Study of Li Adsorption on Graphdiyne Using Hybrid DFT Calculations.

Promising applications of graphdiyne have often been initiated by theoretical predictions especially using DFT known as the most powerful first-principles electronic structure calculation method. However, there is no systematic study on the reliability of DFT for the prediction of the electronic properties of the graphdiyne. Here, we performed a study of Li adsorption on the graphdiyne using hybrid DFT with LC-ωPBE and compared the results with those of PBE, because accurate prediction of the Li adsorption is important for performance as a Li storage that was first theoretically suggested and then experimentally realized. Our results show that PBE overestimates the adsorption energy inside a pore and the barrier height at the transition state of in-plane diffusion compared to the those of LC-ωPBE. In particular, LC-ωPBE predicted almost barrier-less in-plane diffusion of Li on the graphdiyne because of the presence of both in-plane and out-of-plane π orbitals. Also, LC-ωPBE favors a high spin state due to the exact exchange energy when several Li atoms are adsorbed on the graphdiyne, whereas PBE favors a low spin state. Thus, the use of the hybrid DFT is critical for reliable predictions on the electronic properties of the graphdiyne.