The Air Stability of Sodium Layered Oxide NaTMO₂ (100) Surface Investigated via DFT Calculations

Air stability caused by the H₂O/CO₂ reaction at the layered oxide NaTMO₂ surface is one of the main obstacles to commercializing sodium-ion batteries (SIBS). The H₂O and CO₂ adsorption properties on the (100) surface of sodium layered transition metal oxide NaTMO₂ (TM = Co, Ni, Mo, Nd) are calculated using the DFT method to study the surface air stability. This study showed that the material bulk phase (symmetry), surface site, element type, and surface termination are all (though not the only) important factors that affect the adsorption strength. Contrary to previous studies, the P phase is not always more air-stable than the O phase; our calculations showed that the NaNiO₂ O phase is more stable than the P phase. The calculated band center and occupation showed a direct relationship with the adsorption energy. The Na site adsorption for CO₂ and H₂O showed the same V-shape trend. However, the TM adsorption for CO₂ and H₂O showed a different trend. With an increased t₂g band center, CO₂ adsorption strength increases. There is no clear trend for H₂O adsorption. Our calculations showed that the electronic structure of the surface atomic of adsorption site plays a decisive role in CO₂ and H₂O adsorption strength. This study demonstrated an effective method for obtaining a stability parameter regarding the electronic structure, which can be used to screen the air-stable layered oxide sodium cathode in the future.