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Title: Magnetic structures of β{sub I}-Li{sub 2}CoSiO{sub 4} and γ{sub 0}-Li{sub 2}MnSiO{sub 4}: Crystal structure type vs. magnetic topology

The magnetic structure and properties of the candidate lithium-ion battery cathode materials Pbn2{sub 1}(≡Pna2{sub 1}) Li{sub 2}CoSiO{sub 4} and P2{sub 1}/n Li{sub 2}MnSiO{sub 4} have been studied experimentally using low-temperature neutron powder diffraction and magnetometry. Both materials undergo long-range antiferromagnetic ordering, at 14 K and 12 K respectively, due to super–super-exchange mediated by bridging silicate groups. Despite having different crystal structures (wurtzite- vs. “dipolar”-type), Li{sub 2}CoSiO{sub 4} and Li{sub 2}MnSiO{sub 4} have the same topology in terms of magnetic interactions, and adopt collinear magnetic structures of the same type with the propagation vectors (0, 1/2, 1/2) and (1/2, 0, 1/2), respectively. The magnetic moments in the two materials are aligned in parallel and obliquely to the distorted closed-packed layers of oxygen atoms. The experimentally observed values of the ordered magnetic moments, 2.9 μ{sub B} and 4.6 μ{sub B}, are close to those expected for d{sup 7} Co{sup 2+} and d{sup 5} Mn{sup 2+}, respectively. - Graphical abstract: Despite the different crystal structures β{sub I}-Li{sub 2}CoSiO{sub 4} and γ{sub 0}-Li{sub 2}MnSiO{sub 4} have similar magnetic topology and as a result adopt magnetic structure of the same type. - Highlights: • Magnetic structures of Li{sub 2}CoSiO{sub 4} and Li{sub 2}MnSiO{sub 4} weremore » studied for the first time. • Both materials antiferromagnetically order around 12–14 K. • Despite different crystal structure magnetic structures are of the same type. • The fact is attributed to similar topology of magnetic interactions.« less
Authors:
 [1] ;  [2] ;  [3] ;  [2]
  1. Bragg Institute, Australian Nuclear Science and Technology Organisation, Lucas Heights, NSW 2234 (Australia)
  2. School of Chemistry, The University of Sydney, Sydney, NSW 2006 (Australia)
  3. (Malaysia)
Publication Date:
OSTI Identifier:
22443369
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Solid State Chemistry; Journal Volume: 216; 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:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ANTIFERROMAGNETISM; ATOMIC FORCE MICROSCOPY; CATHODES; COBALT IONS; INTERACTIONS; LITHIUM; LITHIUM ION BATTERIES; MAGNETIC MOMENTS; MAGNETIC PROPERTIES; MANGANESE IONS; MONOCLINIC LATTICES; NEUTRON DIFFRACTION; ORTHORHOMBIC LATTICES; OXYGEN; SILICATES