▎ 摘　　要

In this work, the Li ordering and its influence on Li intercalation and plating on graphite, bilayer, and single-layer graphene are investigated by first-principles calculation with two-dimensional cluster expansion and van der Waals corrections. The results show that Li intercalation has a multistage feature for graphite and bilayer graphene at Li concentrations from C-2 to LiC6. Beyond LiC6, Li atoms are crowded in graphite and bilayer graphene, resulting in a negative discharge voltage. The calculated overpotential indicates Li plating easily happens on graphite but is unlikely on bilayer graphene. For single-layer graphene, Li atoms uniformly cover the graphene surface from C-2 to LiC4 with the presence of voltage stages, while forming an atomic island at a higher Li concentration. Our findings not only give a good recount on recent Li plating phenomena in Li-ion batteries but also provide a rationale for circumventing those side reactions on graphene and its variants.& nbsp;Published under an exclusive license by AIP Publishing.