Dual‐Functional Acetate Intercalation in NiMn‐LDH Cathode: Interlayer Pillaring and Electronic Delocalization Toward Advanced Aqueous Zinc‐Ion Batteries

ABSTRACT Aqueous zinc‐ion batteries (AZIBs) are regarded as attractive candidates for safe and sustainable energy storage, but their further development remains constrained by sluggish ion/electron transport and limited structural stability of cathode materials. To overcome these limitations, we designed an acetate‐intercalated NiMn layered double hydroxide cathode (Ac‐NiMn‐LDH) using a template‐guided assembly route. This approach effectively mitigates the restacking of NiMn‐LDH nanosheets, endowing the material with a robust structure and enlarged active surface area. Serving as functional pillars, the intercalated acetate anions expand the interlayer gallery and weaken Zn 2+ ‐host interactions, thereby reducing ion‐migration resistance and reinforcing the layered structure. Furthermore, the strong electronic coupling between the acetate groups and the host layers triggers localized charge redistribution, promoting d‐electron delocalization at Mn/Ni sites and enhancing charge transport. Benefiting from this coupled structural and electronic regulation, the Ac‐NiMn‐LDH cathode achieves a capacity of 274.6 mAh g −1 at 0.1 A g −1 and retains stable cycling at 1 A g −1 , corresponding to a low capacity decay of 0.002% per cycle over 2200 cycles. Moreover, flexible AZIBs assembled with this cathode operate steadily under bending deformation. This work offers a synergistic strategy for modulating both the physical architecture and electronic states of layered cathodes for advanced AZIBs.