Abstract
AbstractThe local structure and electronic states of Co3+ substituted lithium manganate spinels of the composition Li(Mn2‐xCox)O4 (0 ≤ x ≤ 0.4) have been probed by X‐ray absorption near‐edge structure (XANES) and extended X‐ray absorption fine structure (EXAFS) spectroscopies at the Mn and Co edges. The substitution of Co3+ into the Mn sites causes an oxidation of Mn3+ to Mn4+, decreasing the localized Jahn‐Teller distortion of the lattice. This in turn leads to a shortening of the Mn‐O(M) bond length and a reduction in local structural disorder of the Mn(Co)O6 octahedra. The data show that the replacement of d4 Mn3+ by d6 Co3+ in the octahedral sites of the spinel structure eliminates the local disorder in the lattice around the Mn3+O6 octahedra which are distorted by Jahn‐Teller stabilization of the electronic state.
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