LAUSR

Lithium (Li) metal, a promising anode for high‐energy‐density rechargeable batteries, typically grows along the low‐surface energy (110) plane in the plating process, resulting in uncontrollable dendrite growth and unstable interface. Herein, an unexpected Li growth behavior by lanthanum (La) doping is reported: the preferred orientation turns to (200) from (110) plane, enabling 2D nuclei rather than the usual 1D nuclei upon Li deposition and thus forming a dense and dendrite‐free morphology even at an ultrahigh areal capacity of 10 mAh cm−2. Noticeably, La doping further decreases the reactivity of Li metal toward electrolytes, thereby establishing a stable interface. The dendrite‐free, stable Li anode enables a high average Coulombic efficiency of 99.30% at 8 mAh cm−2 for asymmetric Li||LaF3–Cu cells. A 3.1 Ah LaF3–Li||LiNi0.8Co0.1Mn0.1O2 pouch cell at a high energy density (425.73 Wh kg−1) with impressive cycling stability (0.0989% decay per cycle) under lean electrolyte (1.76 g Ah−1) and high cathode loading (5.77 mAh cm−2) using this doped Li anode is further demonstrated.