Cation Additive Enabled Rechargeable LiOH‐Based Lithium–Oxygen Batteries

Lithium-oxygen (Li-O2 ) batteries have attracted extensive research interest due to their high energy density. Other than Li2 O2 (a typical discharge product in Li-O2 batteries), LiOH has proved to be electrochemically active as an alternative product. Here we report a simple strategy to achieve a reversible LiOH-based Li-O2 battery by using a cation additive, sodium ions, to the lithium electrolyte. Without redox mediators in the cell, LiOH is detected as the sole discharge product and it charges at a low charge potential of 3.4 V. A solution-based reaction route is proposed, showing that the competing solvation environment of the catalyst and Li+ leads to LiOH precipitation at the cathode. It is critical to tune the cell chemistry of Li-O2 batteries by designing a simple system to promote LiOH formation/decomposition.