Steering lithium and potassium storage mechanism in covalent organic frameworks by incorporating transition metal single atoms

Organic electrodes mainly consisting of C, O, H, and N are promising candidates for advanced batteries. However, the sluggish ionic and electronic conductivity limit the full play of their high theoretical capacities. Here, we integrate the idea of metal-support interaction in single-atom catalysts with π–d hybridization into the design of organic electrode materials for the applications of lithium (LIBs) and potassium-ion batteries (PIBs). Several types of transition metal single atoms (e.g., Co, Ni, Fe) with π–d hybridization are incorporated into the semiconducting covalent organic framework (COF) composite. Single atoms favorably modify the energy band structure and improve the electronic conductivity of COF. More importantly, the electronic interaction between single atoms and COF adjusts the binding affinity and modifies ion traffic between Li/K ions and the active organic units of COFs as evidenced by extensive in situ and ex situ characterizations and theoretical calculations. The corresponding LIB achieves a high reversible capacity of 1,023.0 mA h g −1 after 100 cycles at 100 mA g −1 and 501.1 mA h g −1 after 500 cycles at 1,000 mA g −1 . The corresponding PIB delivers a high reversible capacity of 449.0 mA h g −1 at 100 mA g −1 after 150 cycles and stably cycled over 500 cycles at 1,000 mA g −1 . This work provides a promising route to engineering organic electrodes.