Light-Assisted Li-O₂ Batteries with Lowered Bias Voltages by Redox Mediators

The enormous overpotential caused by sluggish kinetics of the oxygen reduction reaction and the oxygen evolution reaction prevents the practical application of Li-O₂ batteries. The recently proposed light-assisted strategy is an effective way to improve round-trip efficiency; however, the high-potential photogenerated holes during the charge would degrade the electrolyte with side reactions and poor cycling performance. Herein, a synergistic interaction between a polyterthiophene photocatalyst and a redox mediator is employed in Li-O₂ batteries. During the discharge, the voltage can be compensated by the photovoltage generated on the photoelectrode. Upon the charge with illumination, the photogenerated holes can be consumed by the oxidization of iodide ions, and thus the external circuit voltage is compensated by photogenerated electrons. Accordingly, a smaller bias voltage is needed for the semiconductor to decompose Li₂ O₂ , and the potential of photogenerated holes decreases. Finally, the round-trip efficiency of the battery reaches 97% with a discharge voltage of 3.10 V and a charge voltage of 3.19 V. The batteries show stable operation up to 150 cycles without increased polarization. This work provides new routes for light-assisted Li-O₂ batteries with reduced overpotential and boosted efficiency.