Locally Confined Polysulfide-Reactive Electrolytes for Shuttle-Free Sodium–Sulfur Batteries

Sodium–sulfur batteries promise high-energy-density and sustainable electrochemical energy storage but suffer from uncontrolled polysulfide dissolution and high sodium reactivity. These challenges fundamentally originate from poor electrolyte–electrode compatibility. Current electrolyte research inadequately addresses the trade-off between minimal polysulfide solvation and stabilizing sodium interfaces. Here, we present a locally confined polysulfide-reactive electrolyte strategy that mediates the polysulfide dissolution dynamics and sodium stability by leveraging an electrophilic solvating species with a localized high-concentration electrolyte. This design enables shuttle-free cell operation by synergistically restricting the global solvating power of the electrolyte through intermolecular interactions and locally scavenging sparingly dissolved polysulfides via electrolyte electrophilicity. The precisely confined surface reaction facilitates a protective cathode–electrolyte interface, realizing a quasi-solid-state sulfur conversion in our liquid ether-based electrolyte, which crucially avoids crossover-induced catastrophic sodium–metal degradation. The proposed electrolyte demonstrates long-term cycling of high-mass-loading sulfur cathodes (>3 mg S cm –2 with commercial carbon host and 70 wt % sulfur content), which afford 710 mA h g –1 over 400 cycles in coin cells and steady pouch cell operation over 180 cycles. This work establishes a scalable electrolyte design protocol that regulates the reaction chemistry of highly reactive electrodes, offering a pathway toward sustainable renewable energy storage.