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Vol. 17 (2025)

In Situ Polymerization in COF Boosts Li-Ion Conduction in Solid Polymer Electrolytes for Li Metal Batteries

https://doi.org/10.1007/s40820-025-01768-3
Junchen Meng
Key Laboratory of Material Chemistry for Energy Conversion and Storage, Ministry of Education, Hubei Key Laboratory of Material Chemistry and Service Failure, School of Chemistry and Chemical Engineering, Huazhong University of Science and Technology, Wuhan 430074, People’s Republic of China
Mengjia Yin
Key Laboratory of Material Chemistry for Energy Conversion and Storage, Ministry of Education, Hubei Key Laboratory of Material Chemistry and Service Failure, School of Chemistry and Chemical Engineering, Huazhong University of Science and Technology, Wuhan 430074, People’s Republic of China
Kairui Guo
Key Laboratory of Material Chemistry for Energy Conversion and Storage, Ministry of Education, Hubei Key Laboratory of Material Chemistry and Service Failure, School of Chemistry and Chemical Engineering, Huazhong University of Science and Technology, Wuhan 430074, People’s Republic of China
Xingping Zhou
Key Laboratory of Material Chemistry for Energy Conversion and Storage, Ministry of Education, Hubei Key Laboratory of Material Chemistry and Service Failure, School of Chemistry and Chemical Engineering, Huazhong University of Science and Technology, Wuhan 430074, People’s Republic of China
Zhigang Xue
Key Laboratory of Material Chemistry for Energy Conversion and Storage, Ministry of Education, Hubei Key Laboratory of Material Chemistry and Service Failure, School of Chemistry and Chemical Engineering, Huazhong University of Science and Technology, Wuhan 430074, People’s Republic of China

Corresponding Author: Zhigang Xue

zgxue@mail.hust.edu.cn

Nano-Micro Letters, Vol. 17 (2025), Article Number: 248

Abstract

Solid polymer electrolytes (SPEs) have garnered considerable interest in the field of lithium metal batteries (LMBs) owing to their exceptional mechanical strength, excellent designability, and heightened safety characteristics. However, their inherently low ion transport efficiency poses a major challenge for their application in LMBs. To address this issue, covalent organic framework (COF) with their ordered ion transport channels, chemical stability, large specific surface area, and designable multifunctional sites has shown promising potential to enhance lithium-ion conduction. Here, we prepared an anionic COF, TpPa-COOLi, which can catalyze the ring-opening copolymerization of cyclic lactone monomers for the in situ fabrication of SPEs. The design leverages the high specific surface area of COF to facilitate the absorption of polymerization precursor and catalyze the polymerization within the pores, forming additional COF-polymer junctions that enhance ion transport pathways. The partial exfoliation of COF achieved through these junctions improved its dispersion within the polymer matrix, preserving ion transport channels and facilitating ion transport across COF grain boundaries. By controlling variables to alter the crystallinity of TpPa-COOLi and the presence of –COOLi substituents, TpPa-COOLi with partial long-range order and –COOLi substituents exhibited superior electrochemical performance. This research demonstrates the potential in constructing high-performance SPEs for LMBs.


Highlights:
1 Solid polymer electrolytes formed in situ via covalent organic framework-induced ring-opening copolymerization.
2 Solid polymer electrolytes with a high lithium-ion transference number and desirable interfacial compatibility.
3 Li⁺ migration mechanisms investigated with density functional theory and molecular dynamics simulations.

Keywords

Covalent organic framework In situ polymerization Ring-opening polymerization Solid polymer electrolyte Lithium metal batteries
Meng, Junchen, Mengjia Yin, Kairui Guo, Xingping Zhou, and Zhigang Xue. 2025. “In Situ Polymerization in COF Boosts Li-Ion Conduction in Solid Polymer Electrolytes for Li Metal Batteries”. Nano-Micro Letters 17 (May):248. https://doi.org/10.1007/s40820-025-01768-3.
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