Na uptake at TiO 2 anatase surfaces under electric field control: A first-principles study

Na-ion batteries (NIBs) are promising devices for large-scale energy-storage facilities. Nanostructured TiO 2 is an efficient NIB negative electrode, showing good cycling performance and rate capability, but its activity depends on the crystalline facets exposed by anatase nanoparticles. Hence, we propose here a DFT+U study of Na + adsorption and insertion at (101), (100) and (001)-TiO 2 surfaces under the influence of external electric fields, which are simulated by adding a sawtooth-like electrostatic potential to the bare ionic potential. We find that field polarization affects Na + uptake as well as titania electronic features, promoting redox processes within Ti sublattice, as in battery charge/discharge cycling. Our results highlight the high-energy (001) surface to be the most active, for both directions of external fields, proving its activity to be exerted reversibly. Besides further insights, these outcomes pave the route for further exploration and design of electrode materials by simulation of battery in operando conditions. Graphical Abstract