TiO2 has drawn increasing research attention as negative electrode material in sodium ion battery because of its natural abundance, low cost, nontoxicity, and facile preparation. Despite tremendous studies carried out, the sodium storage mechanism is still under discussion, and the electronic and local structures of TiO2 during sodiation/desodiation process are not well understood either. Herein, we reported a mechanism study of graphene-supported oxygen-deficient anatase TiO2 nanotubes (nanowires) as the negative electrode material for sodium ion batteries. Different from the previous reports, the insertion/extraction of Na+ ions leads to almost no changes of titanium valence state but there is a charge redistribution of O 2p orbitals which alters the hybridization between O 2p and Ti 3d states, suggested by the combined electrochemical and X-ray spectroscopic study. Both the electronic and local structures of TiO2 during the reversible sodiation/desodiation process are revealed from the Ti L-edge and O K-edge spectra. This detailed study would shed light on the material design and structural optimization of TiO2 as energy storage material in different systems.
Keywords: graphene; local and electronic structures; oxygen-deficient; storage mechanism; titanium dioxide.