GeO₂ Thin Film Deposition on Graphene Oxide by the Hydrogen Peroxide Route: Evaluation for Lithium-Ion Battery Anode

A peroxogermanate thin film was deposited in high yield at room temperature on graphene oxide (GO) from peroxogermanate sols. The deposition of the peroxo-precursor onto GO and the transformations to amorphous GeO₂, crystalline tetragonal GeO₂, and then to cubic elemental germanium were followed by electron microscopy, XRD, and XPS. All of these transformations are influenced by the GO support. The initial deposition is explained in view of the sol composition and the presence of GO, and the different thermal transformations are explained by reactions with the graphene support acting as a reducing agent. As a test case, the evaluation of the different materials as lithium ion battery anodes was carried out revealing that the best performance is obtained by amorphous germanium oxide@GO with >1000 mAh g^-1 at 250 mA g^-1 (between 0 and 2.5 V vs Li/Li⁺ cathode), despite the fact that the material contained only 51 wt % germanium. This is the first demonstration of the peroxide route to produce peroxogermanate thin films and thereby supported germanium and germanium oxide coatings. The advantages of the process over alternative methodologies are discussed.