A High-Energy Four-Electron Zinc Battery Enabled by Evoking Full Electrochemical Activity in Copper Sulfide Electrode

The growing global demand for sustainable and cost-effective energy storage solutions has driven the rapid development of zinc batteries. Despite significant progress in recent years, enhancing the energy density of zinc batteries remains a crucial research focus. One prevalent strategy involves the development of high-capacity and/or high-voltage cathode materials. CuS, a commonly used electrode material, exhibits a two-electron transfer mechanism; however, the reduced sulfion lacks electrochemical activity and thereby limits its discharge capacity and redox potential. In this study, we activate a CuS cathode to form a high-valence Cu²⁺&S compound using a deep-eutectic-solvent (DES)-based electrolyte. The presence of Cl^- in the DES-based electrolyte is crucial to the reversibility of the redox chemistry, and the liquid-phase-involved electrochemical process facilitates redox kinetics. A four-electron transfer pathway involving five reaction steps is identified for the CuS electrode, which unleashes the full electrochemical activity of the S element. Consequently, the full cell delivers a large discharge capacity of ∼800 mAh g^-1 at 0.2 A g^-1 and yields a high discharge plateau starting at 1.58 V, contributing to energy densities of up to 650 Wh kg^-1 (based on CuS). This work offers a promising approach to developing high-energy zinc batteries. © 2023 American Chemical Society.