Synergistic Suppression of Dissolved Oxygen and Proton Corrosion on Zinc Anodes by the Glutathione/Oxidized Glutathione Redox Couple

Abstract

The practical application of aqueous zinc-ion batteries (AZIBs) requires addressing the key challenge of temperature range limitations, facing thermodynamics dominated corrosion at high temperatures and kinetics dominated mass transfer obstruction at low temperatures. Although these temperature-related failure mechanisms have been extensively studied, the corrosion of dissolved oxygen (DO) remains frequently overlooked, necessitating further research of wide-temperature failure mechanisms in AZIBs. Herein, we demonstrate that DO corrosion occurs over a wide-temperature range and significantly exacerbates Zn corrosion and byproducts formation, surpassing the well-recognized proton corrosion. We introduce antioxidant glutathione (GSH) as an electrolyte additive to address the corrosion caused by DO and proton. Coexisting glutathione/oxidized glutathione redox couple can spontaneously capture DO and eliminate the generated H₂. Moreover, GSH disrupts the intrinsic H-bond networks, depresses the electrolyte freezing point, and enhances the low-temperature mass-transfer kinetics. A self-healing hybrid solid electrolyte interphase (SEI) can also be formed during battery operation, which suppresses dendrite growth. Consequently, the Zn||Zn symmetric cell with GSH-modified electrolyte achieves an extended lifespan of up to 5000 h at −10 °C, 1700 h at 25 °C, and 2500 h at 40 °C. This work reveals a dynamic chemical self-deoxygenation/self-dehydrogenation strategy to design a non-corrosive and dendrite-free Zn anode from −10 to 40 °C for stable AZIBs.