Engineering a High-Voltage Durable Cathode/Electrolyte Interface for All-Solid-State Lithium Metal Batteries via In Situ Electropolymerization

Poly(ethylene oxide) (PEO)-based polymer electrolytes have been widely studied as a result of their flexibility, excellent interface contact, and high compatibility with a lithium metal anode. Owing to the poor oxidation resistance of ethers, however, the PEO-based electrolytes are only compatible with low-voltage cathodes, which limits their energy density. Here, a high-voltage stable solid-state interface layer based on polyfluoroalkyl acrylate was constructed via in situ solvent-free bulk electropolymerization between the LiNi_0.8Mn_0.1Co_0.1O₂ (NCM811) cathode and the PEO-based solid polymer electrolyte. The electrochemical oxidation window of the as-synthesized electrolyte was therefore expanded from 4.3 V for the PEO-based matrix electrolyte to 5.1 V, and the ionic conductivity was improved to 1.02 × 10^-4 S cm^-1 at ambient temperature and 4.72 × 10^-4 S cm^-1 at 60 °C as a result of the improved Li⁺ migration. This fabrication process for the interface buffer layer by an in situ electrochemical process provides an innovative and universal interface engineering strategy for high-performance and high-energy-density solid-state batteries, which has not been explicitly discussed before, paving the way toward the large-scale production of the next generation of solid-state lithium batteries.