Jiang Guoxing, Zou Wenwu, Ou Zhaoyuan, Zhang Weifeng, Huo Junlang, Qi Shengguang, Wang Liming, Du Li
Guangdong Provincial Key Laboratory of Fuel Cell Technology, School of Chemistry and Chemical Engineering, South China University of Technology, Guangzhou, 510641, China.
Guangdong Provincial Laboratory of Chemistry and Fine Chemical Engineering Jieyang Center, Jieyang, 515200, China.
Angew Chem Int Ed Engl. 2025 Mar 3;64(10):e202420333. doi: 10.1002/anie.202420333. Epub 2025 Feb 9.
Charged channels are considered an effective design for achieving efficient monovalent cation transport; however, it remains challenging to establish a direct relationship between charge microenvironments and ionic conductivity within the pores. Herein, we report a series of crystalline covalent organic frameworks (COFs) with identical skeletons but different charge microenvironments and explore their intra-pore charge-driven ion transport performance and mechanism differences. We found that the charged nature determines ion-pair action sites, modes, host-guest interaction, thereby influencing the dissociation efficiency of ion pairs, the hopping ability of cations, and the effective carrier concentration. The order of transport efficiency for Li, Na, and H follows anion > zwitterion > cation > neutrality. Ionic COFs exhibit up to 11-fold higher ionic conductivity than neutral COFs. Notably, the ionic conductivity of anionic COF achieves 2.0 × 10 S cm for Li at 30 °C and 3.8 × 10 S cm for H at 160 °C, surpassing most COF-based ionic conductors. This COF platform for efficient ion migration and stable battery cycling in lithium-metal quasi-solid-state batteries has also been verified as proof of concept. This work offers new insights into the development and structure-activity relationship studies of the next generation of solid-state ionic conductors.
带电通道被认为是实现高效单价阳离子传输的有效设计；然而，在孔内电荷微环境与离子电导率之间建立直接关系仍然具有挑战性。在此，我们报道了一系列具有相同骨架但不同电荷微环境的结晶共价有机框架（COF），并探索了它们的孔内电荷驱动离子传输性能和机理差异。我们发现，带电性质决定了离子对的作用位点、模式、主客体相互作用，从而影响离子对的解离效率、阳离子的跳跃能力和有效载流子浓度。Li、Na和H的传输效率顺序为阴离子>两性离子>阳离子>中性。离子型COF的离子电导率比中性COF高11倍。值得注意的是，阴离子型COF在30°C时Li的离子电导率达到2.0×10 S cm，在160°C时H的离子电导率达到3.8×10 S cm，超过了大多数基于COF的离子导体。这种用于锂金属准固态电池中高效离子迁移和稳定电池循环的COF平台也已作为概念验证得到验证。这项工作为下一代固态离子导体的开发和结构-活性关系研究提供了新的见解。
