Magnetic structures of the {alpha}-Li{sub 3}Fe{sub 2}(PO{sub 4}){sub 3-} {sub x} (AsO{sub 4}) {sub x} (x=1, 1.5, 2, 3) solid solution
Journal Article
·
· Journal of Solid State Chemistry
- Dpto. Quimica Inorganica, Facultad de Ciencia y Tecnologia, UPV/EHU, Apdo. 644, E-48080 Bilbao (Spain)
- Dpto. de Mineralogia y Petrologia, Facultad de Ciencia y Tecnologia, UPV/EHU, Apdo. 644, E-48080 Bilbao (Spain)
- Institut de Chimie de la Matiere Condensee de Bordeaux (ICMCB-CNRS), 33608 Pessac Cedex (France)
Moessbauer spectroscopy and neutron diffraction studies have been carried out for the {alpha}-Li{sub 3}Fe{sub 2}(PO{sub 4}){sub 3-} {sub x} (AsO{sub 4}) {sub x} (x=1, 1.5, 2, 3) solid solution, potential candidate for the cathode material of the lithium secondary batteries. The crystal and magnetic structures of all these phases are based on the structural and magnetic model corresponding to the {alpha}-Li{sub 3}Fe{sub 2}(PO{sub 4}){sub 3} phosphate parent, but with some differences promoted by the arsenate substitution. The PO{sub 4} and AsO{sub 4} groups have a random distribution in the structure. In all compounds the coupling of the magnetic moments takes place in the (001) plane, but the value of the angle between the moments and the x direction decreases from 38.3 deg. ({alpha}-Li{sub 3}Fe{sub 2}(AsO{sub 4}){sub 3}) to 4.7{sup o} ({alpha}-Li{sub 3}Fe{sub 2}(PO{sub 4}){sub 2}(AsO{sub 4}){sub 1}). This rotation arises from the change in the tilt angle between the Fe(1)O{sub 6} and Fe(2)O{sub 6} crystallographically and magnetically independent octahedra in the structures, and affects the effectiveness of the magnetic exchange pathways. The ordering temperature T{sub N} decreases with the increase of phosphate amount in the compounds. The existence of a phenomenon of canting and the evolution of the ferrimagnetic behavior in this solid solution is also discussed.
- OSTI ID:
- 20784834
- Journal Information:
- Journal of Solid State Chemistry, Journal Name: Journal of Solid State Chemistry Journal Issue: 1 Vol. 179; ISSN 0022-4596; ISSN JSSCBI
- Country of Publication:
- United States
- Language:
- English
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