Precise Regulation of Intra‐Nanopore Charge Microenvironment in Covalent Organic Frameworks for Efficient Monovalent Cation Transport

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^-4 S cm^-1 for Li⁺ at 30 °C and 3.8 × 10^-2 S cm^-1 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.