An Atomistic Study of Reactivity in Solid-State Electrolyte Interphase Formation for Li/Li7P3S11

作者：Bryant Y. Li, Vir Karan, Aaron D. Kaplan, Mingjian Wen, Kristin A. Persson · 发表于：The Journal of Physical Chemistry C · 年份：2025 · DOI：10.1021/acs.jpcc.5c03589 · 被引用次数：6 · 研究领域：Advancements in Battery Materials、Advanced Battery Materials and Technologies、Extraction and Separation Processes

High Resolution Image Download MS PowerPoint Slide Lithium metal batteries offer superior volumetric and gravimetric specific capacities compared to those based on traditional graphite anodes. Although advancements in solid-state electrolytes address safety concerns, challenges remain, particularly regarding interphase formation in lithium metal anodes. This work presents a computational framework based on high-throughput first-principles density functional theory and machine-learning interatomic potentials (MLIPs) including automated iterative, active learning to enable robust computational exploration of interphase formation between lithium metal anodes and an inorganic solid-state electrolyte. As a demonstration, we apply the framework to a Li/Li 7 P 3 S 11 interface and find that it accurately identifies the experimentally observed, thermodynamically stable interphase products as well as their overall spatial arrangement within a heterogeneous, amorphous layered structure, with Li 2 S domains of nanocrystallinity. Our simulations show two stages, a fast and slow diffusion reaction regime, that corroborate the relative phase formation rate of Li x P, Li 2 S, and Li 3 P. Using the Onsager transport theory, we capture time-dependent ionic diffusion within the reacting interface, including cross-correlation effects. We found that cross-correlation effects between Li–P and P–S ionic motion significantly influence P-ion diffusion, making it highly sensitive to the local environ...