Achieving 1300 Wh/L in Anode‐Free Li Batteries With Integrated 3D Printed Cathode and Electrolyte

ABSTRACT Anode‐free Li batteries employing ultra‐thick cathodes offer exceptional volumetric energy density, yet are hindered by side reactions and limited Li reservoirs. This study develops an anode‐free pouch cell using a 3D‐printed ultra‐thick cathode (120 mg cm ‒2 ) and a dual‐salt/dual‐solvent electrolyte. The electrolyte forms an anion‐rich solvation structure, fostering an elastic‐plastic solid‐electrolyte interphase layer that enables highly reversible Li plating/stripping on bare Cu current collectors and stable prolonged cycling, even under low temperature conditions. The configuration delivers energy densities of 1,308 Wh L ‒1 and 424 Wh kg ‒1 , alongside a remarkable areal capacity of 19.11 mAh cm ‒2 . This work establishes a scalable and cost‐effective technical route for high‐energy, safe anode‐free batteries, which is expected to expedite their commercialization in electric aviation and the fast‐growing low‐altitude economy.