Mechanochemical Landscapes of Carbon Electrodes Differentially Modulate Li, Na, and K Interactions

Carbon-based electrodes are widely used anodes for Li-, Na-, and K-ion batteries. Using first-principles calculations, we show that the mechanochemical landscape of rippled graphene distinctly modulates Na/K and Li binding and diffusion. The vectorial nature of curvature−positive valley-shaped versus negative mountain-shaped regions−strongly affects Na− and K−graphene interactions, whereas Li−graphene interactions remain comparatively insensitive. Na and K binding is governed by the number of weak ion−C interactions: valley regions support a more delocalized interaction network, while mountain regions favor localized binding. In contrast, Li binding remains largely local and is therefore less affected by curvature. Consequently, Na and K are more susceptible than Li to longer-range deformation effects and exhibit anisotropic diffusion on curved electrodes, whereas Li diffusion remains largely isotropic. These results identify deformation-aware nanostructuring as a promising route toward improved Na- and K-ion battery electrodes.