Space-Charge Layers in All-Solid-State Batteries; Important or Negligible?

All-solid state batteries have the promise to increase the safety of Li-ion batteries. A prerequisite for high-performance all-solid-state batteries is a high Li-ion conductivity through the solid electrolyte. In recent decades, several solid electrolytes have been developed which have an ionic conductivity comparable to that of common liquid electrolytes. However, fast charging and discharging of all-solid-state batteries remains challenging. This is generally attributed to poor kinetics over the electrode-solid electrolyte interface because of poorly conducting decomposition products, small contact areas, or space-charge layers. To understand and quantify the role of space-charge layers in all-solid-state batteries a simple model is presented which allows to asses the interface capacitance and resistance caused by the space-charge layer. The model is applied to LCO (LiCoO2) and graphite electrodes in contact with an LLZO (Li7La3Zr2O12) and LATP (Li1.2Al0.2Ti1.8(PO4)3) solid electrolyte at several voltages. The predictions demonstrate that the space-charge layer for typical electrode–electrolyte combinations is about a nanometer in thickness, and the consequential resistance for Li-ion transport through the space-charge layer is negligible, except when layers completely depleted of Li-ions are formed in the solid electrolyte. This suggests that space-charge layers have a negligible impact on the performance of all-solid-state batteries.