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Crystallographic structure of LiFe1−x Mnx PO4 solid solutions studied by neutron powder diffraction

Published online by Cambridge University Press:  11 March 2014

X.Y. Li ,
B. Zhang ,
Z.G. Zhang ,
L.H. He ,
H. Li ,
X.J. Huang  and
F.W. Wang
X.Y. Li
Affiliation:
Beijing National Laboratory for Condensed Matter Physics, Institute of Physics, Chinese Academy of Sciences, Beijing 100190, China
B. Zhang
Affiliation:
Beijing National Laboratory for Condensed Matter Physics, Institute of Physics, Chinese Academy of Sciences, Beijing 100190, China
Z.G. Zhang
Affiliation:
Beijing National Laboratory for Condensed Matter Physics, Institute of Physics, Chinese Academy of Sciences, Beijing 100190, China
L.H. He
Affiliation:
Beijing National Laboratory for Condensed Matter Physics, Institute of Physics, Chinese Academy of Sciences, Beijing 100190, China
H. Li
Affiliation:
Beijing National Laboratory for Condensed Matter Physics, Institute of Physics, Chinese Academy of Sciences, Beijing 100190, China
X.J. Huang
Affiliation:
Beijing National Laboratory for Condensed Matter Physics, Institute of Physics, Chinese Academy of Sciences, Beijing 100190, China
F.W. Wang*
Affiliation:
Beijing National Laboratory for Condensed Matter Physics, Institute of Physics, Chinese Academy of Sciences, Beijing 100190, China
*
a) Author to whom correspondence should be addressed. Electronic mail: fwwang@aphy.iphy.ac.cn
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Abstract

High-resolution neutron powder diffraction (NPD) data were recorded on a series of cathode material LiFe1−x Mnx PO4 (x = 0, 0.2, 0.5, 0.8, and 1.0) solid solutions using the HRPD machine at SINQ/PSI, Switzerland. Ab initio crystal structure solution via program FOX indicates demonstrably that the space group of LiFePO4 is Pnma with Li1+ occupying octahedral (4a) sites and Fe2+ octahedral (4c) sites, respectively, in the olivine structure. Rietveld refinement (program FullProf suite version July-2011), complementary with X-ray diffraction data, shows that Fe2+ may partially (about 2%) distribute over Li1+ sites. NPD data for LiFe1−x Mnx PO4 (x = 0, 0.2, 0.5, 0.8, and 1.0) reveal that the Mn2+ replaces Fe2+ at the octahedral (4c) sites. The cell parameters a, b, and c increase linearly and the interatomic distances (in Å) of Li–O(2) and Li–O(1) increase, while the interatomic distances (in Å) of Li–O(3) decrease on the addition of Mn, respectively, partially explaining a higher potential plateau of ~4.1 eV in LiMnPO4 compared to ~3.5 eV in LiFePO4.

Keywords

LiFe1−x Mnx PO4 compoundsneutron diffractionab initio82.47.Aa61.05.fm31.15.A-

Information

Type
Technical Articles
Information
Powder Diffraction , Volume 29 , Issue 3 , September 2014 , pp. 248 - 253
Copyright
Copyright © International Centre for Diffraction Data 2014 

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