Long cyclic stability of acidic aqueous zinc-ion batteries achieved by atomic layer deposition: the effect of the induced orientation growth of the Zn anode

Abstract

Aqueous Zn-ion batteries with economical ZnSO₄ solution as the electrolyte suffer from a tremendous tendency of dendrite formation under mildly acidic conditions; moreover, utilization of Zn(CF₃SO₃)₂ delivers superior performance, but is expensive. Herein, we optimize the ZnSO₄ electrolyte by inducing 50 μL of 10 M sulfuric acid in 10 mL electrolyte, which can achieve long cycle life (1000 h at 0.1 mA cm⁻², 300 h at 1 mA cm⁻² and 250 h at 10 mA cm⁻²) when the Zn foil is protected by three metallic oxides deposited by atomic layer deposition (ALD). The nucleation behaviour of the (002) facet has proved to play a critical role in the reversible lifespan. The Al₂O₃ layer would restrict the stripping procedure, leading to the highest overpotential, while the TiO₂ layer and Fe₂O₃ layer tended to strip all orientations but the (002) facet. Al₂O₃@Zn demonstrated a preference for a compact hillock-like (101) orientation texture in the deposition procedure, while TiO₂@Zn and Fe₂O₃@Zn were favourable to obtain a smooth terrace texture. Additionally, symmetric cells with Fe₂O₃@Zn expressed the lowest overpotential (31.64 mV) and minimal voltage hysteresis (23.6 mV) at 1 mA cm⁻². A Zn-MnO₂ battery with Fe₂O₃@Zn also displayed superior capacity, which could reach 280 mA h g⁻¹ at a current density of 1 A g⁻¹. The diffusion coefficient of Zn²⁺ discloses that among the three ALD layers, full cells with Fe₂O₃@Zn are the most favourable for diffusion of Zn²⁺ in acidic electrolyte.