Superhydrophobic and robust hetero-metal-polymer hybrid interphase enables deep-cycling zinc metal anodes†
Abstract
Realizing stable zinc (Zn) metal anodes under deep cycling conditions is a prerequisite for practical rechargeable Zn batteries, but it remains a significant challenge due to severe water erosion and dendrite growth on Zn. Herein, a robust hetero-metal-polymer hybrid interphase composed of Pb nanoparticles embedded on the polyvinylidene difluoride (PVDF) matrix is integrated on the Zn anode in situ by a one-step chemical displacement reaction to tackle these dilemmas. This concept can be readily extended to construct Bi-PVDF and Sn-PVDF hybrid interphases on Zn. Unlike the commonly developed hydrophilic and thick metal-based interphases, the superhydrophobic, thin, and seamless Pb-PVDF interphase, as a model example, can prevent water access to the Zn surface and exhibit an ultralow H2 evolution reaction potential, thus avoiding water-induced side reactions. Moreover, the flexible Pb-PVDF hybrid interphase with strong zincophilicity enables the dendrite-free and epitaxial Zn deposition. Consequently, the Pb-PVDF@Zn electrode manifests an ultralong lifespan over 8100 h (0.5 mA h cm−2 at 1 mA cm−2) and unprecedented deep cycling stability under 85.3% depth-of-discharge over 800 h (10 mA h cm−2 at 20 mA cm−2), which is a 160-fold elongation of lifespan compared with that of a bare Zn electrode. Moreover, Pb-PVDF@Zn assures the stable operation of full Zn batteries with conventional V/Mn-oxide cathodes using both coin and pouch configurations.