Donald Siegel

Abstract:

The mechanisms and efficiency of charge transport in lithium peroxide (Li2O2) are key factors in understanding the performance of non-aqueous Li-air batteries. Towards revealing these mechanisms, we use first-principles calculations to predict the concentrations and mobilities of charge carriers in Li2O2 as a function of cell voltage. Our calculations reveal that changes in the charge state of O2 dimers control the defect chemistry and conductivity of Li2O2. Negative lithium vacancies and small hole polarons are identified as the dominant charge carriers. The electronic conductivity associated with polaron hopping (10-20 S/cm) is comparable to the ionic conductivity arising from the migration of Li-ions (10-19 S/cm), suggesting that charge transport in Li2O2 occurs through a mixture of ionic and polaronic contributions. These data indicate that the bulk regions of crystalline Li2O2 are insulating, with appreciable charge transport occurring only at moderately high charging potentials that drive partial delithiation. The implications of limited charge transport on discharge and recharge mechanisms are discussed, and a two-stage charging process linking charge transport, discharge product morphology, and overpotentials are described. We conclude that achieving both high discharge capacities and efficient charging will depend upon access to mechanisms that bypass bulk charge transport.