The abundant availability of zinc and its environmentally friendly properties have increasingly drawn attention to the potential of aqueous zinc-ion batteries (AZIBs). However, their development is hindered by the formation of zinc dendrites and severe side reactions during charge/discharge cycles. In this work, a novel strategy is introduced to address these challenges by constructing a ferroelectric porous PVDF-HFP protective layer (PH-ZF) on the zinc anode surface using 3D printing technology. This approach not only simplifies the fabrication process but also achieves a high content of β-phase PVDF-HFP without the need for post-treatment. The ferroelectric porous polymer layer effectively regulates ion concentration distribution on the zinc anode surface, promoting uniform Zn deposition. As a result, symmetric batteries exhibit cycle lifetimes of 1200 and 2000 h at current densities of 0.5 and 1.0 mA cm, respectively. Furthermore, full batteries with MnO cathodes maintained a discharge specific capacity of ≈88.3 mA g after 1000 cycles at a current density of 1.0 A g, in contrast to bare zinc electrodes, which retain only 51 mAh g under the same conditions. This method offers a promising approach for enhancing zinc anode protection and advancing ZIB performance.
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