Facile Synthesis of Ge@TiO₂ Nanotube Hybrid Nanostructure Anode Materials for Li-Ion Batteries

Utilizing nanostructures of Li-alloying anode materials (e.g., Si, Ge, Sn, etc.) has been proposed as a key strategy to improve the electrochemical performance. However, the main challenge lies in the costly and complex nanostructure synthesis processes. Notably, the nanostructure growth processes are mainly supported by Li-inactive templates, which later need to be removed, and the template removal process results in the destruction of the desired nanostructures. In this report, we demonstrated the use of a Li-active, self-organized TiO₂ nanotube template to fabricate germanium (Ge)-based nanostructured anodes. This has been achieved as follows: first, TiO₂ nanotubes are fabricated via electrochemical anodization of titanium foil. Then, the nanotubes are coated with a Ge film in the second step via electrodeposition. Besides the effective nanostructure growth using a Li-active template, the implemented electrochemical synthesis methods are cost-effective, accessible, and scalable. Furthermore, the electrochemical methods allow the fabrication of nanostructures with well-controlled structures, morphology, and compositions. Accordingly, a Ge-coated TiO₂ nanotube (Ge@TiO₂) nanocomposite anode has been successfully fabricated, and its electrochemical performance has been tested for Li-ion batteries. The study has shown the important roles of TiO₂ nanotube arrays in improving the performance by providing strong mechanical support to buffer the volume expansion and offering a high surface area to enhance Ge-active mass loading. Moreover, the direct contact of the nanotubes with a Ti current collector facilitates one-dimensional (1D) electron transport and avoids the need of adding inactive binders or conductive additives.