Unique Ordered TiO 2 Superstructures with Tunable Morphology and Crystalline Phase for Improved Lithium Storage Properties

Unique ordered TiO 2 superstructures with tunable morphology and crystalline phase were successfully prepared by the use of different counterions. Dumbbell‐shaped rutile TiO 2 and nanorod‐like rutile mesocrystals constructed from ultrathin nanowires, and quasi‐octahedral anatase TiO 2 mesocrystals built from tiny nanoparticle subunits were achieved. Interestingly, the obtained anatase mesocrystals have a fine microporous structure and a large surface area. The influence of the counterions in the reaction system is discussed and possible mechanisms responsible for the formation of the unique ordered TiO 2 superstructures with different morphologies and crystalline phases are also proposed based on a series of experimental results. The obtained TiO 2 superstructures were used as anode materials in lithium ion batteries, and exhibited higher capacity and improved rate performance; this is attributed to the intrinsic characteristics of the mesoscopic TiO 2 superstructures, which have a single‐crystal‐like and porous nature.