High-Performance Aqueous Calcium Ion Batteries Enabled by Zn Metal Anodes with Stable Ion-Conducting Interphases

Aqueous calcium ion batteries, promising for energy storage, are still challenged by very limited anode choices. Although a Zn metal anode is popular in aqueous batteries, interface instability due to incessant corrosion and severe Zn dendrites hinders its development. Here, an interphase layer with densely packed nanocrystals of Ca₃(CO₃)₂(OH)₂·1.5H₂O and ZnF₂, and amorphous organic species, is demonstrated for a Zn metal anode with 1 M calcium trifluoromethyl sulfonate aqueous electrolyte. The hybrid interface fully avoids direct Zn-H₂O contact, maintains fast ion conductivity, and effectively prevents corrosion and dendrite growth. Therefore, the symmetric cell stably lasts for 1600 h at 0.5 mA cm^-2 and 2.5 mAh cm^-2, far superior to 150 h for the control cell. Furthermore, the device maintains 80% capacity retention after 700 cycles at 1 A g^-1, outperforming 13% retention after 200 cycles for the control device. This work indicates that interface and interphase engineering is also crucial for aqueous batteries.