Exploring the Effect of Cation Vacancies in TiO₂: Lithiation Behavior of n‑Type and p‑Type TiO₂

TiO₂ offers several advantages over graphite as an anode material for Li-ion batteries (LIBs) but suffers from low electrical conductivity and Li-diffusion issues. Control over defect chemistry has proven to be an effective strategy to overcome these issues. However, defect engineering has primarily been focused on oxygen vacancies (V_O). The role of another intrinsic TiO₂ vacancy [i.e., titanium vacancies (V_Ti)] with regard to the Li⁺ storage behavior of TiO₂ has largely evaded attention. Hence, a comparison of V_O- and V_Ti-defective TiO₂ can provide valuable insight into how these two types of defects affect Li⁺ storage behavior. To eliminate other factors that may also affect the Li⁺ storage behavior of TiO₂, we carefully devised synthesis protocols to prepare TiO₂ with either V_O (n-TiO₂) or V_Ti (p-TiO₂). Both TiO₂ materials were verified to have a very similar morphology, surface area, and crystal structure. Although V_O provided additional sites that improved the capacity at low C-rates, the benefit obtained from over-lithiation turned out to be detrimental to cycling stability. Unlike V_O, V_Ti could not serve as an additional lithium reservoir but could significantly improve the rate performance of TiO₂. More importantly, the presence of V_Ti prevented over-lithiation, significantly improving the cycling stability of TiO₂. We believe that these new insights could help guide the development of high-performance TiO₂ for LIB applications.