Acetic anhydride as oxygen donor in the non-hydrolytic sol-gel synthesis of mesoporous TiO2 with high electrochemical lithium storage performances.

An original, halide-free non-hydrolytic sol-gel route to mesoporous anatase TiO2 with hierarchical porosity and high specific surface area is reported. This route is based on the reaction at 200 °C of titanium (IV) isopropoxide with acetic anhydride, in the absence of a catalyst or of a solvent. NMR studies indicated that this method provides an efficient, truly non-hydrolytic and aprotic route to TiO2. Formation of the oxide involves acetoxylation and condensation successive reactions, both with ester elimination. The resulting TiO2 materials were nanocrystalline, even before calcination. Small (≈10 nm) anatase nanocrystals spontaneously aggregated to form mesoporous micron sized particles with high specific surface area (260 m2 g-1 before calcination). Evaluation of the lithium storage performances showed a high reversible specific capacity, particularly for the non-calcined sample with the highest specific surface area favoring pseudo-capacitive storage: 253 mAh g-1 at 0.1C and 218 mAh g-1 at 1C (C = 336 mA g-1). This sample also showed good cyclability (>92% retention after 200 cycles at 336 mA g-1) with a high coulombic efficiency (99.8 %). Synthesis in the presence of a solvent (toluene or squalane) offers the possibility to tune the morphology and texture of the TiO2 nanomaterials.