<i>In Situ</i> Raman Spectroscopy of Li<sup>+</sup> and Na<sup>+</sup> Storage in Anodic TiO<sub>2</sub> Nanotubes: Implications for Battery Design
Mewin Vincent, Damian Kowalski
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 ) d E –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.