Capacity-limiting mechanisms in Li/O2 batteries.

A continuum model of an aprotic lithium/oxygen battery is validated against experimental first-discharge data and used to examine how the apparent cell capacity is affected by macroscopic multicomponent mass transfer, interfacial kinetics, and electronic conduction or tunneling through the discharge product. The model accounts for the three-phase nature of the positive electrode in detail, including an explicit discharge-product layer whose properties and volume distribution generally depend on the local discharge depth. Several hypothetical positive-electrode reaction mechanisms involving different product morphologies and electron-transfer sites are explored within the theoretical framework. To match experimental discharge-voltage vs. capacity and capacity vs. discharge-current trends qualitatively, the discharge-product layer must be assumed to have electronic resistivity several orders of magnitude lower than typical insulators, supporting the notion that the presence of lithium peroxide does not wholly prevent electrons from reaching dissolved reactants. The discharge product also appears to allow charge transport over length scales longer than electron tunneling permits. 'Sudden death' of voltage in lithium/oxygen cells is explained by macroscopic oxygen-diffusion limitations in the positive electrode at high rates, and by pore clogging associated with discharge-product formation at low rates.