Origin of High Interfacial Resistance in Solid‐State Batteries: LLTO/LCO Half‐Cells**

The interface between cathode and electrolyte is a significant source of large interfacial resistance in solid-state batteries (SSBs). Spark plasma sintering (SPS) allows densifying electrolyte and electrodes in one step, which can improve the interfacial contact in SSBs and significantly shorten the processing time. In this work, we proposed a two-step joining process to prepare cathode (LiCoO2, LCO)/electrolyte (Li0.33La0.57TiO3, LLTO) half cells via SPS. Interdiffusion between Ti4+/Co3+ was observed at the interface by SEM/STEM, resulting in the formation of the Li−Ti−La−Co−O and Li−Ti−Co−O phases in LLTO and the Li−Co−Ti−O phase in LCO. Computational modeling was performed to verify that the Li−Ti−Co−O phase has a LiTi2O4 host lattice. In a study of interfacial electrical properties, the resistance of this interdiffusion layer was found to be 105 Ω, which is 40 times higher than the resistance of the individual LLTO phase. The formation of an interdiffusion layer is identified as the origin of the high interface resistance in the LLTO/LCO half-cell