Caging Lithium Deposition: High‐Entropy Metal–Organic Framework Interfaces for Anode‐Free Batteries

ABSTRACT Anode‐free lithium metal batteries (AF‐LMBs) offer high energy density systems and simplified design through the complete elimination of excess lithium. However, their practical development is hindered by sluggish lithium‐ion (Li + ) transport and uneven lithium deposition at the anode interface. Here, we introduce a nanoconfined ion‐regulator based on a high‐entropy metal–organic framework (HE‐MOF). The simulation results demonstrate that the multi‐metal channels provide heterogeneous local coordination environments, broadening the distribution of Li + binding sites, facilitating Li + migration, suppressing local ion retention, and regulating interfacial electrolyte decomposition, ultimately leading to the formation of a thin LiF‐rich SEI layer. As a result, the Li||HE‐MOF/C half‐cell delivers an initial Coulombic efficiency of 97.74% at 0.5 mA cm −2 , the HE‐MOF/C@Li symmetric cell exhibits stable cycling for over 10000 h at 60 mA cm −2 /1 mAh cm −2 , and the anode‐free HE‐MOF/C||NCM‐811 full cell remains stable for 2300 cycles with a capacity decay rate per cycle of 0.026%. This work provides a proof‐of‐concept high‐entropy MOF interfacial strategy for regulating Li deposition in AF‐LMBs.