Hydrogen-Bond-Mediated In Situ Polymerization Enables High-Voltage PDOL-Based Solid-State Lithium Batteries

Abstract The practical deployment of poly(1,3-dioxolane) (PDOL) electrolytes is hindered by traditional Lewis acid-catalyzed 1,3-dioxolane polymerization, which cannot achieve precise control over the polymerization process to adapt to high-voltage cathodes. Hence, we developed a hydrogen-bond-mediated in situ polymerization approach through hydrogen bonds between LiTFSI and the interlayer crystalline water in zirconium phosphate (ZP), which induces proton transfer to boost Brønsted acidity of ZP, eventually enabling the controllable PDOL polymerization and establishing a correlation among molecular weight, monomer residue, and high-voltage performance. Ultimately, the PDOL-ZP electrolyte possesses a wide voltage window up to 5.0 V due to a uniform long-chain macromolecular structure, an extremely low polydispersity index (1.45), and a high polymerization conversion of 91.2%, which enables the stable cycling of high-voltage solid-state lithium batteries. This work offers a new solution for the hydrogen-bond-mediated in situ polymerization of solid-state electrolytes.