Lithiation Thermodynamics and Kinetics of Anatase TiO₂ Nanoparticles Having Varying Sizes: Implications for Nanosized Li-Intercalation Electrodes

Using TiO 2 as a model system, we reveal size-dependent thermodynamics and kinetics in Li-intercalation electrodes. Smaller particles have lower equilibrium potential ( E eq ) and smaller entropy change during lithiation, which is 15.9 J K –1 (mol Li) −1 for the 10 nm sample and 34.7 J K –1 (mol Li) −1 for the 84 nm sample. Charge transfer energy barrier ( E a,ct ) increases from 199.7 to 278.8 meV while resistance ( R ct ) decreases with decreasing particle size from 84 to 10 nm, suggesting R ct plays a more important role in determining the electrochemical performance. This study may guide the design of Li-intercalation electrodes with superior rate performance.