P123‐Directed Synthesis of MnO ₂ Cathode through Coordination with Mn ²⁺ for Enhanced H ⁺ /Zn ²⁺ Storage in Zinc‐Ion Batteries

ABSTRACT Manganese dioxide (MnO 2 ) is a promising cathode material for aqueous zinc‐ion batteries (AZIBs), but its performance is limited by slow ion transport kinetics and poor structural stability. In this study, the supramolecular sacrificial template strategy is introduced to overcome these challenges. Specifically, the removable P123 surfactant is selected as a dynamic template to regulate the reaction between Mn 2+ and MnO 4 − , controlling the formation pathway and final structure of MnO 2 (denoted as PMO). Experimental analyses and theoretical calculations show that ether oxygen and hydroxyl oxygen in the P123 molecule coordinate with Mn 2+ . This interaction promotes the formation of a 2D nanosheet morphology, enhances the hybridization of Mn 3d and O 2p orbitals, and facilitates the emergence of oxygen defects. The multi‐level structural design optimizes carrier transport dynamics and matrix stability, which results in PMO exhibiting superior cycling stability (203 mAh g −1 after 1000 cycles at 2 A g −1 ) and rate performance (122 mAh g −1 at 10 A g −1 ). Reversible and stable structural evolution during cycling is confirmed through in situ and ex situ characterization methods. This work elucidates the role of surfactants in MnO 2 synthesis and paves the way for the design of high‐performance electrode materials.