POS10-1547
Molecular Insights into Temperature-Dependent Interfacial Decomposition of Elastomeric Electrolytes in Lithium Metal Batteries
Topic
S10. AI-assisted Design and Simulation of Polymers
When and Where
Sep 30, 2026
08:30 - 09:30
Room 301 (Grand Ballroom)
Session Chairs
Heesuk KIM
Jinhye BAE
Presenter(s)
Junsu Son (Hanyang University)
Co-Author(s)
Abstract
Lithium metal batteries (LMBs) offer high energy density. However, their performance under low-temperature conditions is limited by unstable solid electrolyte interphases (SEIs) and sluggish interfacial Li+ transport. These limitations can increase polarization and accelerate the formation of lithium dendrites, leading to rapid performance degradation. Fluorinated polymer electrolytes are promising because their decomposition can promote the formation of robust lithium fluoride (LiF)-rich SEIs, thereby stabilizing the lithium metal interface and suppressing undesirable side reactions. However, the molecular mechanisms governing the temperature-dependent decomposition of fluorinated polymer electrolytes remain poorly understood. In this study, we investigated the effect of formation temperature on the interfacial decomposition behavior of a hexafluorobutyl acrylate (HFBA)-based elastomer matrix at the lithium metal surface using multiscale molecular simulations. Molecular dynamics simulations revealed that lower temperature increased the interfacial accumulation of poly(HFBA)-derived fluorinated moieties near the lithium metal surface by suppressing polymer chain mobility, thereby enhancing interactions between the polymer and the lithium metal surface. Ab initio molecular dynamics simulations further demonstrated that C-F bond cleavage in poly(HFBA) was promoted at low temperature, accompanied by earlier decomposition events and more extensive bond-breaking reactions. These atomistic findings indicate that a low formation temperature promotes the interfacial decomposition of fluorinated polymer electrolytes by enhancing interfacial contact and accelerating bond dissociation, providing computational guidelines for engineering LiF-rich SEIs and improving the stability of LMBs.
