Hybrid Solid Electrolyte Interphases Enabled Ultralong Life Ca-Metal Batteries Working at Room Temperature

Currently, the application of calcium metal anodes is challenged by rapidly degenerated plating/stripping electrochemistry without suitable solid electrolyte interphases (SEIs) capable of fast Ca²⁺ transport kinetics and superior ability to resist anion oxidation. Here, through in situ evolved Na/Ca hybrid SEIs, symmetrical Ca//Ca batteries readily remain stable for more than 1000 h deposition-dissolution cycles (versus less than 60 h for those with pure Ca SEIs under the same condition). Coupled with a specially designed freestanding lattice-expanded graphitic carbon fiber membrane and tailored operation voltages, the proof-of-concept Ca-metal batteries reversibly run for almost 1900 cycles with ≈83% capacity retention and a high average discharge voltage of 3.16 V. The good performance not only benefits from the stable SEIs at the Ca metal surface which affords free Ca²⁺ transports and prohibits out-of-control fluridation of Ca (forming CaF₂ ion-/electron-insulating layer) but is also attributed to reversible relay insertion/extraction electrochemistry in the cathode. This work sheds new light on durable metal battery technology.