High Quality Pyrazinoquinoxaline-Based Graphdiyne for Efficient Gradient Storage of Lithium Ions

N-doping of graphdiyne with atomic precision is very important for the study of heteroatom doping effect and the structure–properties relationships of graphdiyne. Here we report the bottom-up synthesis and characterizations of high-quality pyrazinoquinoxaline-based graphdiyne (PQ-GDY) film. First-principle studies of the layered structure were performed to examine the stacking mode, lithium binding affinity, and bulk lithium storage capacity. Three-stage insertion of 14 lithium atoms with binding affinities in the order of pyrazine nitrogen > diyne carbon > central aromatic ring were confirmed by both lithium-ion half-cell measurements and DFT calculations. More than half of the lithium atoms preferentially bind to pyrazine nitrogen, and a reversible capacity of 570.0 mA h g–1 at a current density of 200 mA g–1 after 800 cycles was achieved. Such a high capacity utilization rate of 97.2% provides a good case study of N-doped GDY with atomic precision.