Flame-retardant in-situ formed gel polymer electrolyte with different valance states of phosphorus structures for high-performance and fire-safety lithium-ion batteries

Lithium-ion batteries (LIBs) have been widely used today owing to portability, high energy storage, and reusability. However, commercial liquid electrolytes in LIBs possess intensive mobility and terrible flammability. Accordingly, leakage, combusting, and even exploding can frequently occur when LIBs work under abuse conditions. Herein, a novel flame-retardant gel polymer electrolyte (GPE) containing + 3 and + 5 phosphorus valence states of phosphorus structures was designed by in-situ thermal polymerization of tri(acryloyloxyethyl) phosphate (TAEP), diethyl vinylphosphonate (DEVP), and pentaerythritol tetraacrylate in electrolytes. After being ignited by fire, this GPE extinguished quickly with a combusting time of only 0.9 s, showing much lower flammability. Besides, the GPE is compatible with graphite anode, LiFePO₄ (LFP), and even LiNi_0.8Co_0.1Mn_0.1O₂ (NCM811) cathodes. The as-assembled LFP and NCM811-based pouch cells (1 Ah-type) with TD-GPE achieved stable cycling, maintaining 88.52 % and 95.2 % of the initial capacities, respectively after 200 and 190 cycles at 0.5C. Moreover, the as-prepared TD-GPE dramatically reduced the fire hazard of NCM811 batteries without sacrificing the electrochemical performance. The thermal abuse test demonstrates that the leakage and combustion of NCM811||TD-GPE||Graphite pouch cell could be significantly suppressed in the test process, indicating that battery safety improves significantly via the combined use of different phosphorus valence structures. This is because the + 5 phosphorus valence of TAEP promoted the formation of carbon layers, and the + 3 phosphorus structure in DEVP captured free radicals by quenching effect. This work paves a different path for designing safe and high-performance GPEs in LIBs based on gaseous-phase and condensed-phase mechanisms. © 2024 Published by Elsevier B.V.