Low‐Concentration Redox‐Electrolytes for High‐Rate and Long‐Life Zinc Metal Batteries

The uncontrolled zinc electrodeposition and side reactions severely limit the power density and lifespan of Zn metal batteries. Herein, the multi-level interface adjustment effect is realized with low-concentration redox-electrolytes (0.2 m KI) additives. The iodide ions adsorbed on the zinc surface significantly suppress water-induced side reactions and by-product formation and enhance the kinetics of zinc deposition. The distribution of relaxation times results reveal that iodide ions can reduce the desolvation energy of hydrated zinc ions and guide the deposition of zinc ions due to their strong nucleophilicity. As a consequence, the Zn||Zn symmetric cell achieves superior cycling stability (>3000 h at 1 mA cm^-2, 1 mAh cm^-2) accompanied by a uniform deposition and a fast reaction kinetics with a low voltage hysteresis (<30 mV). Additionally, coupled with an activated carbon (AC) cathode, the assembled Zn||AC cell delivers a high-capacity retention of 81.64% after 2000 cycles at 4 A g^-1. More importantly, the operando electrochemical UV-vis spectroscopies show that a small number of I₃ ^- can spontaneously react with the dead zinc as well as basic zinc saltsand regenerate iodide ions and zinc ions; thus, the Coulombic efficiency of each charge-discharge process is close to 100%.