Abstract

Considering the lack of solid electrolytes that are electrochemically stable when in contact with a high-voltage cathode and a low-voltage metallic anode, bilayer separators in all-solid-state batteries are gaining increasing attention. However, previous studies have shown that the chemical reactivity between materials comprising the electrolyte bilayer is one of the contributing factors to the deterioration of battery performance during cycling. Here, we computationally screen the chemical compatibility of an extensive range of materials forming a bilayer separator using first-principles calculations. Notably, several bilayer separators are found to be thermodynamically stable; among them, the stability of the Li₃PO₄/Li₃InCl₆ pairing is further verified experimentally using a combination of X-ray diffraction, solid-state nuclear magnetic resonance, and X-ray photoelectron spectroscopy. This study underscores the importance of understanding the chemical compatibility of bilayer separators when engineering high-energy-density all-solid-state batteries.