Unlock Restricted Capacity via OCe Hybridization for LiOxygen Batteries

Abstract The aprotic Li‐O 2 battery (LOB) has the highest theoretical energy density of any rechargeable batteries. However, such system is largely restricted by the electrochemically formed lithium peroxide (Li 2 O 2 ) on the cathode surface, leading ultimately to low actual capacities and early cell death. In contrast to the surface‐mediated growth of thin film with a thickness <50 nm, a non‐crystalline Li 2 O 2 film with a thickness of >400 nm can be formed via an optimal OCe hybridized electronic structure. Specially, oxygen can react with dissolved cerium cations in the electrolyte via a cerium‐oxygen reaction to form a high‐energy faceted cerium oxide catalyst, which not only generates a great number of non‐saturable active sites, but also erects electron transport bridges between the lattice O and adjacent Ce atoms. Such CeO orbital hybridization also forms a direct charge transfer channel from Ce‐4f of CeO 2 to ‐π* of Li 2 O 2 , eventually leading to submicron‐thick Li 2 O 2 shells via a subsequent lithium‐oxygen reaction. Relying on the above merits, this work unlocks the rechargeable capacities of LOB from restricted 1000 to unprecedented 10 000 mAh g −1 with good cyclabilities and reduced charge–discharge overpotentials.