Synergistic Effect of 3D Elastomer/Super‐Ionic Conductor Hybrid Fiber Networks Enables Zinc Anode Protection for Aqueous Zinc‐Ion Batteries

Abstract Aqueous zinc‐ion batteries (AZIBs) with the merits of superior security, natural abundance, and inexpensive Zn hold great promises for next‐generation energy storage. Nevertheless, the instabilities of the Zn anodes arising from the unsatisfactory dendrite growth and parasitic reactions have seriously restricted their practical application. Herein, an interfacial protection engineering approach is proposed for stabilizing Zn anode via in ‐ situ constructing 3D hybrid fiber networks within high elastic polyether‐type polyurethane (TPEU) and super‐ionic conductor NaTi 2 (PO 4 ) 3 (NTP). This 3D NTP@TPEU fiber framework demonstrates synergistic effects of enhancing Zn 2+ immigration kinetics and improving the desolvation process. Subsequently, such a superior protected interface induces a highly reversible Zn (002) deposition/stripping with a dendrites‐free feature. Moreover, the NTP@TPEU/Zn displays an ultralong lifespan of over 2000 cycles with an average Coulombic efficiency (CE) of 99.5% in the half‐cell configuration. To highlight, a full battery matched with Ca‐doped VO 2 on carbon cloth cathode acquires an enhanced CE as high as 99.8% and delivers good cycling stability with a capacity retention of 81.6% at 2 A g −1 over 3000 cycles. These excellent outcomes provide a distinctive perspective of designing a highly stable zinc anode for the practical application of AZIBs.