Highly Reversible Zn Metal Anode Stabilized by Dense and Anion‐Derived Passivation Layer Obtained from Concentrated Hybrid Aqueous Electrolyte.

Zinc metal is considered a promising anode material for aqueous zinc ion batteries. However, it suffers from dendrite growth, corrosion, and low coulombic efficiency (CE) during plating/stripping. Herein, a concentrated hybrid (4 m Zn(CF3SO3)2 + 2 m LiClO4) aqueous electrolyte (CHAE) to overcome the challenges facing the Zn anode is reported. The developed electrolyte achieves dendrite‐free Zn plating/stripping and obtains an excellent CE of ≈100%, surpassing the previously reported values. The combination of synchrotron‐based in operando transmission X‐ray microscopy, X‐ray diffraction, and ex situ X‐ray photoelectron spectroscopy analyses indicate that the denser, anion‐derived passivation layer formed using the CHAE facilitates homogeneous current distribution and better prevents freshly deposited Zn from directly contacting the electrolyte than the looser, solvent‐derived layers formed from a dilute hybrid aqueous electrolyte (DHAE). The beneficial effects of the CHAE on the compact, dense, and stable salt‐anion‐derived passivation layer can be attributed to its unique solvation structure, which suppresses the water‐related side reactions and widens the electrochemical potential window. In the hybrid Zn||LiFePO4 configuration, the CHAE‐based cell delivered a stable performance of CE >99% and capacity retention >90% after 285 cycles. In contrast, the DHAE‐based cell exhibits capacity retention of <65% after 170 cycles. [ABSTRACT FROM AUTHOR]