Metallic Zinc Anode Working at 50 and 50 mAh cm−2 with High Depth of Discharge via Electrical Double Layer Reconstruction

Abstract Achieving high‐rate and high‐areal‐capacity Zn anode with high depth of discharge (DOD) offers a bright future for large‐scale aqueous batteries. However, Zn deposition suffers from severe dendrite growth and side reactions, which compromises achievable lifetime. Herein, an electrical double layer (EDL) reconstruction strategy is proposed by employing acetone as electrolyte additive to fully address these issues. Experimental and theoretical simulation results reveal that the adsorption priority of acetone to water on Zn creates a water‐poor inner Helmholtz layer. Meanwhile, the intense hydrogen bonding effect between acetone and water confines the activity of free water and weakens the Zn 2+ solvation in the outer Helmholtz layer and diffusion layer. Such ion/molecule rearrangement in EDL suppresses hydrogen evolution, facilitates the desolvation process, and promotes the Zn 2+ diffusion kinetics, which guides homogeneous Zn nucleation and uniform growth, even in extreme situations. At both ultrahigh current density of 50 mA cm −2 and areal capacity of 50 mAh cm −2 , the addition of 20 v/v% acetone in 2 m ZnSO 4 extends the lifespan of Zn//Zn symmetric cells from 12 to 800 h, with a high DOD of 73.5%. The effectiveness of this strategy is further demonstrated in the Zn‐MnO 2 full batteries at wide temperature range from −30 to 40 °C.