Ab Initio Exploration of Energetically and Kinetically Favorable ORR Activity on a 1T-ZrO 2 Monolayer for a Nonaqueous Lithium-Oxygen Battery.

Herein, we explore the potential applications of the experimentally synthesized ZrO 2 monolayer as the cathode catalyst for nonaqueous lithium-oxygen batteries. First, we show that a new peroxide-like adsorption geometry is the most stable configuration for LiO 2 , which is distinct from the previously known O-Li-O triangular geometry. The proposed most stable adsorption configuration is because the Zr atoms in the substrate play a critical role in stabilizing the LiO 2 cluster. Second, our ab initio calculations indicate that both the ORR and OER catalytic activities are most likely to adopt the four-electron mechanism with a considerably low overpotential of only 0.44 and 0.76 V, respectively. Finally, we show that the adsorption energy of Li 2 O 2 is a good descriptor for both ORR and OER catalytic activities, and weak Li 2 O 2 adsorption behavior is positively related to low overpotentials and satisfactory catalytic performance.