Metal–Organic Frameworks Derived Electrolytes Build Multiple Wetting Interfaces for Integrated Solid‐State Lithium–Oxygen Battery

Abstract Solid‐state lithium–oxygen (Li–O 2 ) batteries are considered as the next‐generation solution for high‐safety energy storage systems to overcome the persistent problems associated with liquid battery systems. However, the absence of stable solid‐state electrolytes (SSEs) and the design complexity of functional solid‐state cathode (SSC) remains a fundamental challenge. Here, a high‐performance solid‐state Li–O 2 battery is presented with Li‐ion‐conducted UiO‐67 (UiO‐67‐Li) as SSEs and UiO‐67‐Li@reduced graphene oxide (rGO) aerogel integrated structure as SSC. The UiO‐67‐Li SSEs reveal exceptional conductivity (0.64 mS cm −1 at 25 °C) along with high chemical/electrochemical robustness. Furthermore, the prepared UiO‐67‐Li@rGO aerogel exhibits continuous and abundant Li + /e − transfer and O 2 diffusion channels. Benefiting from the unique chemical properties of the UiO‐67‐Li SSEs layer, the solid‐state Li–O 2 battery achieves suppression of anode dendrite formation, resistance to air‐corrosion, and presence of multiple low‐impedance wetting interfaces including anode/electrolyte and electrolyte/cathode. This ingenious arrangement endows the solid‐state Li–O 2 battery with low overpotential (0.8 V), superior rate capability, and stable cycling life (up to 115 cycles). This novel design and exciting result will open up one avenue for the development of MOF‐based SSEs and cathodes for high‐performance solid‐state Li–O 2 batteries and other solid‐state energy‐storage devices.