Surface Degradation of Single‐crystalline Ni‐rich Cathode and Regulation Mechanism by Atomic Layer Deposition in Solid‐State Lithium Batteries

Single-crystalline Ni-rich cathode (SC-NCM) has attracted increasing interest owing to its greater capacity retention in advanced solid-state lithium batteries (SSLBs), while suffers from severe interfacial instability during cycling. Here, via atomic layer deposition, Li₃ PO₄ is introduced to coat SC-NCM (L-NCM), to suppress undesired side reaction and enhance interfacial stability. The dynamic degradation and surface regulation of SC-NCM are investigated inside a working SSLB by in situ atomic force microscopy (AFM). We directly observe the uneven cathode electrolyte interphase (CEI) and surface defects on pristine SC-NCM particle. Remarkably, the formed amorphous LiF-rich CEI on L-NCM maintains its initial structure upon cycling, and thus endows the battery with improved cycling stability and excellent rate capability. Such on-site tracking provides deep insights into surface mechanism and structure-reactivity correlation of SC-NCM, and thus benefits the optimizations of SSLBs.