering of the symmetry and Raman activation of modes which are optically inactive or only infrared active in LiMn{sub 2}O{sub 4}. The results support a model for the Li{sub 0.5}Mn{sub 2}O{sub 4} lattice in which the lithium ions are ordered. The deformation vibrations of lattice hydroxyl defects in {lambda}-MnO{sub 2} have also been calculated; comparison of the calculated and experimental vibrational data supports a model in which hydroxyl species are localized at octahedral Mn vacancies.

OSTI ID:
682094
Journal Information:
Journal of Physical Chemistry B: Materials, Surfaces, Interfaces, amp Biophysical, Journal Name: Journal of Physical Chemistry B: Materials, Surfaces, Interfaces, amp Biophysical Journal Issue: 25 Vol. 103; ISSN 1089-5647; ISSN JPCBFK
Country of Publication:
United States
Language:
English

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