The performance of electrochemical energy storage devices (e.g., batteries and electrochemical capacitors) is largely determined by the physicochemical properties of the active electrode materials, such as the thermodynamic potential associated with the charge-storage reaction, ion-storage capacity, and long-term electrochemical stability. In the case of mixed ion/electron-conducting metal oxides that undergo cation-insertion reactions, the presence of cation vacancies in the lattice structure can enhance one or more of these technical parameters without resorting to a drastic change in material composition. Examples of this enhancement include the charge-storage properties of certain cation-deficient oxides such as γ-MnO2 and γ-Fe2O3 relative to their defect-free analogues. The optimal cation-vacancy fraction is both material- and application-dependent because cation vacancies enhance some materials properties at the expense of others, potentially affecting electronic conductivity or thermal stability. Although the advantages of structural cation vacancies have been known since at least the mid-1980s, only a handful of research groups have purposefully integrated cation vacancies into active electrode materials to enhance device performance.
Three protocols are available for the incorporation of cation vacancies into transition metal oxides to improve performance in both aqueous and nonaqueous energy storage. Through a processing approach, researchers induce point defects in conventional oxides using traditional solid-state-ionics techniques that treat the oxide under appropriate atmospheric conditions with a driving force such as temperature. In a synthetic approach, substitutional doping of a highly oxidized cation into a metal-oxide framework can significantly increase cation-vacancy content and corresponding charge-storage capacity. In a scaling approach, electrode materials that are expressed in morphologies with high surface areas, such as aerogels, contain more defects because the increased fraction of surface sites favors the formation of cation vacancies.
In this Account, we review studies of cation-deficient electrode materials from the literature and our laboratory, focusing on transition metal oxides and the impact cation vacancies have on electrochemical performance. We also discuss the challenges and limitations of these defective structures and their promise as battery materials.