Disorder in LixFePO4: From glasses to nanocrystallites

Abstract

LixFePO4 glasses have been prepared by fast-quenching method in the whole range of composition 0⩽ x ⩽1. The amorphous state of glassy materials is confirmed by X-ray diffraction. Information concerning the local environment of Li and Fe cations and the configuration of (PO4)3− oxo-anions is obtained by Fourier transform infrared (FTIR) spectroscopy. While the LiFePO4 crystalline materials undergo a transition from the paramagnetic to the antiferromagnetic ordering at 52K, no magnetic ordering is observed in the vitreous samples that realize random field systems, so that a spin glass-like freezing is observed at low temperature. The paramagnetic Curie temperature of LixFePO4 is independent of x and shifted to θ=−60K in the glassy state, due to a significant distortion of the FeO6 octahedra that alters the superexchange path inside the atomic FeO4 layers of the crystallized structure. On another hand, the PO4 tetrahedra are not significantly distorted in the glassy phase. The results are compared with highly disordered, but nanocrystallized LiFePO4 recently obtained at the early stage of synthesis by solid state reaction at 300°C. In this latter case, the lack of long-range antiferromagnetic ordering is due to substitutional disorder among the cationic sublattice.