3D Printing of MXene‐Enhanced Ferroelectric Polymer for Ultrastable Zinc Anodes

Abstract Zinc (Zn) metal anodes of aqueous zinc‐ion batteries (AZIBs) have attracted significant attention due to their high theoretical capacities, low redox potentials, and low cost. However, uncontrollable dendrite formation and side reactions can result in limited reversible cycling and quick failure of the batteries. Herein, a polyvinylidene fluoride (PVDF)‐based protection layer (PVDF‐MXene) with high β‐phase content is built by the 3D printing method. The synergistic effect attributed to the 3D printing approach and MXene nanosheets contributes to phase transition of the PVDF polymer chains from α‐phase to β‐phase, improving the ferroelectric properties of the printed PVDF films. Such a protection layer can manipulate the concentration distribution of zinc ions and enable the uniform growth of zinc plates. As a result, symmetrical zinc batteries using such anodes (PVDF‐MXene‐Zn) exhibit reversible Zn plating/stripping with low voltage hysteresis at 1.0 mA cm −2 , 1.0 mAh cm −2 for over 4200 h, and a high‐rate capability up to 10 mA cm −2 . When assembled with MnO 2 and activated carbon, the resulting Zn‐MnO 2 battery and zinc‐ion capacitor exhibited significantly enhanced cycling stability. The proposed strategy in this study provides a novel strategy for the protection of the zinc anode, thus promoting the practical application of ZIBs.