Raman spectroscopic study of the phase transitions sequence in Li3Fe2(PO4)3 and Na3Fe2(PO4)3 at high temperature

The phase transition properties of A(3)Fe(2)(PO4)(3) (A = Li, Na) were studied by Raman spectroscopy. Several Raman bands change continuously in 25-400 degrees C temperature range, indicating a phase transition from the gamma, beta to the alpha-phase occurring at this range of temperature. Bands caused by vibrations of phosphate anion and different ions have been found. The spectra analysis reveals that the modes, located at low frequency range 100-400 cm(-1), near 500 cm(-1) at room temperature, are the most thermo-sensitive. In addition, the modes corresponding to bond valence stretching of (PO4) unit in the frequency region 970-1200 cm(-1) show also evolution with temperature but less sensitive than the above ones. It is observed that phosphate groups show some ordering with temperature. According to our Raman study, we can state that each of the compounds LiFeP and NaFeP shows two reversible phase transformations in the temperature range studied. (C) 2009 Elsevier B.V. All rights reserved.