Interfacial charge transfer between solid electrolytes (SEs) and Li metal is a key factor limiting all-solid-state battery performance. Conventional density functional theory and nudged elastic band calculations are performed at 0 K along a single minimum-energy path and therefore neglect concerted multi-ion motion and finite-temperature effects, which can lead to inaccurate activation barriers. Here, we trained moment tensor potentials (MTPs) for garnet LLZO systems (t-LLZO, c-LLZO, and Ga-LLZO) and Li metal, enabling machine-learning molecular dynamics (MLMD) simulations of ${\mathrm{Li}}^{+}$ diffusion in the bulk and across Li/SE interfaces. We also introduce a residence-time window method that filters out ion rattling at the interface and isolates genuine charge-transfer events. The resulting charge-transfer activation energy at the Li/Ga-LLZO interface is only $167\pm 18\mathrm{meV}$, below the 200 meV barrier for vacancy-mediated Li migration in bulk Ga-LLZO. The corresponding intrinsic charge-transfer resistance is $\sim {10}^{-5}\mathrm{\Omega }{\mathrm{cm}}^2$, almost four orders of magnitude below the lowest experimentally reported $R_{\mathrm{ct}}$. These results indicate that intrinsic charge transfer across the Li/Ga-LLZO interface is not rate-limiting and Li transport within the electrolyte instead governs the overall kinetics. Taken together, our findings clarify the fast interfacial kinetics in Li/LLZO systems, and the proposed methodology can aid further interface optimization in solid-state batteries.

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• Lithium batteries
• Solid-state batteries
• Interfaces
• Density functional calculations
• First-principles calculations
• Machine learning