Manipulating stable four-electron zinc-iodine batteries via the introduction of diamine ligand sites

Abstract

Zinc-iodine batteries (ZIBs) are considered a promising energy storage system, but are still plagued by low energy density and rampant side reactions originating from active H₂O molecules in the liquid electrolyte. Realizing the coupled redox reactions within I^-/I₀/I⁺ species, i.e., four-electron transfer reactions, is deemed an effective strategy for boosting the energy density of ZIBs, which is mainly blocked by the rapid hydrolysis of nucleophilic I⁺ ions. To address these issues, urea with diamine ligand sites (-NH₂) was introduced into the liquid electrolyte [urea electrolyte (UE)] to achieve durable four-electron ZIBs. As demonstrated by the spectroscopic characterization results, -NH₂ groups can bundle the active H₂O molecules by reconfiguring the hydrogen bonds, and provide additional electrophilic ligand sites for I⁺ ions. Based on these advantages, both the side reactions on the Zn anode and the I⁺ hydrolysis reaction on the I₂@AC cathode are remarkably mitigated, and four-electron transfer is realized at low zinc salt concentrations. As a result, the optimized UE electrolyte effectively stabilizes the zinc metal anode, and endows the I₂@AC cathode with a high reversible capacity of 187.2 mAh g^-1 after 250 cycles at 1 A g^-1. The disclosed intermolecular force modulation strategy in this work will offer a comprehensive perspective for the future design of liquid electrolytes for high-energy-density ZIBs.

Keywords

Zinc-iodine batteries / four electron transfer / urea / hydrolysis reaction of I⁺ ions / hydrogen bonds

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