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Vol. 17 (2025)

Constructing Donor–Acceptor-Linked COFs Electrolytes to Regulate Electron Density and Accelerate the Li+ Migration in Quasi-Solid-State Battery

https://doi.org/10.1007/s40820-024-01509-y
Genfu Zhao
School of Materials and Energy, International Joint Research Center for Advanced Energy Materials of Yunnan Province, Yunnan University, Kunming 650091, People’s Republic of China
Hang Ma
Yunnan Yuntianhua Co., Ltd, R & D Center, Kunming 650228, People’s Republic of China
Conghui Zhang
School of Materials and Energy, International Joint Research Center for Advanced Energy Materials of Yunnan Province, Yunnan University, Kunming 650091, People’s Republic of China
Yongxin Yang
School of Materials and Energy, International Joint Research Center for Advanced Energy Materials of Yunnan Province, Yunnan University, Kunming 650091, People’s Republic of China
Shuyuan Yu
School of Materials and Energy, International Joint Research Center for Advanced Energy Materials of Yunnan Province, Yunnan University, Kunming 650091, People’s Republic of China
Haiye Zhu
School of Materials and Energy, International Joint Research Center for Advanced Energy Materials of Yunnan Province, Yunnan University, Kunming 650091, People’s Republic of China
Yongjiang Sun
School of Materials and Energy, International Joint Research Center for Advanced Energy Materials of Yunnan Province, Yunnan University, Kunming 650091, People’s Republic of China
Hong Guo
School of Materials and Energy, International Joint Research Center for Advanced Energy Materials of Yunnan Province, Yunnan University, Kunming 650091, People’s Republic of China

Corresponding Author: Hong Guo

guohong@ynu.edu.cn

Nano-Micro Letters, Vol. 17 (2025), Article Number: 21

Abstract

Regulation the electronic density of solid-state electrolyte by donor–acceptor (D–A) system can achieve highly-selective Li+ transportation and conduction in solid-state Li metal batteries. This study reports a high-performance solid-state electrolyte thorough D–A-linked covalent organic frameworks (COFs) based on intramolecular charge transfer interactions. Unlike other reported COF-based solid-state electrolyte, the developed concept with D–A-linked COFs not only achieves electronic modulation to promote highly-selective Li+ migration and inhibit Li dendrite, but also offers a crucial opportunity to understand the role of electronic density in solid-state Li metal batteries. The introduced strong electronegativity F-based ligand in COF electrolyte results in highly-selective Li+ (transference number 0.83), high ionic conductivity (6.7 × 10–4 S cm−1), excellent cyclic ability (1000 h) in Li metal symmetric cell and high-capacity retention in Li/LiFePO4 cell (90.8% for 300 cycles at 5C) than substituted C- and N-based ligands. This is ascribed to outstanding D–A interaction between donor porphyrin and acceptor F atoms, which effectively expedites electron transferring from porphyrin to F-based ligand and enhances Li+ kinetics. Consequently, we anticipate that this work creates insight into the strategy for accelerating Li+ conduction in high-performance solid-state Li metal batteries through D–A system.


Highlights:
1 Donor–acceptor-linked covalent organic framework (COF)-based electrolyte can not only fulfill highly-selective Li+ conduction, but also offer a crucial opportunity to understand the role of electronic density in quasi-solid-state Li metal batteries.
2 Donor–acceptor-linked COF electrolyte results in Li+ transference number 0.83, high ionic conductivity 6.7 × 10–4 S cm−1 and excellent cyclic ability in Li metal batteries.
3 In situ characterizations, density functional theory calculation and time-of-flight secondary ion mass spectrometry are adopted to expound the mechanism of the rapid migration of Li+ in the “donor–acceptor” electrolyte system.

Keywords

Electronic modulation engineering Donor–acceptor-linked covalent organic frameworks Quasi-solid-state Li metal battery
Zhao, Genfu, Hang Ma, Conghui Zhang, Yongxin Yang, Shuyuan Yu, Haiye Zhu, Yongjiang Sun, and Hong Guo. 2024. “Constructing Donor–Acceptor-Linked COFs Electrolytes to Regulate Electron Density and Accelerate the Li+ Migration in Quasi-Solid-State Battery”. Nano-Micro Letters 17 (September):21. https://doi.org/10.1007/s40820-024-01509-y.
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