Low-Temperature and High-Performance Vanadium-Based Aqueous Zinc-Ion Batteries

Abstract

Aqueous zinc-ion batteries have attracted attention due to their low cost and high safety. Unfortunately, dendrite growth, hydrogen evolution reactions, cathodic dissolution, and other problems are more serious; not only that, but also the cathodic and anodic materials' lattices contract when the temperature drops, and charge transfer and solid phase diffusion become slow, seriously aggravating dendrite growth. At present, there are few studies on the low-temperature system, and studies on retaining high specific capacity are even more rare. Herein, ethylene glycol (EG) and manganese sulfate (MSO) are selected as additives, and the manganese vanadate (MVO) cathode is used to find a high-performance solution at low temperature. MVO can provide higher specific capacity and better structural stability than MnO 2 to adapt to a low-temperature environment. At the same time, Mn 2+ in MSO can produce a cationic shield covering the initial zinc tip at an appropriate concentration to avoid the tip effect and inhibit the dissolution of MVO. EG can not only reduce the freezing point of the electrolyte but also promote the desolvation of [Zn(H 2 O) 6 ] 2+ . The synergistic effect of the three elements prevents the dissolution equilibrium of Mn 2+ in MVO from fluctuating greatly due to the change of temperature. Therefore, when we use EG@0.2 M MnSO 4 + 2 M ZnSO 4 (EG + 0.2Mn/2ZSO) electrolyte at −30 °C, the Zn||Zn batteries which used this type of electrolyte can remain 350 h at 1 mA cm −2 without failure. The Zn||Cu batteries can retain 100% Coulombic efficiency after more than 2000 cycles at 0.2 mA cm −2 . The Zn||MVO battery can reach 231.13 mA h g −1 at its first cycle, and the capacity retention rate is still above 85% after 1000 cycles, which is higher than that of the existing low-temperature research system.