• Supplements
• Publisher-DOI

Rechargeable aqueous zinc‐air batteries (ZABs) promise high energy density and safety. However, the use of conventional zinc anodes affects the energy output from the battery, so that the theoretical energy density is not achievable under operation conditions. A large portion of the zinc is shielded by anode passivation during the discharge process and remains electrochemically unused, making the operation of rechargeable ZABs inefficient up to date. In a metal anode‐free ZAB, there is no unnecessary excess zinc if the zinc reservoir can be precisely adjusted by electrodeposition of zinc from the electrolyte. In this respect, an anode‐free battery uses the electrolyte offering a dual‐mode functionality not only providing ionic conductivity but also being the source of zinc. In addition, it is shown that a defined porous anode architecture is crucial for high rechargeability in this new type of ZAB. 3D‐spatially arranged carbon nanotubes as geometrically defined host structures allow a homogeneous zinc deposition from the electrolyte. Together with carbon nanohorns as an active 2e⁻ catalyst on the cathode side, the rechargeability of this new concept reaches up to 92%.