TiO2 Microboxes with Controlled Internal Porosity for High‐Performance Lithium Storage

Titanium dioxide (TiO₂) is considered a promising anode material for high‐power lithium ion batteries (LIBs) because of its low cost, high thermal/chemical stability, and good safety performance without solid electrolyte interface formation. However, the poor electronic conductivity and low lithium ion diffusivity of TiO₂ result in poor cyclability and lithium ion depletion at high current rates, which hinder them from practical applications. Herein we demonstrate that hierarchically structured TiO₂ microboxes with controlled internal porosity can address the aforementioned problems for high‐power, long‐life LIB anodes. A self‐templating method for the synthesis of mesoporous microboxes was developed through Na₂EDTA‐assisted ion exchange of CaTiO₃ microcubes. The resulting TiO₂ nanorods were organized into microboxes that resemble the microcube precursors. This nanostructured TiO₂ material has superior lithium storage properties with a capacity of 187 mAh g^?1 after 300 cycles at 1 C and good rate capabilities up to 20 C.