Metallic zinc (Zn) is a highly promising anode material for aqueous energy storage systems due to its low redox potential, high theoretical capacity, and low cost. However, rampant dendrites/by-products and torpid Zn2+ transfer kinetics at electrode/electrolyte interface severely threaten the cycling stability, which deteriorate the electrochemical performance of Zn-ion batteries. Herein, an interfacial engineering strategy to construct alkaline earth fluoride modified metal Zn electrodes with long lifespan and high capacity retention is reported. The compact fluoride layer is revealed to guide uniform Zn stripping/plating and accelerate the transfer/diffusion of Zn2+ via Maxwell-Wagner polarization. A series of in situ and ex situ spectroscopic studies verified that the fluoride layer can guide uniform Zn stripping/plating. Electrochemical kinetics analyses reveal that positive effect on the removal of Zn2+ solvation sheath provided by fluoride layer. Meanwhile, this fluoride coating layer can act as a barrier between the Zn electrode and electrolyte, providing a high electrode overpotential toward hydrogen evolution reaction to hold back H2 evolution. Consequently, the fluoride-modified Zn anode exhibited a capacity retention of 88.2% after 4000 cycles under10 A g-1 . This work opens up a new path to interface engineering for propelling the exploration of advanced rechargeable aqueous Zn-ion batteries.
Keywords: aqueous Zn-ion batteries; interfacial engineering; maxwell-wagner polarization; ultrastable anodes.
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