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 $\mathrm{Li}/\mathrm{LiPON}/{\mathrm{Li}}_x{\mathrm{CoO}}_2$ system. The model predicts interfacial potential drops driven by both electron transfer and ${\mathrm{Li}}^{+}$ space-charge layers that vary with the SSB’s state of charge. The results suggest a lower electronic ionization potential in the solid electrolyte favors ${\mathrm{Li}}^{+}$ transport, leading to higher discharge power.