Influence of electric fields on metal self-diffusion barriers and its consequences on dendrite growth in batteries.

Based on the results of periodic density functional theory calculations, we have recently proposed that the height of self-diffusion barriers can serve as a descriptor for dendrite growth in batteries [M. Jäckle et al., Energy Environ. Sci. 11, 3400 (2018)]. However, in the determination of the self-diffusion barriers, the electrochemical environment has not been taken into account. Still, due to the presence of electrical double layers at electrode/electrolyte interfaces, strong electric fields can be present close to the interfacial region. In a first step toward including the electrochemical environment, we have calculated barriers for terrace-diffusion on lithium, magnesium, and silver surfaces and across-step self-diffusion on lithium in the presence of electric fields. Whereas the electric field effect is more pronounced on a stepped surface than on flat terraces, overall we find a negligible influence of electric fields on self-diffusion barriers which we explain by the good screening properties of metals.