STEM-EELS Spectrum Imaging of an Aerosol-Deposited NASICON-Type LATP Solid Electrolyte and LCO Cathode Interface

All-solid-state batteries (ASSBs) are promising candidates for application as next-generation high-power supply and storage devices in electric vehicles. ASSBs offer excellent safety and a high energy density; however, the high interfacial resistance between the positive electrode and solid electrolyte due to solid–solid contact reactions at elevated temperatures limits their applications. To address these issues, the effect of thermal annealing on the interfacial structure between a sodium super ionic conductor (NASICON)-type Li_1.3Al_0.3Ti_1.7(PO₄)₃ (LATP) solid electrolyte and a LiCoO₂ (LCO) cathode in an ASSB fabricated by aerosol deposition was investigated experimentally. Specifically, spectrum imaging was conducted by combining scanning transmission electron microscopy and electron energy loss spectroscopy. Metastable degraded low-density transition layers were formed between LATP and LCO in the as-deposited sample. A significant reduction in interfacial resistance was achieved after thermal annealing at 250–300 °C, which was mainly attributed to structural recovery in this temperature range. However, thermal annealing at 400 °C resulted in increased interfacial resistance due to the formation of a Co₃O₄-like spinel blocking layer at the LATP/LCO interface. These findings provided valuable insights into the electronic properties of the ASSB composite under investigation and were consistent with theoretical predictions of Li and O transfer between the layers due to thermal annealing.