Interdiffusion suppression at the cathode‐electrolyte interface of all‐solid‐state‐batteries by Li3PO4 conformal coating.

All‐solid‐state lithium batteries (ASSLBs) are promising energy‐storage devices with high energy density and safety. However, the discharge capacity of ASSLBs that use sulfide solid electrolytes (SEs) and Ni‐rich cathode active materials (CAMs) deteriorates significantly during electrochemical cycling. Interfacial coatings between CAM and sulfide SEs are known to effectively alleviate capacity deterioration. Among the various coating materials, lithium phosphate (LPO) was selected and synthesized via atomic layer deposition (ALD). The crystal phase of the LPO thin film irreversibly changed, and the Li‐ion conductivity deteriorated after heat treatment. Additionally, particle ALD (P‐ALD) of LPO was successfully performed to completely passivate the CAM particles. Torque cells with the LPO‐coated CAMs showed excellent capacity retention, whereas the cells without the LPO coating showed a significantly deteriorated discharge capacity with increased internal resistances. The passivation effect of the LPO coating was confirmed by the cross‐sectional images from a FIB and scanning electron microscopy with energy‐dispersive X‐ray spectroscopy (SEM–EDS) dual system. We believe that the study will help us investigate the effects of side reactions between sulfide SEs and CAMs on the performance and stability of P‐ALD. [ABSTRACT FROM AUTHOR]