Direct Evidence of Lithium-Induced Atomic Ordering in Amorphous TiO2 Nanotubes

In this paper, we report the first direct chemical and imaging evidence of lithium-induced atomic ordering in amorphous TiO 2 nanomaterials and propose new reaction mechanisms that contradict the many works in the published literature on the lithiation behavior of these materials. The lithiation process was conducted in situ inside an atomic resolution transmission electron microscope. Our results indicate that the lithiation started with the valence reduction of Ti 4+ to Ti 3+ leading to a Li x TiO 2 intercalation compound. The continued intercalation of Li ions in TiO 2 nanotubes triggered an amorphous to crystalline phase transformation. The crystals were formed as nano-islands and identified to be Li 2 Ti 2 O 4 with cubic structure ( a = 8.375 Å). The tendency for the formation of these crystals was verified with density functional theory (DFT) simulations. The size of the crystalline islands provides a characteristic length scale (∼5 nm) at which the atomic bonding configuration has been changed within a short time period. This phase transformation is associated with local inhomogeneities in Li distribution. On the basis of these observations, a new reaction mechanism is proposed to explain the first cycle lithiation behavior in amorphous TiO 2 nanotubes.