Interfacial Lattice‐Strain‐Driven Generation of Oxygen Vacancies in an Aerobic‐Annealed TiO₂(B) Electrode

Abstract Oxygen vacancies play crucial roles in defining physical and chemical properties of materials to enhance the performances in electronics, solar cells, catalysis, sensors, and energy conversion and storage. Conventional approaches to incorporate oxygen defects mainly rely on reducing the oxygen partial pressure for the removal of product to change the equilibrium position. However, directly affecting reactants to shift the reaction toward generating oxygen vacancies is lacking and to fill this blank in synthetic methodology is very challenging. Here, a strategy is demonstrated to create oxygen vacancies through making the reaction energetically more favorable via applying interfacial strain on reactants by coating, using TiO₂(B) as a model system. Geometrical phase analysis and density functional theory simulations verify that the formation energy of oxygen vacancies is largely decreased under external strain. Benefiting from these, the obtained oxygen‐deficient TiO₂(B) exhibits impressively high level of capacitive charge storage, e.g., ≈53% at 0.5 mV s⁻¹, far surpassing the ≈31% of the unmodified counterpart. Meanwhile, the modified electrode shows significantly enhanced rate capability delivering a capacity of 112 mAh g⁻¹ at 20 C (≈6.7 A g⁻¹), ≈30% higher than air‐annealed TiO₂ and comparable to vacuum‐calcined TiO₂. This work heralds a new paradigm of mechanical manipulation of materials through interfacial control for rational defect engineering.