Issue

Vol. 17 (2025)

Molecule-Level Multiscale Design of Nonflammable Gel Polymer Electrolyte to Build Stable SEI/CEI for Lithium Metal Battery

https://doi.org/10.1007/s40820-024-01508-z
Qiqi Sun
Key Laboratory for Liquid‑Solid Structural Evolution and Processing of Materials (Ministry of Education), School of Materials Science and Engineering, Shandong University, Jinan 250061, People’s Republic of China
Zelong Gong
Key Laboratory for Liquid‑Solid Structural Evolution and Processing of Materials (Ministry of Education), School of Materials Science and Engineering, Shandong University, Jinan 250061, People’s Republic of China
Tao Zhang
Key Laboratory for Liquid‑Solid Structural Evolution and Processing of Materials (Ministry of Education), School of Materials Science and Engineering, Shandong University, Jinan 250061, People’s Republic of China
Jiafeng Li
Key Laboratory for Liquid‑Solid Structural Evolution and Processing of Materials (Ministry of Education), School of Materials Science and Engineering, Shandong University, Jinan 250061, People’s Republic of China
Xianli Zhu
Key Laboratory for Liquid‑Solid Structural Evolution and Processing of Materials (Ministry of Education), School of Materials Science and Engineering, Shandong University, Jinan 250061, People’s Republic of China
Ruixiao Zhu
Key Laboratory for Liquid‑Solid Structural Evolution and Processing of Materials (Ministry of Education), School of Materials Science and Engineering, Shandong University, Jinan 250061, People’s Republic of China
Lingxu Wang
Key Laboratory for Liquid‑Solid Structural Evolution and Processing of Materials (Ministry of Education), School of Materials Science and Engineering, Shandong University, Jinan 250061, People’s Republic of China
Leyuan Ma
Key Laboratory for Liquid‑Solid Structural Evolution and Processing of Materials (Ministry of Education), School of Materials Science and Engineering, Shandong University, Jinan 250061, People’s Republic of China
Xuehui Li
Key Laboratory for Liquid‑Solid Structural Evolution and Processing of Materials (Ministry of Education), School of Materials Science and Engineering, Shandong University, Jinan 250061, People’s Republic of China
Miaofa Yuan
Key Laboratory for Liquid‑Solid Structural Evolution and Processing of Materials (Ministry of Education), School of Materials Science and Engineering, Shandong University, Jinan 250061, People’s Republic of China
Zhiwei Zhang
Key Laboratory for Liquid‑Solid Structural Evolution and Processing of Materials (Ministry of Education), School of Materials Science and Engineering, Shandong University, Jinan 250061, People’s Republic of China
Luyuan Zhang
Key Laboratory for Liquid‑Solid Structural Evolution and Processing of Materials (Ministry of Education), School of Materials Science and Engineering, Shandong University, Jinan 250061, People’s Republic of China
Zhao Qian
Key Laboratory for Liquid‑Solid Structural Evolution and Processing of Materials (Ministry of Education), School of Materials Science and Engineering, Shandong University, Jinan 250061, People’s Republic of China
Longwei Yin
Key Laboratory for Liquid‑Solid Structural Evolution and Processing of Materials (Ministry of Education), School of Materials Science and Engineering, Shandong University, Jinan 250061, People’s Republic of China
Rajeev Ahuja
Condensed Matter Theory, Department of Physics and Astronomy, Uppsala University, Uppsala 75120, Sweden
Chengxiang Wang
Key Laboratory for Liquid‑Solid Structural Evolution and Processing of Materials (Ministry of Education), School of Materials Science and Engineering, Shandong University, Jinan 250061, People’s Republic of China

Corresponding Author: Chengxiang Wang

wcxmat@sdu.edu.cn

Nano-Micro Letters, Vol. 17 (2025), Article Number: 18

Abstract

The risk of flammability is an unavoidable issue for gel polymer electrolytes (GPEs). Usually, flame-retardant solvents are necessary to be used, but most of them would react with anode/cathode easily and cause serious interfacial instability, which is a big challenge for design and application of nonflammable GPEs. Here, a nonflammable GPE (SGPE) is developed by in situ polymerizing trifluoroethyl methacrylate (TFMA) monomers with flame-retardant triethyl phosphate (TEP) solvents and LiTFSI–LiDFOB dual lithium salts. TEP is strongly anchored to PTFMA matrix via polarity interaction between -P = O and -CH2CF3. It reduces free TEP molecules, which obviously mitigates interfacial reactions, and enhances flame-retardant performance of TEP surprisingly. Anchored TEP molecules are also inhibited in solvation of Li+, leading to anion-dominated solvation sheath, which creates inorganic-rich solid electrolyte interface/cathode electrolyte interface layers. Such coordination structure changes Li+ transport from sluggish vehicular to fast structural transport, raising ionic conductivity to 1.03 mS cm−1 and transfer number to 0.41 at 30 °C. The Li|SGPE|Li cell presents highly reversible Li stripping/plating performance for over 1000 h at 0.1 mA cm−2, and 4.2 V LiCoO2|SGPE|Li battery delivers high average specific capacity > 120 mAh g−1 over 200 cycles. This study paves a new way to make nonflammable GPE that is compatible with Li metal anode.


Highlights:
1 Nonflammable gel polymer electrolyte (SGPE) is developed by in situ polymerizing trifluoroethyl methacrylate (TFMA) monomers with flame-retardant triethyl phosphate (TEP) solvents and LiTFSI–LiDFOB dual lithium salts.
2 Molecular polarity interaction between TEP and PTFMA mitigates interfacial reactions and changes the solvation of Li+.
3 SGPE forms stable inorganic-rich solid electrolyte interface/cathode electrolyte interface layer, exhibiting well compatibility with Li anode and LiCoO2-type high-voltage cathode.

Keywords

Anchoring effect Nonflammable gel electrolyte In situ cross-linked Electrode–electrolyte interface Li metal battery
Sun, Qiqi, Zelong Gong, Tao Zhang, Jiafeng Li, Xianli Zhu, Ruixiao Zhu, Lingxu Wang, Leyuan Ma, Xuehui Li, Miaofa Yuan, Zhiwei Zhang, Luyuan Zhang, Zhao Qian, Longwei Yin, Rajeev Ahuja, and Chengxiang Wang. 2024. “Molecule-Level Multiscale Design of Nonflammable Gel Polymer Electrolyte to Build Stable SEI/CEI for Lithium Metal Battery”. Nano-Micro Letters 17 (September):18. https://doi.org/10.1007/s40820-024-01508-z.
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