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Sudden Olivine LiFePO4 Nanocrystallisation by Progressive Introduction of Li into Ferrous Phosphate Structure

Published online by Cambridge University Press:  01 February 2011

Y. Sundarayya ,
K.C. Kumaraswamy  and
C. S. Sunandana
Y. Sundarayya
Affiliation:
csssp@uohyd.ernet.in, University of Hyderabad, Physics, School of Physics, Central University P.O., Hyderabad - 500046, Andhra Pradesh, INDIA, Hyderabad, N/A, India, 914023134324
K.C. Kumaraswamy
Affiliation:
kckssc@uohyd.ernet.in, University of Hyderabad, School of Chemistry, Central University P.O.,, Hyderabad, 500 046, India
C. S. Sunandana
Affiliation:
csssp@uohyd.ernet.in, University of Hyderabad, School of Physics, Central University P.O., Hyderabad, 500 046, India
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Abstract

Homogeneous sub-micron sized particles of surface carbon coated phase pure LiFePO4 are synthesized by a novel non-aqueous oxalate-based sol-gel route. X-ray diffractogram of LiFePO4 reveals nanocrystals with average crystallite size 32(7) nm. The very large QS (nearly five times greater than that of Fe3+) value observed from Mossbauer spectrum is due to high spin configuration of 3d electrons and the asymmetric local environment at Fe site in LiFePO4. A uniform particle size distribution with grain size 100 - 150nm was observed in SEM with few irregular growths. Our synthetic route successfully overcomes the incidence of Fe3+, effectively controls undesirable particle growth and has the potential for upscaling and application as Li-ion battery cathodes. Progressive evolution of olivine structure by the interlock of FeO6 octahedra and PO4 tetrahedra with Li concentration is studied by introducing lithium in to LixFePO4 (0.0 × 1.0 ). A fairly abrupt phase transformation from monoclinic Fe3(PO4)2 to orthorhombic LiFePO4 shows up for x∼0.2 accompanied by structural disorder which gets stabilized at x 0.35. A systematic study of X-ray diffractograms shows nanocrystal nucleation and growth from an unstable low symmetry crystalline phase with considerable disorder.

Keywords

LiFeionic conductor
Type
Research Article
Information
MRS Online Proceedings Library (OPL) , Volume 1023: Symposium JJ – Functional Nanoscale Ceramics for Energy Systems , 2007 , 1023-JJ03-06
Copyright
Copyright © Materials Research Society 2007

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