High Substitution Rate in TiO₂ Anatase Nanoparticles with Cationic Vacancies for Fast Lithium Storage

Doping is generally used to tune and enhance the properties of metal oxides. However, their chemical composition cannot be readily modified beyond low dopant amounts without disrupting the crystalline atomic structure. In the case of anatase TiO₂, we introduce a new solution-based chemical route allowing the composition to be significantly modified, substituting the divalent O^2- anions by monovalent F^- and OH^- anions resulting in the formation of cationic Ti⁴⁺ vacancies (-) whose concentration can be controlled by the reaction temperature. The resulting polyanionic anatase has the general composition Ti_1-x-y-_x+yO_2-4(x+y)F_4x(OH)_4y, reaching vacancy concentrations of up to 22%, i.e., Ti_0.78-_0.22O_1.12F_0.4(OH)_0.48. Solid-state ¹⁹F NMR spectroscopy reveals that fluoride ions can accommodate up to three different environments, depending on Ti and vacancies (i.e. Ti₃-F, Ti₂-₁-F, and Ti₁-₂-F), with a preferential location close to vacancies. DFT calculations further confirm the fluoride/vacancy ordering. When its characteristics were evaluated as an electrode for reversible Li-ion storage, the material shows a modified lithium reaction mechanism, which has been rationalized by the occurrence of cationic vacancies acting as additional lithium hosting sites within the anatase framework. Finally, the material shows a fast discharging/charging behavior, compared to TiO₂, highlighting the benefits of the structural modifications and paving the way for the design of advanced electrode materials, based on a defect mediated mechanism.