The development of flexible zinc‐air batteries (FZABs) has attracted broad attention in the field of wearable electronic devices. Gel electrolyte is one of the most important components in FZABs, which is urgent to be optimized to match with Zn anode and adapt to severe climates. In this work, a polarized gel electrolyte of polyacrylamide‐sodium citric (PAM‐SC) is designed for FZABs, in which the SC molecules contain large amount of polarized −COO− functional groups. The polarized −COO− groups can form an electrical field between gel electrolyte and Zn anode to suppress Zn dendrite growth. Besides, the −COO− groups in PAM‐SC can fix H2O molecules, which prevents water from freezing and evaporating. The polarized PAM‐SC hydrogel delivers a high ionic conductivity of 324.68 mS cm−1 and water retention of 96.85 % after being exposed for 96 h. FZABs with the PAM‐SC gel electrolyte exhibit long cycling life of 700 cycles at −40 °C, showing the application prospect under extreme conditions.

Lithium metal is a desirable anode for high-energy density lithium–sulfur (Li–S) batteries. However, its reliability is severely limited by dendrite growth and side reactions with polysulfides, which are yet challenging to solve simultaneously. Herein, we report a protective layer that works the same way as the ion-permselective cell membrane, yielding a corrosion-resistant and dendrite-free Li metal anode specially for Li–S batteries. A self-limited assembly of octadecylamine together with Al3+ ions on a Li metal anode surface produces a dense, stable yet thin layer with ionic conductive Al–Li alloy uniformly embedded in it, which prevents the passage of polysulfides but regulates the penetrated Li ion flux for uniform Li deposition. As a result, the assembled batteries show excellent cycling stability even with a high sulfur-loaded cathode, suggesting a straightforward but promising strategy to stabilize highly active anodes for practical applications.