Bioinspired hierarchical dual-gate ion regulation across electrolyte transport regimes for lithium–sulfur batteries

Lithium–sulfur (Li–S) batteries promise high theoretical energy density but are still hindered by slow polysulfide conversion, shuttle effects, and unstable solid electrolyte interphases (SEIs), issues that become more pronounced when moving from quasi-solid to all-solid electrolytes. In polyether electrolytes, these problems are compounded by crystalline domains and competing ion-coordination environments that limit ion transport. Here, we show a bioinspired dual-gate ion regulation strategy based on tris(hydroxypropyl)phosphine (THPP) that operates consistently across different electrolyte regimes. The hydroxyl groups of THPP function as structural gates, disrupting polyether crystallinity through hydrogen bonding and facilitating Li + transport, while the phosphorus-centered unit serves as a chemical gate that regulates polysulfide conversion and mitigates shuttle effects. Furthermore, the lower LUMO of the THPP cluster is conducive to the formation of a LiF-Li 3 P-rich SEI. The assembled battery shows a capacity decay rate of only 0.053% per cycle when cycled at 0.3 C for 700 cycles. Additionally, the Li||Li symmetric battery can be stably cycled (＞2200 h). High-loading (4.0 mg cm −2 ), lean-electrolyte (E/S = 7.5 µL mg −1 ) Li–S batteries can also operate stably for 30 cycles. Together, these effects lead to enhanced kinetics and cycling stability in both quasi-solid and all-solid poly(ethylene oxide) electrolytes, pointing to a unified molecular strategy for regulating ion transport in Li–S batteries. • THPP enables a bioinspired dual-gate ion regulation strategy for high-performance polyether electrolytes in lithium–sulfur batteries. • Hydrogen-bond interactions with hydroxyl groups reduce polymer crystallinity and pave more continuous pathways for Li + migration. • The phosphorus center accelerates soluble polysulfide conversion and promotes uniform LiF/Li 3 P-rich solid electrolyte interphases. • The dual-gate ion regulation strategy improves reaction kinetics and cycling durability across quasi-solid-state and all-solid-state lithium–sulfur batteries.