Li-O₂ kinetic overpotentials: Tafel plots from experiment and first-principles theory

We report the current dependence of the fundamental kinetic overpotentials for Li-O₂ discharge and charge (Tafel plots) that define the optimal cycle efficiency in a Li-air battery. Comparison of the unusual experimental Tafel plots obtained in a bulk electrolysis cell with those obtained by first-principles theory is semiquantitative. The kinetic overpotentials for any practical current density are very small, considerably less than polarization losses due to iR drops from the cell impedance in Li-O₂ batteries. If only the kinetic overpotentials were present, then a discharge-charge voltaic cycle efficiency of ∼85% should be possible at ∼10 mA/cm² superficial current density in a battery of ∼0.1 m² total cathode area. We therefore suggest that minimizing the cell impedance is a more important problem than minimizing the kinetic overpotentials to develop higher current Li-air batteries.