Ion Transport at Polymer–Argyrodite Interfaces

Solid-state electrolytes, particularly polymer/ceramic composite electrolytes, are emerging as promising candidates for lithium-ion batteries due to their high ionic conductivity and mechanical flexibility. The interfaces that arise between the inorganic and organic materials in these composites play a crucial role in ion transport mechanisms. While lithium ions are proposed to diffuse across or parallel to the interface, few studies have directly examined the quantitative impact of these pathways on ion transport and little is known about how they affect the overall conductivity. Here, we present an atomistic study of lithium-ion (Li⁺) transport across well-defined polymer-argyrodite interfaces. We present a force field for polymer-argyrodite interfacial systems, and we carry out molecular dynamics and enhanced sampling simulations of several composite systems, including poly(ethylene oxide) (PEO)/Li₆PS₅Cl, hydrogenated nitrile butadiene rubber (HNBR)/Li₆PS₅Cl, and poly(vinylidene fluoride-<i>co</i>-hexafluoropropylene) (PVDF-HFP)/Li₆PS₅Cl. For the materials considered here, Li-ion exhibits a preference for the ceramic material, as revealed by free energy differences for Li-ion between the inorganic and the organic polymer phase in excess of 13 <i>k</i>_B<i>T</i>. The relative free energy profiles of Li-ion for different polymeric materials exhibit similar shapes, but their magnitude depends on the strength of interaction between the polymers and Li-ion: the greater the interaction between the polymer and Li-ions, the smaller the free energy difference between the inorganic and organic materials. The influence of the interface is felt over a range of approximately 1.5 nm, after which the behavior of Li-ion in the polymer is comparable to that in the bulk. Near the interface, Li-ion transport primarily occurs parallel to the interfacial plane, and ion mobility is considerably slower near the interface itself, consistent with the reduced segmental mobility of the polymer in the vicinity of the ceramic material. These findings provide insights into ionic complexation and transport mechanisms in composite systems, and will help improve design of improved solid electrolyte systems.