Energy storage systems are essential for a broad range of applications with requirements as diverse as powering a continuously increasing number of portable devices, as traction power sources in electrically powered vehicles, or to stabilize the power level in electricity networks. Therefore, industrially viable materials for energy storage systems need to be adapted to various use cases , which requires detailed mechanistic understanding of underlying processes in batteries and capacitors . The energy density and the power density are two essential parameters, the former describing the amount of energy that can be stored and the latter how quickly this energy can be stored or released. Very generally, the distinction can be made between faradaic electrochemical processes such as intercalation of ions into the material, which are slow but allow for a high energy density, and non-faradaic physical processes such as double layer formation, which are fast and, therefore, facilitate a high power density. Faradaic processes are intensively studied in the context of battery materials, but the origin of their non-faradaic processes contribution, which can be dominant in high surface materials, is still unclear. It was summarized that "for the further advancement of electrical energy storage" systems "the influence of the surface chemistry on the electrochemical properties of materials" needs to be understood. The interplay between surface and bulk in sense of faradaic and non-faradaic processes are therefore of broad interest. In general the characterization of pristine materials for batteries is of importance to understand their fundamental properties . These properties can be tuned by several strategies, like doping with other atoms, by particle size adaption, and by modification of the surface structure. The last two approaches effected different bulk properties for the same bulk material. Therefore the cycling behavior and rate capability in batteries are commonly tested to correlate changes of surface and particle size with changes in the performance. It is well accepted that surface processes play a crucial role for the properties and performance of batteries and capacitors, yet there are still large gaps in our understanding of the relevant mechanisms. TiO2, for example, is an important, much studied material that exhibits faradaic and non-faradaic properties, which both depend on particle size and manufacturing process . There seems to be a dynamic dependence between the observed bulk characteristics of active materials and the nature of their surface. Surface modification dependent changes in a bulk material are difficult to observe. A publication by Lee et al. reported on a direct observable examples of a strong conductivity change in bulk AgX caused by surface modification with Al2O3. Compounds from the binary LiO2-TiO2 composition line such as Li4Ti5O12 (LTO), for example, have shown both very good cycling stability and very high rate capability . On the other hand, Li ion mobility in stoichiometric LTO appears to be low , yet strongly morphology dependent, with nanostructured LTO showing considerably faster Li ion dynamics . Furthermore, the addition of small amounts of lithium cause the resulting Li4+XTi5O12 to be a fast conducting material. Other publications on the diffusion of Li + in rutil and LTO support the idea of polaron hopping. Polarons are, in a simplified picture, mobile negatively charged quasi-particles with an ionic bond portion. For LTO, recently developed simulation techniques were able to show that polarons are more stable at the surface than in the bulk. However, as soon as a material is inserted into an electrochemical cell for testing, a multitude of additional processes occur, which hinders the individual investigation of specific mechanisms. Here, dry LTO is compared to LTO in contact with different electrolytes to analyze potential effects on bulk properties of the solid material. It is investigated whether, in principle, chemical surface reactions are induced, and if these changes affect the Li ion mobility. Nuclear magnetic resonance (NMR) relaxation is used to identify changes of the dynamics in the material. By employing Laplace inversion of the data, fractional differences in relaxation behavior due to Li mobility in different sample environments can be identified without a priori assumptions regarding the number of individual components. Thereby, it would be possible to distinguish between core-shell relaxation behavior if a surface layer changes its properties, and bulk effects if changes on the surface have a long-range impact on the physical properties of the material.