Résumé
Fluoride-based materials have regained interest within the field of Li-ion batteries largely due to the advent of nanosizing which has transformed the insulating insertion compounds into attractive electrode materials. Herein we demonstrate the effectiveness of ionothermal synthesis in the preparation of nanometric LiFePO4F and LiTiPO4F phases with structures isotopic to tavorite LiFePO4(OH) at temperatures of only 260 °C, while temperatures of 600−700 °C are required to obtain coarse powders via the ceramic method. However, the redox-active phases, which are obtained in a high state of division, have lower redox voltages than LiFePO4 despite the presence of fluorine. Additionally, LiTiPO4F shows staircase charge/discharge profiles with Ti2/3+ and Ti3/4+ couples. Though quite unusual in lithium intercalation oxides, a hint of a Li-driven Fe3/4+ transition has been detected in LiFePO4F.