Li2MoO4 Tailored Anion‐enhanced Solvation Sheath Layer Promotes Solution‐phase Mediated Li‐O2 Batteries

The high overpotential of Li‐O2 batteries (LOBs) is primarily triggered by sluggish charge transfer kinetics at the reaction interfaces. A typical LiBr redox mediator (RM) catalyst can effectively reduce the battery's overpotential. However, it is prone to shuttling and corroding the Li anode, leading to RM loss and reduced energy efficiency. To address these challenges, we introduced Li2MoO4 into the LiBr‐containing electrolyte to promote the solution‐phase mediated LOBs. This addition tailors the anion‐enhanced Li+ solvation sheath layer and forms a robust anion‐derived solid electrolyte interphases (SEI) on the Li anode. The robust SEI effectively mitigates the corrosion of soluble Br3−/Br2 and attacks by highly reactive oxygen species. Additionally, the dispersed and high‐density Li2MoO4 exhibits strong adsorption capabilities for O2/LiO2 and Br‐related species during the discharge/charge process, thereby promoting the growth and decomposition of Li2O2 in the solution phase and inhibiting the shuttle effect of Br‐related species in LOBs. Consequently, the LOBs demonstrate exceptional cycling stability (415 cycles) and high energy efficiency (86.2 %), paving the way for the sustainable development and practical application of these battery systems. The development of strategies to inhibit the shuttle effect of redox mediator can effectively reduce the high overpotential and prolong the cycle stability of Li‐O2 batteries. In this manuscript, Li2MoO4 was introduced to LiBr‐containing electrolyte to modify the Li+ solvation structure and forms an anion‐rich derived protective solid electrolyte interphase on Li anode. Additionally, the dispersed Li2MoO4 promotes the O2 conversion in solution phase and inhibits the shuttle effect of Br‐related species via adsorption capabilities. This work opens new avenues for the sustainable development and practical application of such battery systems.