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Magnetic Properties of Phospho-Olivine Li(Fe _{1-x} Mn _{x} )PO _{4} Investigated With Mössbauer Spectroscopy

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3 Author(s)
In Kyu Lee ; Dept. of Phys., Kookmin Univ., Seoul, South Korea ; Kim, Sam Jin ; Chul Sung Kim

The crystalline structure of the Li(Fe1-xMnx)PO4 (x = 0.0, 0.2) samples was determined to be olivine-type orthorhombic with Pnma space group. The contraction ofunit cell volume from LiFe0.8Mn0.2PO4 (V = 293.296 Å3) to LiFePO4 (V = 291.445 Å3) can be explained by the different ionic radii of high-spin Fe2+ and Mn2+. The temperature-dependent magnetic susceptibility and Curie-Weiss fitted reciprocal susceptibility curves of Li(Fe1-xMnx)PO4 indicates that there are antiferromagnetic ordering with different values of magnetic Neel temperature and effective moment between LiFe0.8Mn0.2PO4 (TN = 49 K, μeff = 5.66μB) and LiFePO4 (TN = 51 K, μeff = 5.37 μB). From the Mossbauer analysis, The distribution of the Mn2+ (3d5) ions in M2 magnetic sites can lead to the reduction of magnetic hyperfine field (Hhf) of LiFe0.8Mn0.2PO4 in Fe2+ (3d6) sites. Also, the isomer shift (δ) and electric quadrupole splitting (ΔEQ) values, increasing with Mn2+ substitution, can be attributed to the decrease of charge density at Fe nucleus ρA (0) due to the 3d-electron penetrating closer to the Fe nucleus with asymmetric charge distribution by the presence of Mn2+ ions on the FeO6 octahedral sites.

Published in:

Magnetics, IEEE Transactions on  (Volume:48 ,  Issue: 4 )

Date of Publication:

April 2012

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