AbstractAchieving ampere‐hour‐scale capacities in pouch‐type zinc–air batteries (ZABs) requires optimizing key factors, such as preventing inactive ZnO dendrite formation on zinc anodes and enhancing catalytic activity with efficient gas diffusion in the air cathode. Here, a pioneering flexible, large‐area, ampere‐hour‐scale quasi‐solid‐state ZAB is introduced, addressing these challenges through a novel preactivation strategy combined with a layered assembly approach. This method employs mass‐producible fibrous carbon textiles to form flexible fabrics that separate functions within multi‐stacked layers. Preactivated carbon fabric layers, independently functionalized and easily reassembled, enhance scalability and manufacturability. A bilayer catalytic air electrode, incorporating hydrophilic NiFe hydroxide and hydrophobic FeNC regions, ensures efficient charge and mass transfer, significantly boosting catalytic activity. To prevent dendrite formation on the zinc anode, a zincophilic copper interlayer is implemented. This configuration supports rapid, stable charge–discharge cycles at a high current density of 20 mA cm⁻2. The large‐area stacked bipolar structure pouch cells, exceeding 36 cm2, achieve a discharge capacity of up to 2500 mAh, maintaining high cycle stability through discharge–charge cycles with 200 mAh per cycle. This approach significantly enhances the scalability, manufacturability, and production potential of ultrahigh‐capacity wearable ZABs, making them practical for widespread application in various portable and flexible devices.
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