Vacancy and Growth Modulation of Cobalt Hexacyanoferrate by Porous MXene for Zinc Ion Batteries

Abstract Prussian blue analogs (PBAs) featuring with 3D open framework are recognized as promising cathode candidates for Zinc‐ion batteries (ZIBs). However, challenges such as unsatisfactory active site utilization, low conductivity, and abundant structural vacancies have impeded fulfillment of their potential. In this work, a conductive in‐plane porous MXene is for the first time adopted as a multifunctional host material to enhance cobalt hexacyanoferrate (CoHCF) growth and crystallinity. Particularly, the uniform surface charges on MXene are identified to induce anisotropic and highly crystalline CoHCF, which are critical to alleviating the practical drawbacks associated with the PBAs family. Empowered by the targeted modification, the CoHCF nanotube/MXene composite realizes high surface area and low defectiveness, resulting in an impressive capacity of 197 mAh g −1 at 0.1 A g −1 and capacity retention of 95.3% over 3000 cycles at 2.0 A g −1 . X‐ray spectroscopy and density functional theory (DFT) reveal that Co─C bonds in the heterostructure facilitate rapid electron/Zn‐ion transfer, enhancing Zn storage kinetics. To validate practical applicability, pouch cells incorporating Zn|CoHCF/MXene are further examined. This composition strategy, utilizing MXene as a multifunctional template, enhances the surface area, conductivity, and crystallinity of PBAs as cathodes for ZIBs, showcasing the significant potential for large‐scale energy storage applications.