Modulating the Proton‐Conducting Lanes in Spinel ZnMn2O4 through Off‐Stoichiometry

The intercalation of protons represents a notable component for energy storage in aqueous zinc‐ion batteries. However, the mechanism of proton transport in metal oxide cathodes, especially related to how the cation distribution modulates the proton‐conducting lanes, remains far from consensus due to the lack of suitable model materials. Here, taking spinel ZnMn2O4 cathode as a prototype, it is disclosed that a deficiency of one half of lattice Zn ions can triple its specific capacity at high rates, which is predominantly contributed by proton storage. This promotion can be rationalized by the emergence of facile concerted proton transport in the Zn‐deficient sample, contrasting with the stoichiometric one, where proton intercalation undergoes a slow consecutive process. Furthermore, the restricted Zn motion in spinel phase causes high structural stability during cycling, preventing the recombination of external Zn ions with Zn vacant sites that readily accommodate protons. This work highlights the key role of controlled off‐stoichiometry in optimizing proton transport and storage for aqueous batteries. Zn deficiency in spinel ZnMn2O4 is shown capable of inducing a surge of proton storage capacity, which is rooted in the alteration of dynamic proton behavior from a slow consecutive character to a facile concerted one.