Li-air batteries can yield exceptionally high predicted energy densities. However, for this technology to become realizable, round-trip efficiency issues and slow kinetics at the cathode require implementation of a catalyst. With design parameters not well understood and limitations on material selection, choosing an ideal catalyst is complex. In Li-air batteries, energy storage is achieved by reactions between Li and O (oxygen reduction reaction for discharge and oxygen evolution reaction for charge). Here, phosphorene is proposed as a solution through simulations of its catalytic behavior toward discharge initiated via either O2 dissociation or Li adsorption. After obtaining intermediate geometries for both nucleation paths leading to either Li2O2 or 2(Li2O), free-energy diagrams are generated to predict the promoted discharge product of Li2O2. Furthermore, considering a final product of Li2O2, the overpotentials are predicted to be 1.44 V for discharge and 2.63 V for charge. Activation barriers for the catalytic decomposition of Li2O2 (during charge) are found to be 1.01 eV for phosphorene versus 2.06 eV for graphene. This leads to a major difference in reaction rate up to 1017 times in favor of phosphorene. These results, complemented by electronic analysis, establish phosphorene as a promising catalyst for Li-air batteries.
Keywords: 2D phosphorene; DFT; Li−air battery; NEB; catalysis; overpotential.