Trinity Cooperative Electrode as a High‐Performance Electrocatalytic Host for Ultra‐Stable, High‐Rate Zinc–Halogen Batteries

Aqueous zinc-halogen batteries (ZHBs) offer safety and low cost but are hindered by halogen dissolution, shuttle effects, and sluggish interfacial kinetics. We present a trinity cooperative electrode (TCE) that integrates a conductive polymer, a supramolecular solvent matrix, and an elastic polymer network to simultaneously enhance electronic conductivity, mechanical/solvent stability, and halogen immobilization. The iodine conversion pathway is elucidated by in situ/ex situ characterizations and molecular dynamics simulations. In ZnI₂ + Zn(CF₃SO₃)₂ electrolytes, TCE-based cells deliver 255 mAh g⁻¹ at 1 A g⁻¹, retain 150 mAh g⁻¹ at 50 A g⁻¹ for > 50 000 cycles, and operate reliably at -10°C. The TCE also catalyzes Br⁻/Br₂ conversion in Zn(CF₃SO₃)₂ + ZnBr₂ and enables sequential multielectron reactions in a ternary Zn(CF₃SO₃)₂ + ZnI₂ + ZnBr₂ electrolyte, achieving ∼200 mAh g⁻¹ at 30 A g⁻¹ for > 22 000 cycles. This approach advances high-energy, long-life ZHBs through pseudocapacitive interfacial chemistry.