Stabilizing Zn Metal Anode Through Regulation of Zn Ion Transfer and Interfacial Behavior with a Fast Ion Conductor Protective Layer

Abstract Aqueous Zn‐ion batteries (AZIBs) attract intensive attention owing to their environmental friendliness, cost‐effectiveness, innate safety, and high specific capacity. However, the practical applications of AZIBs are hindered by several adverse phenomena, including corrosion, Zn dendrites, and hydrogen evolution. Herein, a Zn anode decorated with a 3D porous‐structured Na 3 V 2 (PO4) 3 (NVP@Zn) is obtained, where the NVP reconstruct the electrolyte/anode interface. The resulting NVP@Zn anode can provide a large quantity of fast and stable channels, facilitating enhanced Zn ion deposition kinetics and regulating the Zn ions transport process through the ion confinement effect. The NASICON‐type NVP protective layer promote the desolvation process due to its nanopore structure, thus effectively avoiding side reactions. Theoretical calculations indicate that the NVP@Zn electrode has a higher Zn ion binding energy and a higher migration barrier, which demonstrates that NVP protective layer can enhance Zn ion deposition kinetics and prevent the unfettered 2D diffusion of Zn ions. Therefore, the results show that NVP@Zn/MnO 2 full cell can maintain a high specific discharge capacity of 168 mAh g −1 and a high‐capacity retention rate of 74.6% after cycling. The extraordinary results obtained with this strategy have confirmed the promising applications of NVP in high‐performance AZIBs.