Dual Active Intermediates Induced LiOH Formation via the OH‐Rich Proton Donor in Li−O2 Batteries

Abstract Generally, water displays a dominated impact on the solution growth mechanism of the aprotic lithium−oxygen (Li−O 2 ) batteries, however, the high reaction activity and laborious secondary chemistry transformation process are associated with the irreversible utilization of water. In this paper, a substituted proton‐containing, highly dispersed and hydroxyl group (−OH)‐rich contained catalyst is employed in the Li−O 2 battery chemistry, and lithium hydroxide (LiOH) is identified as the primary discharge product. Intriguingly, the hydrogen (H) in LiOH comes solely from the added −OH‐rich onion carbon (OLC), which is capable of building a high‐speed proton transfer bridge between the generated moieties of dual active intermediates superoxide species (O 2 − ) and the moderate hydroperoxide (HO 2 − ) over the platinum (Pt) active sites. The new mechanism involving the HO 2 − intermediate realizes a hydrogen transfer process via O 2 − nucleophilic attack toward OLC, which significantly suppresses the O 2 − ‐related side reactions. Thereby, the batteries with Pt/OLC attain a high specific capacity of 12 500 mAh g −1 at a current density of 100 mA g −1 , exceptional energy efficiency (100%), and remarkable rechargeability. In addition, the strong OLC‐DMSO interaction inhibits the lithium metal corrosion caused by the shuttle reactions and ensures favorable battery cycling stability. The promising results open up a new reaction pathway for Li−O 2 battery electrochemistry.