Abstract Aqueous Zn‐I 2 batteries are promising for sustainable energy storage, exhibit excellent safety, low cost, and high energy density. However, their practical application is limited by the two‐electron I − /I⁰ redox reaction and the severe shuttle effect of polyiodide species. Here, a multifunctional ionic liquid, 1‐butyl‐3‐methylimidazolium bromide (BmimBr), is introduced to establish a dynamic interhalogen coupling between iodine and bromine species, which enables a six‐electron transfer pathway involving I − /I⁰/I⁺ and Br − /Br⁰. In situ characterizations and theoretical calculations show that Br − acts as a dynamic mediator, forming an IBr 2 − intermediate with iodine. This significantly lowers the energy barrier for oxidizing I⁰ to I⁺, thereby contributing additional capacity and accelerating kinetics. Simultaneously, Bmim⁺ provides dual interfacial functions: confining polyiodides at the cathode to suppress shuttling, and forming a protective layer on the zinc anode, which reduces interfacial water, inhibits dendrite growth and side reactions. Leveraging this synergistic design, the Zn‐I 2 battery achieves a high specific capacity of 511 mAh g −1 at 1 A g −1 and retains 90.22% of its capacity after 30 000 cycles at 10 A g −1 . The dynamic interhalogen coupling strategy offers a novel route to activate multielectron reactions and stabilize electrode interfaces in Zn‐I 2 batteries.
Huang et al. (2025) studied this question.