Manipulating Uniform Nucleation to Achieve Dendrite-Free Zn Anodes for Aqueous Zn-Ion Batteries

The essence of Zn dendrite formation is ultimately derived from Zn nucleation and growth during the repeated Zn plating/stripping process. Here, the nucleation process of Zn has been analyzed using ex situ scanning electron microscopy to explore the formation of the initial Zn dendrite, demonstrating that the formation of tiny protrusions (the initial state of Zn dendrites) is caused by the inhomogeneity of Zn nucleation. Based on this, the uniform Zn nucleation is promoted by the Ni₅Zn₂₁ alloy coating (ZnNi) on the surface of Zn foil by electrodeposition, and the mechanism of ZnNi-promoted even nucleation is further analyzed with the assistance of density functional theory (DFT). The DFT results indicate that the ZnNi displays a stronger binding ability to Zn compared to the bare Zn, suggesting that Zn nuclei will preferentially form around ZnNi instead of continuing to grow on the surface of the initial Zn nuclei. Therefore, the designed Zn metal anode (Zn@ZnNi) can be ultra-stable for over 2200 h at a current density of 2 mA cm^-2 in the symmetric cell. Even at a much higher current density of 20 mA cm^-2, the extra-long life of over 2200 cycles (over 530 h) can be achieved. Moreover, the full cell with the Zn@ZnNi anode exhibits extra-long cycling performance for 500 cycles with a capacity of 207.7 mA h g^-1 and 1100 cycles (148.5 mA h g^-1) at a current density of 0.5 and 1 A g^-1, respectively.