Abstract
Lithium-oxygen has one of the highest specific energies among known electrochemical couples and holds the promise of substantially boosting the energy density of portable batteries. Mechanistic knowledge of oxygen electroreduction by Li is scarce at the present time, and the factors limiting the discharge and charge efficiencies of the Li-oxygen cathode are not understood. To shed light on the fundamental surface chemistry of this oxygen reduction
reaction by Li (Li-ORR), we have performed periodic density functional theory calculations in conjunction with thermodynamic modeling for two metal surfaces, Au(111) and Pt(111). The inertness of Au(111) results in a low reversible potential of 1.51 V for initial O2 reduction via superoxide (LiO2). On Pt(111), initially the dissociative adsorption of O2 is rapid and reduction
involves atomic O with a reversible potential of 1.76 V, whereas the associative LiO2 channel (at 1.93 V) is expected to dominate once O2 dissociation becomes hindered by surface species. On both Au(111) and Pt(111) the lithiation of O2 significantly weakens the O-O bond, and so the selectivity of the Li-ORR products is mainly to monoxides (LixO), not peroxides (LixO2). LixO units are energetically driven to form (LixO)n aggregates, and the interfaces between (LixO)n and the metal surfaces are found also to be active sites for stabilizing LiO2 and dissociating the O-O bond. During cycling, an oxygen reduction half-cycle is expected to begin with the reduction of atomic O instead of O2 at steady state. On Au(111) this occurs at 2.27 V, whereas the greater stability of O on Pt(111) lowers the reversible potential to a maximum of 1.93 V, being limited by the delithaition of (LixO)n products to atomic O. Therefore the intrinsic reactivity of Pt(111) renders it less effective for Li-ORR than Au(111).