Epitaxial Induced Plating Current‐Collector Lasting Lifespan of Anode‐Free Lithium Metal Battery

Abstract Anode‐free designs can obtain the ultimate energy density of lithium metal batteries. However, without a continuous Li supply from the anode side, it is much more challenging to achieve high capacity retention with a competitive energy density. Here, the lifespan of an anode‐free Li metal battery is prolonged by applying an epitaxial induced plating current‐collector (E‐Cu). The functional layer on E‐Cu initiates Li storage by an alloying approach, forming an epitaxial induce layer, which exhibits speedy surface diffusion for of Li‐ions, resulting in the block like epitaxial growth of Li. Moreover, this alloying process also promotes the formation of a LiF‐rich solid electrolyte interphase (SEI), which is very useful for uniform Li plating. Due to the benefits of epitaxial Li plating and LiF‐rich SEI, the initial coulombic efficiency of the E‐Cu/Li asymmetric cell increases from 93.24 to 98.24%, and the capacity retention of anode‐free NCM811/E‐Cu pouch cell increases from 66 to 84% with a remarkable energy density of 420 Wh kg −1 in the condition of limited electrolyte addition (E/C ratio of 2 g Ah −1 ). This strategy is promising in the development of high energy batteries in extending their lifespans.