Multifunctional MXene‐Bonded Transport Network Embedded in Polymer Electrolyte Enables High‐Rate and Stable Solid‐State Zinc Metal Batteries

Sluggish transport kinetics and unstable electrode–electrolyte interface are the main obstacles that greatly impair the electrochemical performance of solid‐state Zn metal batteries. Herein, the concept of multifunctional MXene bonded transport network‐embedded poly(vinylidene fluoride co‐hexafluoropropylene)/Zn(OTf)2 solid polymer electrolyte (PH/MXene SPE) is proposed as “all‐in‐one” strategy for designing robust SPE. In order to uncover the mechanism of such rational designed SPE on regulating the ion transport, as well as the interphase chemistry and Zn deposition, comprehensive research including density functional theory calculation, simulation, and multiple characterization techniques are carried out. As the results indicate, the formation of hydrogen bond network between the MXene nanofiller and PH polymer benefits fast and homogeneous ion transport. Then, the in situ formation of stable organic/inorganic hybrid interphase is capable to ensure the efficient interfacial transport kinetics and uniform Zn deposition. When such PH/MXene SPE is applied, ultrastable Zn plating/stripping behavior with small polarization voltage can be realized. In addi, solid‐state Zn/VO2 batteries with significantly improved rate performance and cyclic stability also can be demonstrated. The unique strategy proposed in this study offer a new insight into SPE design and the development of high‐performance solid‐state Zn metal batteries. Sluggish transport kinetics and an unstable electrode–electrolyte interface are the main obstacles for solid‐state Zn metal batteries. This work reports the design concept of multifunctional MXene bonded transport network‐embedded solid polymer electrolyte (SPE). Uniform Zn deposition enabled by the designed SPE via regulating the ion transport behavior and in situ built stable interphase. High‐rate and stable solid‐state Zn/VO2 batteries also can be constructed.