First-Principles Study of Nitrogen-, Boron-Doped Graphene and Co-Doped Graphene as the Potential Catalysts in Nonaqueous Li–O₂ Batteries

Abstract

In this work, we perform a first-principles study of graphene, nitrogen-, boron-doped graphene, and codoped graphene as the potential catalysts in nonaqueous lithium− oxygen (Li−O 2 ) batteries. Among the samples studied, borondoped graphene exhibits the lowest discharge and charge overpotentials, suggesting that boron-doped graphene is the best catalyst for both the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER) in nonaqueous Li− O 2 batteries. Another significant finding is that codoping of nitrogen and boron atoms does not enhance the ORR/OER in the presence of lithium atoms, indicating that the synergistic effect in the presence of protons does not appear in nonaqueous Li−O 2 batteries. This behavior is attributed to the fact that the existence of lithium atoms can change the most stable adsorption sites and adsorption energies of intermediates. Finally, on the basis of our calculation results, we propose that the adsorption energy of intermediates in the rate-determining step (RDS) can be the descriptor of the overpotential, and the lower adsorption energy in RDS represents the lower overpotential. The findings reported in this work contribute to the understanding of the ORR/OER in nonaqueous Li−O 2 batteries and provide useful insight into the catalyst design.

Understanding Rechargeable Li−O2 Batteries via First‐Principles Computations

“…These results indicate that graphene/ Cu is an excellent catalyst towards both ORR and OER in LiÀO 2 batteries. Then, Tu et al [50] reported that the catalyst of Ndoped graphene shell encapsulating Co is promising for LiÀO 2 batteries and the prediction was confirmed in experiments. Lee et al [51] reported that h-BN/Ni(111) can be a good cathode catalyst for LiÀO 2 batteries.…”

“…Jing and Zhou [45] systematically investigated the initial ORR processes on the surface of various kinds of N-doped (graphitic N, pyridinic N, and pyrrolic-like N) graphene ( Figure 5) in comparison with those on the pristine graphene based on DFT computations. Jiang et al [48] also reported that B-doped graphene is a good catalyst for LiÀO 2 batteries. The in-plane pyridinic N could reduce the overpotential more effectively than the graphitic N, facilitating the nucleation of Li 2 O 2 , which can be attributed to the electron-withdrawing configurations.…”

Computational electrochemistry of doped graphene as electrocatalytic material in fuel cells

“…The first pioneering computational studies on chemically modified graphene as an electrocatalyst focus on the nitrogen‐doped graphene, but suggests that chemical doping, in general, could be one of the key factors to build an excellent carbon‐based electrocatalyst. Indeed, further computational studies on O 2 adsorption, which is the first step of ORR, or on the full electrochemical process, have followed dealing with both metal and non‐metal impurities, edges as well as carbon vacancies . For example, bulk‐substituted N‐doped graphene was found to require an overpotential for ORR of 0.72 V, while edge‐substituted N‐doped nanoribbons are characterized by lower overpotentials both for ORR and OER .…”

MnCo2O4/MoO2 Nanosheets Grown on Ni foam as Carbon‐ and Binder‐Free Cathode for Lithium–Oxygen Batteries

“…[9][10][11][12] However,t he discharge products,s uch as Li 2 O 2 and LiO 2 ,c ould react with carbon to form an insulating lithium carbonate layer,r esulting in cathode passivation and capacity fading in Li-O 2 batteries. [9][10][11][12] However,t he discharge products,s uch as Li 2 O 2 and LiO 2 ,c ould react with carbon to form an insulating lithium carbonate layer,r esulting in cathode passivation and capacity fading in Li-O 2 batteries.…”

“…Carbon-basedm aterials, ap romising candidate for the air electrode, have been extensivelys tudied. [9][10][11][12] However,t he discharge products,s uch as Li 2 O 2 and LiO 2 ,c ould react with carbon to form an insulating lithium carbonate layer,r esulting in cathode passivation and capacity fading in Li-O 2 batteries. [13,14] This problem can be circumvented by replacing carbon with other noncarbonm aterials.…”