Nano-Scale ZrN Film Modified Zn Anode with Ultra-Long Cycle Life Over 5000 H

Abstract

Dendrite growth, corrosion, and hydrogen evolution are major issues for Zn anodes, which seriously hinder the further practical application of aqueous zinc-ion batteries. To address these issues, Zirconium Nitride (ZrN) layer with a thickness of 110 nm is uniformly deposited on the surface of Zn anode using plasma-enhanced atomic layer deposition (PE-ALD). In/ex situ characterizations verify that the as-introduced ZrN layer has excellent anticorrosive and zincophilic ability, which can suppress corrosion and hydrogen evolution, lower the nucleation energy barrier for Zn²⁺ deposition, and effectively inhibit dendrite growth. Theoretical calculations also reveal that ZrN exhibits significantly higher adsorption capacity for Zn²⁺ compared to bare Zn, which is conducive to regulating the Zn deposition behavior. This innovative interface significantly extends battery cycle life and enhances coulombic efficiency. Encouragingly, under a current density of 5 mA cm⁻² and areal capacity of 1 mAh cm⁻², the Zn@ZrN symmetrical cells demonstrate an extraordinary cycling life of up to 5000 h, significantly surpassing other reported Zn anodes modified by films/coatings. In addition, it also exhibits an impressive cycling life of 1200 h at 1 mA cm⁻² and 1 mAh cm⁻². The full cells of Zn@ZrN||MnO₂ retain high capacity after 1000 cycles, markedly outperforming conventional Zn||MnO₂ batteries.