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Cation Ordering in Substituted LiMn2O4 Spinels

Published online by Cambridge University Press:  11 February 2011

P. Strobel,
A. Ibarra-Palos and
C. Poinsignon
P. Strobel
Affiliation:
Laboratoire de Cristallographie CNRS, BP 166, 38042 Grenoble Cedex 9, France
A. Ibarra-Palos
Affiliation:
Laboratoire de Cristallographie CNRS, BP 166, 38042 Grenoble Cedex 9, France
C. Poinsignon
Affiliation:
LEPMI, ENSEEG, BP 75, 38402 Saint-Martin d'Hères Cedex, France
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Abstract

In order to overcome the capacity fading of LiMn2O4 in lithium batteries, various substitutions for Mn have been proposed. The structural implications of substitution in LiMn2-xMxO4 with x = 0.5, i.e. with exactly 1/4 octahedral (16d-site) cations replaced, are investigated here. For this stoichiometry, cationic ordering was known previously for M = Mg and Zn, resulting in a superstructure with primitive cubic symmetry. Given the poor chemical contrast of X-ray diffraction between Mn and Co, Ni or Cu, LiMn1.5M0.5O4 samples were studied by neutron diffraction and IR spectroscopy. Both techniques show the occurence of cationic ordering for M = Ni and Cu, but not for Co or Ga. In the case of M = Zn, further complication due Li/Zn ordering on the tetrahedral (8a) site is well resolved by FTIR. This investigation shows that the main driving force for octahedral cation ordering is the charge difference between Mn and M atoms.

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