A template-free sol–gel method for the synthesis of hierarchically nano-structured lithium-titanium-oxide films is proposed involving a p-type doping of titanium isopropoxide sols with lithium. The structures of the films are analyzed by scanning electron microscopy, X-ray powder diffraction and Raman spectroscopy. Different phases can be accessed by controlling the annealing temperature. Supersaturated anatase (Ti, Li)O2 is formed at 400 °C, whereas anatase and/or rutile interspersed with Li2TiO3 and Li4Ti5O12 are observed between 450 °C and 800 °C. The nanostructure formation is explained by a dissolution–crystallization–self-assembly mechanism.
