The effect of competition between solvation and cathode surface adsorption on the kinetics of lithium−oxygen batteries: A model study based on nanoarray electrodes

• Nanoarray models were prepared to explore cathode material and solvent effects . • Competition between solvation and adsorption determines the discharge mechanism. • The mechanism of strong-adsorption cathodes is determined by solvent donicities. • Weak-adsorption cathodes only exhibit a solution mechanism. The donor number (DN) of electrolyte solvents was reported to be the key factor determining LiO 2 intermediate solvation and lithium−oxygen battery (LOB) kinetics. In low-DN solvents, LiO 2 tends to adsorb onto cathode surfaces and undergoes surface-mediated reduction to Li 2 O 2 , while in high-DN solvents, LiO 2 is preferentially solvated and subsequently disproportionates to Li 2 O 2 . However, prior studies overlooked a critical issue: whether cathode surfaces can provide sufficiently strong adsorption for LiO 2 , particularly in low-DN solvents. Herein, this study proposes MnO 2 , NiO, and Co 3 O 4 nanoarray models alongside carbon nanotubes to simultaneously investigate LiO 2 adsorption on different cathodes and solvent DN effects under consistent cathode architectures. Experimental and theoretical analyses reveal that the discharge of oxygen cathodes involves a competition between the solvation of LiO 2 intermediates and their adsorption on cathodes. When an oxygen cathode has strong adsorption of LiO 2 , the adsorption and solvation compete with each other, leading to a solution mechanism in high-DN solvents and a surface mechanism in low-DN solvents. Conversely, if an oxygen cathode shows weak adsorption of LiO 2 , a solution mechanism predominately occurs, regardless of whether in high- or low-DN solvents. Thus, when evaluating solvent effects on LOB kinetics, the adsorption capacity of cathode materials must be fully considered.