Lithium Bromide-Induced Organic-Rich Cathode/Electrolyte Interphase for High-Voltage and Flame-Retardant All-Solid-State Lithium Batteries

Poly(ethylene oxide) (PEO)-based solid electrolyte suffers from limited anodic stability and an intrinsic flammable issue, hindering the achievement of high energy density and safe all-solid-state lithium batteries. Herein, we surprisingly found out that a bromine-rich additive, decabromodiphenyl ethane (DBDPE), could be preferably oxidized at an elevated voltage and decompose to lithium bromide at an elevated potential followed by inducing an organic-rich cathode/electrolyte interphase (CEI) on NCM811 surface, enabling both high-voltage resistance (up to 4.5 V) and flame-retardancy for the PEO-based electrolyte. On the basis of this novel solid electrolyte, all-solid-state Li/NCM811 batteries deliver an average reversible capacity of 151.4 mAh g–1 over the first 150 cycles with high capacity retention (83.0%) and high average Coulombic efficiency (99.7%) even at a 4.5 V cutoff voltage with a unprecedented flame-retardant properties. In view of these exploration, our studies revealed the critical role of LiBr in inducing an organic-rich thin and uniform CEI passivating layer with enhanced lithium ion surface diffusion and high-voltage resistant properties, which provides a new protocol for the further design of a high-voltage PEO-based all-solid-state electrolyte.