First-Principles Study of Discharge Products and Their Stability for Lithium-Nitrogen Batteries

Li-N₂ batteries present a relatively novel approach to N₂ immobilization, and an advanced N₂/Li₃N cycling method is introduced in this study. The low operating overpotential of metal-air batteries is quite favorable to their stable cycling performance, providing a prospect for the development of a new type of battery with extreme voltage. The battery system of Li-N₂ uses N₂ as the positive electrode, lithium metal as the negative electrode, and a conductive medium containing soluble lithium salts as the electrolyte. In accordance with its voltage-distribution trend, a variety of lithium-nitrogen molecule intermediates are produced during the discharge process. There is a lack of theoretical description of material changes at the microscopic level during the discharge process. In this paper, the first-principles approach is used to simulate and analyze possible material changes during the discharge process of Li-N₂ batteries. The discharge process is simulated on a 4N-graphene anode substrate model, and simulations of its electrostatic potential, Density of States (DOS), HOMO (Highest Occupied Molecular Orbital) and LUMO (Lowest Unoccupied Molecular Orbital) aspects confirm that the experimentally found Li₃N becomes the final stabilized product of the Li-N₂ battery. It can also be seen in the density of states that graphene with adsorption of 4N transforms from semiconducting to metallic properties. In addition, the differential charge also indicates that the Li-N₂ material has a strong adsorption effect on the substrate, which can play the dual role of electricity storage and nitrogen fixation.