The Polymer Society of Korea

Abstract

All-solid-state batteries (ASSBs) promise high-energy, safer storage, but practical use is hindered by polyethylene oxide (PEO) electrolytes with poor salt dissociation, crystallinity, slow segmental dynamics, and low Li⁺ transference. Here, we introduce a beyond-PEO design that programs ion transport via structural ordering, entropy regulation, and dynamic ionic crosslinking. COF single-ion conductors deliver directional Li⁺ pathways; entropy-driven monomer-in-salt and zwitterionic dry polymers raise carrier density and accelerate hopping; ionic dimer elastomers provide robust, reversible crosslinks that decouple conductivity from mechanics. These PEO-free electrolytes enable high conductivity and tLi⁺, dendrite suppression, and compatibility with high-areal-capacity electrodes for scalable ASSB fabrication.