Understanding Cathode–Electrolyte Interphase Formation in Solid State Li‐Ion Batteries via 4D‐STEM

Abstract Interphase layers that form at contact points between the solid electrolyte (SE) and cathode active material in solid‐state lithium‐ion batteries (SS‐LIBs) increase cell impedance, but the mechanisms for this interphase formation are poorly understood. Here, we demonstrate a simple workflow to study cathode–electrolyte interphase (CEI) formation using 4D‐scanning transmission electron microscopy (4D‐STEM) that does not require SS‐LIB assembly. We show benefits of MoCl 5 :EtOH as a chemical delithiating agent, and prepare chemically delithiated cathode LiNi 0.6 Co 0.2 Mn 0.2 O 2 (NMC) powder in contact with Li 10 GeP 2 S 12 (LGPS) SE powder as a SS‐LIB CEI surrogate. We map the composition and structure of the CEI layers using 4D‐STEM, energy dispersive X‐ray spectroscopy (EDS), and electron pair distribution function analysis (ePDF). EDS indicates O migration from NMC into LGPS. ePDF analysis indicates sulfate and phosphate formation localized on the surface of LGPS, as well as Li 2 O formation within the LGPS phase, and self‐decomposition of NMC. These results are consistent with an electrochemical self‐discharge mechanism for interphase formation arising from coupled redox reactions of sulfur oxidation in LGPS and transition metal reduction in NMC. This suggests that coatings which stop anion transport but allow Li + and e − transport may prevent interphase formation and reduce impedance in SS‐LIBs.