A First-Principles Study of Lithium Adsorption and Diffusion on Graphene and Defective-Graphene as Anodes of Li-Ion Batteries

Defective graphene has emerged as a promising strategy to enhance electrochemical performance of pristine graphene (p-Gr) as anodes in lithium-ion batteries (LIBs). Herein, we perform a comprehensive first-principles study based on density functional theory (DFT) to systematically investigate the Li adsorption, charge transfer, and diffusion behaviors of p-Gr and defective graphene (d-Gr) with single vacancy (SV Gr) and double vacancy (DV5-8-5 Gr) defects, aiming to clarify the mechanism by which defects modulate Li storage performance. Structural optimization reveals that SV Gr undergoes notable out-of-plane distortion after Li adsorption, while DV5-8-5 Gr retains planar geometry but exhibits more significant C-C bond length variations compared to p-Gr. Binding energy results confirm that defects enhance Li adsorption stability, with DV5-8-5 Gr showing the strongest Li–graphene interaction, followed by SV Gr and p-Gr. Bader charge analysis and charge density difference plots further validate that defects enhance charge transfer from Li ions to graphene. Using the nudged elastic band (NEB) method, we find that defects reduce Li diffusion barriers: DV5-8-5 Gr exhibits a lower barrier than p-Gr. Our findings demonstrate that DV5-8-5 Gr exhibits the most favorable Li storage performance, providing a robust theoretical basis for designing high-performance graphene anodes for next-generation LIBs.