Iodine/Chlorine Multi-Electron Conversion Realizes High Energy Density Zinc-Iodine Batteries

Aqueous zinc-iodine (Zn-I2) batteries are promising energy storage devices; however, the conventional single-electron reaction potential and energy density of iodine cathode are inadequate for practical applications. Activation of high-valence iodine cathode reactions has evoked a compelling direction to developing high-voltage zinc-iodine batteries. Herein, ethylene glycol (EG) is proposed as a co-solvent in a water-in-deep eutectic solvent (WiDES) electrolyte, enabling significant utilization of two-electron-transfer I+/I0/I- reactions and facilitating an additional reversibility of Cl0/Cl- redox reaction. Spectroscopic characterizations and calculations analyses reveal that EG integrates into the Zn2+ solvation structure as a hydrogen-bond donor, competitively binding O atoms in H2O, which triggers a transition from water-rich to water-poor clusters of Zn2+, effectively disrupting the H2O hydrogen-bond network. Consequently, the aqueous Zn-I2 cell achieves an exceptional capacity of 987 mAh gI2-1 with an energy density of 1278 Wh kgI2-1, marking an enhancement of approximate to 300 mAh g-1 compared to electrolyte devoid of EG, and enhancing the Coulombic efficiency (CE) from 68.2% to 98.7%. Moreover, the pouch cell exhibits 3.72 mAh cm-2 capacity with an energy density of 4.52 mWh cm-2, exhibiting robust cycling stability. Overall, this work contributes to the further development of high-valence and high-capacity aqueous Zn-I2 batteries.