Insight into the effect of fracture surfaces in graphdiyne on the anode performance for lithium ion batteries

Two-dimensional (2D) materials are promising anode materials for the next generation of lithium ion batteries. While the Li storage and kinetics at the surface and intercalation sites of 2D materials are widely explored, the effects of the fracture surfaces (FSs) are rarely considered despite the fact that there are numerous FSs in real 2D materials. Herein, we investigate how the FSs in graphdiyne (GDY) affect the anode performance based on first-principles calculations. Results show that both the internal and external FSs have much lower binding energies to Li atoms than perfect GDY, meaning FSs are more active in storing Li atoms. Then, the diffusion barriers of Li atoms on the internal and external FSs are only 0.42 and 0.47 eV, respectively, close to the 0.315 eV of surface sites and lower than the 0.638 eV of intercalation sites, indicating a good kinetics of Li atoms. In addition, due to the new electronic states from the C atoms with dangling bonds, the FSs convert the semiconductor characteristics of perfect GDY to metallic ones, which is helpful to the electronic conductivity. Our work demonstrates that the FSs in 2D materials are beneficial to the anode performance, which may enlighten the design of anode materials.