Electrically Insulating Rigid Multi-Channel Electrolyte Container for Customizable Electron Transfer in Zn-Halogen Batteries

• A rigid electrolyte container (SiO2@PVDF-hfp) was designed to immobilize the liquid halogen-ion electrolyte, enabling separator-free Zn-halogen batteries. • The container regulates Zn2+ solvation via hydrogen bonding regulation, while providing multi-channel structure for enhanced mass transfer, jointly enabling durable Zn plating/stripping. • Effective confinement of intermediates ensures high reversibility across multi-electron transfer mechanisms, achieving an exceptionally low-capacity decay of 0.02‰ over 4500 cycles and a high areal capacity of 11.9 mAh cm−2. • This work presents a novel “container engineering” approach to halogen-ion electrolyte design, providing fundamental insights into redox reversibility and reaction kinetics.