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Title: Structural, magnetic, and electrochemical properties of LiMn{sub 1−x}Ni{sub x}PO{sub 4}

Highlights: • LiMn{sub 1−x}Ni{sub x}PO{sub 4} nanomaterials were synthesised via a hydrothermal route up to x = 0.45. • Structure and elemental analyses show solid solution behaviour obeying Vegard's law. • Magnetic properties reflect the substitution of Mn{sup 2+} by Ni{sup 2+}. • Mn{sup 2+/3+} reduction potential rises with increasing nickel concentration. - Abstract: A solid solutions series of LiMn{sub 1−x}Ni{sub x}PO{sub 4} nanomaterials with 0 ≤ x ≤ 0.45 was produced by a low-temperature microwave-assisted hydrothermal process. The materials have been systematically studied regarding structure, morphology, magnetism, and electrochemical properties. The lattice parameters in the orthorhombic olivine structure obey Vegard's law and linearly depend on x. Similarly, the static magnetisation reflects the decrease of the transition metal paramagnetic moment upon substitution of Mn{sup 2+} by Ni{sup 2+}. At low temperatures, antiferromagnetic long range order appears for all Ni-concentrations. The potential of the Mn{sup 2+/3+} redox couple is found to linearly increase with x. This is explained by a larger electronegativity of Ni{sup 2+} as compared to Mn{sup 2+} and associated changes in the covalency of the Mn-O bond.
Authors:
 [1] ;  [1] ;  [2] ;  [1] ;  [3]
  1. Kirchhoff Institute for Physics, Heidelberg University, 69120 Heidelberg (Germany)
  2. Institute of Earth Sciences, Heidelberg University, 69120 Heidelberg (Germany)
  3. (Germany)
Publication Date:
OSTI Identifier:
22420821
Resource Type:
Journal Article
Resource Relation:
Journal Name: Materials Research Bulletin; Journal Volume: 63; Other Information: Copyright (c) 2014 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; ANTIFERROMAGNETISM; CONCENTRATION RATIO; COVALENCE; ELECTROCHEMISTRY; ELECTRONEGATIVITY; LATTICE PARAMETERS; LITHIUM COMPOUNDS; MAGNETIC PROPERTIES; MAGNETIZATION; MANGANESE IONS; MANGANESE PHOSPHATES; MICROWAVE RADIATION; NANOMATERIALS; NICKEL COMPOUNDS; NICKEL IONS; ORTHORHOMBIC LATTICES; PARAMAGNETISM; SOLID SOLUTIONS; X-RAY DIFFRACTION