In Situ Raman Spectroscopy of Li⁺ and Na⁺ Storage in Anodic TiO₂ Nanotubes: Implications for Battery Design

Abstract

Anodizing is a powerful method to form electrochemically active materials, among which self-organized TiO 2 nanotubes (TiNTs) are of high interest in the battery field due to a unique one-dimensional (1D) geometry offering high volume expansion tolerance and applications without binders and conductive additives. Herein, we report in situ Raman spectroscopy study under current control for a better fundamental understanding of Li + /Na + storage in TiNTs and correlate the structural fingerprints with the electrochemical data on differential capacity plots of d(Q−Q 0 ) dE −1 . Real-time measurements revealed that the nanotubes had undergone two major phase transformations with increasing lithium content, disclosing the sequential steps of a lithium intercalation type of storage. In contrast, sodium-ion insertion induced no significant crystal structure modification but instead a slight crystallinity rupture, signifying a dominant nondiffusion-limited capacitive type of storage. The insight into the charge storage in a 1D material is mandatory for further scale-up of the nanotubes formation and their application as negative electrodes in a lithium-ion battery.

Lithiation of Anodic Magnetite–Hematite Nanotubes Formed on Iron

“…One-dimensional (1D)-type nanotubular structures synthesized by anodization have attracted wide attention in recent years due to well-defined control over the oxide geometry. – 1D-type structures, such as nanotubes, have many advantages over the classic nanoparticulate electrodes composed of randomly distributed three-dimensional (3D)-type spheres; for example, the specific architecture facilitates an excellent charge transport pathway along the z -axis of nanotube impart enormous electrochemical volume expansion tolerance . The tubular design is expected to lower diffusion length and let faster ion kinetics that eventually enhance the rate capability .…”