Investigation of the Li-Ion Insertion Mechanism for Amorphous and Anatase TiO2 Thin-Films

S. Moitzheim, S. De Gendt, P. M. Vereecken
2019 Journal of the Electrochemical Society  
Titania is considered an interesting anode candidate for Li + -ion batteries, as it offers a high theoretical capacity (1280 mAh cm −3 or 336 mAh g −1 ) and long term cycling stability. Unfortunately, the most commonly investigated anatase structure never reaches the theoretical capacity at practical charging rates (i.e. above 1 C). In this work, we compare amorphous (am-TiO 2 ) to anatase TiO 2 thin-films, and investigate the exceptional performance of am-TiO 2 as Li + -ion insertion
more » ... insertion electrode. An in-depth electrochemical characterization using cyclic voltammetry (CV), constant current lithiation and delithiation, and potentiostatic intermittent titration technique (PITT) is performed. From CV, the insertion and extraction kinetics of am-TiO 2 is found to be unrestricted by diffusion, contrary to anatase. Based on our combined electrochemical results, two different mechanisms are formulated for anatase and am-TiO 2 . Whereas anatase is filled from the "top-down", with a buildup of Li near the electrode/electrolyte interface, am-TiO 2 shows a "bottom-up" filling mechanism. This discrepancy is ascribed to the difference in diffusion coefficient measured for am-TiO 2 and anatase. This work highlights the differences of Li-ion insertion into amorphous TiO 2 compared to anatase, and gives guidance on material development for high capacity and fast charging electrodes. Reports given in units of gravimetric capacity (mAh g −1 ) were converted to volumetric capacities (mAh cm −3 ) by assuming a density of 3.8 g cm −3 . φ A rate of 1 C corresponds here to 336 mA g −1 or 1280 mA cm −3 . ) unless CC License in place (see abstract). ecsdl.org/site/terms_use address. Redistribution subject to ECS terms of use (see 109.128.44.123
doi:10.1149/2.1091816jes fatcat:6wgoxirqyvdhxfjarpvchyo5ri