LAUSR

The layered V2O5 cathode exhibits appealing features of multiple electron redox processes and versatile cation‐storage capacities. However, the huge volume respiration induces structural collapse and limits its commercial‐scale deployment. Herein, a scalable water‐bath strategy is developed to tailor the (001) spacing of the bulk V2O5 from the original 4.37 Å to its triple value (14.2 Å). The intercalated polyaniline (PANI) molecules act as pillars in the V2O5 interlayer, thus affording the abundant storage sites and enhanced cation diffusivities of Li+, Na+, or hydrated Zn2+. Upon various cations (de‐)intercalation, transmission‐mode operando X‐ray diffraction is employed to document the zero‐strain behavior of the PANI‐intercalated V2O5. This scalable intercalation‐polymerization strategy, coupled with the compatibility study of the ionic radius and the c‐lattice for the layered structure, enables the rational engineering of the intercalation‐type cathodes toward facile reaction kinetics.