▎ 摘　　要

van der Waals heterostructures can preserve the desired features of their individual components and induce new functions due to interlayer coupling. In this work, based on the dispersion-corrected density functional theory and vibrational analysis techniques, the blue phosphorene/graphene (BlueP/G) heterostructure was systematically studied as a potential anode for Li-ion batteries. It was found that the semi-metal characteristics of graphene are well preserved in the BlueP/G heterostructure, endowing it with excellent electrical conductance for fast electron transport. The binding energy of Li in the BlueP/G system is greatly increased due to the interfacial synergistic effect, as compared to pristine BlueP and graphene monolayers. Consequently, the theoretical specific capacity can be up to 626 mA h g(-1), even exceeding that of the black phosphorene/G heterostructure (485 mA h g(-1)). The minimum diffusion barrier of Li on the BlueP/G system is only 0.13 eV, resulting in a room-temperature diffusivity of 2.61 x 10(-5) cm(2) s(-1), which is two orders of magnitude faster than that on graphene. The impact of the vibrational contribution on the ionic diffusion is material-dependent and significant. More importantly, the BlueP/G heterostructure and its charge products display ultrahigh stiffness in the range of 353-422 N m(-1) and an extremely small effective volume expansion of 10.89% for the fully charged product, which might alleviate the safety concerns commonly associated with huge volume expansion/contraction upon lithiation. These results demonstrate that the BlueP/G heterostructure could be a promising anode material for high-performance Li-ion batteries due to its excellent conductivity, strong adsorption and fast diffusion of Li, high energy capacity, and ultrahigh mechanical stability.