Observing Li Nucleation at the Li Metal–Solid Electrolyte Interface in All-Solid-State Batteries

Benefiting from the significantly improved energy density and safety, all-solid-state lithium batteries (ASSLBs) are considered to be one of the most promising next-generation energy technologies. Their practical applications, however, are strongly impeded by Li dendrite formation. Despite this recognized challenge, a comprehensive understanding of the Li dendrite nucleation and formation mechanism remains elusive. In particular, the initial locations of Li dendrite formation are still ambiguous: do Li clusters form directly at the Li anode surface, inside the bulk solid electrolyte (SE), or within the solid-electrolyte interphase (SEI)? Here, based on the deep-potential molecular dynamics simulations combined with enhanced sampling techniques, we investigate the atomic-level mechanism of Li cluster nucleation and formation at the Li anode/SE interface. We observe that an isolated Li cluster initially forms inside the SEI between the Li₆PS₅Cl SE and the Li metal anode, located ∼1 nm away from the Li anode/SEI boundary. The local electronic structure of the spontaneously formed SEI is found to be a key factor enabling the Li cluster formation within the SEI, in which a significantly decreased band gap could facilitate electronic conduction through the SEI and reduce Li⁺ ions to metallic Li atoms therein. Our work provides atomic-level insights into Li-dendrite nucleation at anode/SE interfaces in ASSLBs and could guide future design for developing Li-dendrite-inhibiting strategies.