Alkynyl Boosted High‐Performance Lithium Storage and Mechanism in Covalent Phenanthroline Framework

The poor conductivity of the pristine bulk covalent organic material is the main challenge for its application in energy storage. The mechanism of symmetric alkynyl bonds (C≡C) in covalent organic materials for lithium storage is still rarely reported. Herein, a nanosized (≈80 nm) alkynyl‐linked covalent phenanthroline framework (Alkynyl‐CPF) is synthesized for the first time to improve the intrinsic charge conductivity and the insolubility of the covalent organic material in lithium‐ion batteries. Because of the high degree of electron conjugation along alkynyl units and N atoms from phenanthroline groups, the Alkynyl‐CPF electrodes with the lowest HOMO–LUMO energy gap (ΔE=2.629 eV) show improved intrinsic conductivity by density functional theory (DFT) calculations. As a result, the pristine Alkynyl‐CPF electrode delivers superior cycling performance with a large reversible capacity and outstanding rate properties (1068.0 mAh g−1 after 300 cycles at 100 mA g−1 and 410.5 mAh g−1 after 700 cycles at 1000 mA g−1). Moreover, by Raman, FT‐IR, XPS, EIS, and theoretical simulations, the energy‐storage mechanism of C≡C units and phenanthroline groups in the Alkynyl‐CPF electrode has been investigated. This work provides new strategies and insights for the design and mechanism investigation of covalent organic materials in electrochemical energy storage. An insoluble alkynyl‐linked covalent phenanthroline framework (Alkynyl‐CPF) is designed, the electronic structure of which can be tuned through the high degree of electron conjugation along alkynyl units and aromatic rings. The Alkynyl‐CPF electrode for lithium‐ion batteries demonstrates large reversible capacities and long cycle life.