Molecular Interfacial Engineering of Lithiophilic Protection Layer Realizing 600 Wh kg ⁻¹ Anode‐Free Lithium Metal Batteries

ABSTRACT Anode‐free lithium (Li) metal batteries (AFLMBs) can achieve higher energy densities at lower costs and easier production processes, but the uneven plating of Li leads to dendrite growth, making safety issues unavoidable. Here, we propose a convenient and scalable molecular interface engineering strategy: the 5‐methyl‐1H‐tetrazole (MTZ) molecule forms chemically bonded, stable self‐assembled monolayer (SAMs) interface on Cu foil surfaces, thereby producing modified Cu foil (MTZ‐Cu). Anchored by strong Cu─N bonds, the SAMs not only introduce high‐density nucleation sites with molecular precision but also promote preferential decomposition of LiNO 3 in electrolytes, forming a stable solid electrolyte interface that enhances plating uniformity and reversibility. When used in combination with LiNi 0.8 Co 0.1 Mn 0.1 O 2 and LiNi 0.9 Co 0.05 Mn 0.05 O 2 cathodes, the assembled 8.44 Ah and 9.96 Ah MTZ‐Cu‐based anode‐free pouch cells achieve benchmark energy densities of 505.31 Wh kg total −1 and 605.96 Wh kg total −1 for 100 cycles, respectively. This work demonstrates the advantages of molecular interface engineering in constructing practical AFLMBs, with the potential for large‐scale production to meet commercial applications.