It was observed that LTO changes its bulk properties by contact with electrolyte in the form of different Li NMR T1 relaxation times. This effect is caused on the one hand by the polarons of surface or near-surface defects and on the other hand controlled by the cations of the electrolyte. On the chemical level, an equilibrium between the liquid and solid phases can be concluded. Lithium ions from the electrolyte can diffuse together with the polarons from the surface into the bulk material. Thus -with respect to a charging process -the ion transport and the electron transport in LTO initially take place separately. Consequently, the here presented work demonstrates the significant effect of surface defects and the associated polarons, on the properties of LTO as lithium storage materials. Hence, we believe the control of surface defects and polarons is an important tool to tune materials like LTO for battery or capacitor application.