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

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 CO₂ reduction/evolution. In Li-CO₂ 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.