Interfacial Super‐Assembled Porous CeO2/C Frameworks Featuring Efficient and Sensitive Decomposing Li2O2 for Smart Li–O2 Batteries

The Li–O₂ battery (LOB) represents a promising candidate for future electric vehicles owing to its outstanding energy density. However, the practical application of LOB cells is largely blocked by the poor cycling performance of cathode materials. Herein, an ultralong 440‐cycle life of an LOB cell is achieved using CeO₂ nanocubes super‐assembled on an inverse opal carbon matrix as the cathode material without any additives. CeO₂ is proved to be effective for the complete and sensitive decomposition of loosely stacked Li₂O₂ films during the oxygen evolution reaction process and full accommodation of volume changes caused by the fast growth of Li₂O₂ films during the oxygen reduction reaction process. The super‐assembled porous CeO₂/C frameworks satisfy critical requirements including controlled size, morphology, high Ce³⁺/Ce⁴⁺ ratio, and efficient volume change accommodation, which dramatically increase the cycle life of LOB cell to 440 cycles. This study reveals the design strategy for high performance CeO₂ catalyst cathodes for LOB cells and the generation mechanisms of Li₂O₂ films during the discharge process by using density functional theory calculations, showing new avenues for improving the future smart design of CeO₂‐based cathode catalysts for Li–O₂ batteries.