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Title: Neutron structural characterization, inversion degree and transport properties of NiMn{sub 2}O{sub 4} spinel prepared by the hydroxide route

Graphical abstract: A pure specimen has been synthesized by the hydroxide route. This spinel, studied by NPD, shows an important inversion degree, λ = 0.80. A bond-valence study shows that 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 Mn{sup 3+}/Mn{sup 4+} accounts for a hopping mechanism between adjacent octahedral sites, leading to a significant conductivity. Highlights: ► A low-temperature hydroxide route allowed preparing almost pure specimens of NiMn{sub 2}O{sub 4}. ► NPD essential to determine inversion degree; contrasting Ni and Mn for neutrons. ► Bond valence establishes valence state of octahedral and tetrahedral Ni and Mn ions. ► Thermal analysis, transport measurements complement characterization of this oxide. ► A structure–properties relationship is established. -- Abstract: 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 Fd3{sup ¯}m, Z = 8, with a = 8.3940(2) Å at 295 K. The crystallographic formula is (Ni{sub 0.202(1)}Mn{sub 0.798(1)}){sub 8a}(Ni{sub 0.790(1)}Mn{sub 1.210(1)}){sub 16d}O{sub 4} where 8a and 16d stand for themore » tetrahedral and octahedral sites of the spinel structure, respectively. There is a significant inversion degree of the spinel structure, λ = 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 NiMn{sub 2}O{sub 4} spinel is not as trivial as expected (Ni{sup 2+} and Mn{sup 3+}), 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 Mn{sup 3+}/Mn{sup 4+} adjacent sites, leads to a significant conductivity, up to 0.85 S cm{sup −1} at 800 °C in air.« less
Authors:
;  [1] ;  [2] ;  [2] ;  [3] ;  [4]
  1. Departamento de Química, Laboratorio de Fisicoquímica Inorgánica, Universidad Nacional del Sur, INQUISUR, 8000 Bahía Blanca (Argentina)
  2. Instituto de Ciencia de Materiales de Madrid, C.S.I.C., Cantoblanco, E-28049 Madrid (Spain)
  3. Institut Laue Langevin, BP 156X, Grenoble F-38042 (France)
  4. Departamento de Química Inorgánica, Facultad de Ciencias Químicas, Universidad Complutense, 28040 Madrid (Spain)
Publication Date:
OSTI Identifier:
22215099
Resource Type:
Journal Article
Resource Relation:
Journal Name: Materials Research Bulletin; Journal Volume: 47; Journal Issue: 6; Other Information: Copyright (c) 2012 Elsevier Science B.V., Amsterdam, The Netherlands, All rights reserved.; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; CRYSTALLOGRAPHY; CUBIC LATTICES; ELECTRICAL PROPERTIES; HYDROXIDES; MANGANESE IONS; NEUTRON DIFFRACTION; NEUTRONS; SPACE GROUPS; SPINELS; THERMAL ANALYSIS