Building Topological‐Disordered High‐Entropy Amorphous Oxides for Adaptive Compensation During Alternating CO ₂ Redox Cycling

Abstract Material fatigue from alternating structural evolution degrades electrochemical performance through local collapse and deactivation, with the key challenge being preservation of active‐site durability. To minimize structural deformation while sustaining reaction kinetics, topological disorder engineering offers a synergistic pathway integrating energy level mergence with high structural freedom. Here, we propose high‐entropy amorphous oxides (HEAOs) as a model system featuring intrinsic self‐adaptive topological disorder. Their dynamic metal–oxygen coordination network enables exceptional structural relaxation, where flexible M–O–M linkages and multicomponent integration cooperatively induce d–d electron transfer and/or d–p orbital coupling. These electronic interactions trigger localized charge redistribution for self‐adaptive compensation under alternating electrochemical conditions such as CO 2 reduction/evolution. In Li–CO 2 batteries, HEAOs deliver an ultra‐high discharge voltage of 3.14 V after long‐term cycling at 100 µA cm −2 , while maintaining ∼90% energy efficiency across different current densities. Unlike conventional strategies emphasizing local structural tuning, this work shifts the focus to long‐range integrity engineering to suppress electrochemical fatigue. The self‐adaptive compensation of HEAOs arises from responsive topologically disordered metal–oxygen polyhedra, effectively mitigating strain accumulation and redefining long‐range topological adaptability as a key design principle for fatigue‐resistant electrochemical materials.