Recent Advances in Polyphenylene Sulfide-Based Separators for Lithium-Ion Batteries

Polyphenylene sulfide (PPS)-based separators have garnered significant attention as high-performance components for next-generation lithium-ion batteries (LIBs), driven by their exceptional thermal stability (>260 °C), chemical inertness, and mechanical durability. This review comprehensively examines advances in PPS separator design, focusing on two structurally distinct categories: porous separators engineered via wet-chemical methods (e.g., melt-blown spinning, electrospinning, thermally induced phase separation) and nonporous solid-state separators fabricated through solvent-free dry-film processes. Porous variants, typified by submicron pore architectures (<1 μm), enable electrolyte-mediated ion transport with ionic conductivities up to >1 mS·cm^-1 at >55% porosity, while their nonporous counterparts leverage crystalline sulfur-atom alignment and trace electrolyte infiltration to establish solid-liquid biphasic conduction pathways, achieving ion transference numbers >0.8 and homogenized lithium flux. Dry-processed solid-state PPS separators demonstrate unparalleled thermal dimensional stability (<2% shrinkage at 280 °C) and mitigate dendrite propagation through uniform electric field distribution, as evidenced by COMSOL simulations showing stable Li deposition under Cu particle contamination. Despite these advancements, challenges persist in reconciling thickness constraints (<25 μm) with mechanical robustness, scaling solvent-free manufacturing, and reducing costs. Innovations in ultra-thin formats (<20 μm) with self-healing polymer networks, coupled with compatibility extensions to sodium/zinc-ion systems, are identified as critical pathways for advancing PPS separators. By addressing these challenges, PPS-based architectures hold transformative potential for enabling high-energy-density (>500 Wh·kg^-1), intrinsically safe energy storage systems, particularly in applications demanding extreme operational reliability such as electric vehicles and grid-scale storage.