First-principles prediction of potentials and space-charge layers in all-solid-state batteries*

As all-solid-state batteries (SSBs) develop as an alternative to traditional cells, a thorough theoretical understanding of driving forces behind battery operation is needed. We present a fully first-principles-informed model of potential profiles in SSBs and apply the model to the Li/LiPON/Li_xCoO₂ system. These profiles, especially the interface dipoles, yield valuable information about lithium distribution and transport and the nature of interfacial electrical double layers. The results suggest design rules to minimize interfacial lithium transport resistance and optimize device performance.