Engineering Vanadium Pentoxide Cathode for the Zero‐Strain Cation Storage via a Scalable Intercalation‐Polymerization Approach

Abstract The layered V 2 O 5 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 V 2 O 5 from the original 4.37 Å to its triple value (14.2 Å). The intercalated polyaniline (PANI) molecules act as pillars in the V 2 O 5 interlayer, thus affording the abundant storage sites and enhanced cation diffusivities of Li + , Na + , or hydrated Zn 2+ . Upon various cations (de‐)intercalation, transmission‐mode operando X‐ray diffraction is employed to document the zero‐strain behavior of the PANI‐intercalated V 2 O 5 . 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.