Neutron structural characterization, inversion degree and transport properties of NiMn2O4 spinel prepared by the hydroxide route

The title compound has been synthesized by the hydroxide route. The crystal structure has been investigated at room temperature from high-resolution neutron powder diffraction. (NPD) data. It crystallizes in a cubic spinel structure, space group Fd (3) over barm, Z = 8, with a = 8.3940(2) angstrom at 295 K. The crystallographic formula is (Ni0.202(1)Mn0.798(1))(8a)(Ni0.790(1)Mn1.210(1))(16d)O-4 where 8a and 16d stand for the tetrahedral and octahedral sites of the spinel structure, respectively. There is a significant inversion degree of the spinel structure, lambda = 0.80. In fact, the variable parameter for the oxygen position, u = 0.2636(4), is far from that expected (u = 0.25) for normal spinels. From a bond-valence study, it seems that the valence distribution in NiMn2O4 spinal is not as trivial as expected (Ni2+ and Mn3+), but clearly the tetrahedral Mn ions are divalent whereas the octahedral Mn and Ni are slightly oxidized from the expected +3 and +2 values, respectively. The mixed valence observed at the octahedral sites provides the charge carriers that, by a hopping mechanism between Mn3+/Mn4+ adjacent sites, leads to a significant conductivity, up to 0.85 S cm(-1) at 800 degrees C in air. (C) 2012 Elsevier Ltd. All rights reserved.