Molecular Surface Engineering of Sulfide Electrolytes with Enhanced Humidity Tolerance for Robust Lithium Metal All-Solid-State Batteries.

Fadillah, Laras; Braks, Leonie; Oh, Jihoon; Liu, Mingliang; Türk, Hanna; Tisi, Davide; Mensi, Mounir; Ceriotti, Michele et al. · Adv Mater · 2026

basic_science · Level V

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Abstract

Solid-state electrolytes (SSEs) enable next-generation batteries due to their intrinsic safety and compatibility with lithium (Li) metal anodes. However, many SSEs, particularly sulfide-based systems, suffer from limited electrochemical stability and high moisture sensitivity. Here, the molecular surface engineering of Li argyrodite SSE, Li<sub>6</sub>PS<sub>5</sub>Cl<sub>0.5</sub>Br<sub>0.5</sub> (LPSClBr), is reported using octadecyl phosphonic acid (OPA) and its lithiated form (Li-OPA) in a single-step coating strategy to stabilize both anode and cathode interfaces. The Li-OPA-coated electrolyte maintains high ionic conductivity (>2.5 mS cm<sup>-1</sup>) and retains >92% of its initial conductivity after 24 h dry room exposure (dew point -50 °C). At 2 wt.% loading, Li-OPA-coated LPSClBr achieves a critical current density of 2.4 mA cm<sup>-1</sup> and supports stable Li plating/stripping for over 400 h at 1.0 mAh cm<sup>-2</sup>. In NCM811 cathode-based all-solid-state cells, it delivers 160 mAh g<sup>-1</sup> at 0.3 C with >99.7% Coulombic efficiency and 85% capacity retention after 100 cycles. In anode-free cell configurations, Li-OPA-modified electrolytes enhance interfacial stability and cycling performance. These results demonstrate Li-OPA as a scalable, high-performance interfacial modifier for sulfide-based solid-state batteries.