Dual-Solvent Supramolecular Assembly Enables Ampere-Hour Halide All-Solid-State Pouch Cell

Halide solid electrolytes (SSEs) hold promise for next-generation all-solid-state batteries (ASSBs), yet scalable fabrication of halide SSE films and ampere-hour-scale all-solid-state pouch cells (ASSPCs) via slurry coating has not been demonstrated. Here, we introduce a dual-solvent supramolecular assembly strategy that precisely regulates the chain organization of a multiblock copolymer binder (SEEPS), enabling low-binder, high-viscosity slurries for uniform halide SSE film formation. Methylcyclohexane and decane are identified as chemically compatible solvents that diminish InCl₃ surface precipitation in Li₃InCl₆, preserving ionic conductivity. The resulting Li₃InCl₆/Li_{6- x}PS_{5- x}Cl_{1+ x} bilayer SSE film exhibits high ionic conductivity (1.26 mS/cm), mechanical robustness, and electrochemical stability. ASSBs using NCM88 cathodes and micro-silicon anodes retain 71.3% capacity after 600 cycles at 0.5 C, while the first ten-layer ampere-hour-scale halide ASSPC delivers 1.45 Ah at 0.2 C with 95.1% capacity retention over 100 cycles. This approach establishes a practical and scalable pathway for fabricating halide ASSPCs, bridging laboratory innovations and commercial deployment.