High-Rate and Long-Cycle Stability with a Dendrite-Free Zinc Anode in an Aqueous Zn-Ion Battery Using Concentrated Electrolytes

Abstract

Recently, metallic zinc (Zn) is becoming a promising ideal anode material for rechargeable aqueous batteries by providing high theoretical capacity (820 mA h/g) with divalent reaction, environmental friendliness, earthy abundance, low cost, low toxicity, higher water compatibility, and low electrochemical potential (-0.762 V vs SHE). However, intensive growth of zinc dendrites while plating/stripping lowers its coulombic efficiency and shortens the cycle life of the rechargeable devices. Here, we report a concentrated aqueous electrolyte (4.2 M ZnSO4 + 0.1 M MnSO4) with improved cycling stability of zinc metal anode achieving an average coulombic efficiency (ACE) ∼99.21% cycling for more than 1000 h at 0.2 mA/cm2 current density using a Zn||Cu cell. However, a frequently used diluted electrolyte (2 M ZnSO4 + 0.1 M MnSO4) only produces ACE ≈ 97.54% with a relatively short life cycle. The developed concentrated electrolyte with strongly aggregated ion pairs shows the synergetic effects of the enhanced solvation/desolvation process, electrostatic shielding, and Le Chatelier's principle. Consequently, the additives simultaneously suppress Zn dendrites and dissolution of Mn2+ ions from the MnO2 cathode. A highly stable and reversible Zn||MnO2 cell retaining about 88.37% retention capacity was obtained after cycling for more than 1200 cycles at 938 mA/g current density.