Spatially Confined Silver Nanoparticles in Mercapto Metal–Organic Frameworks to Compartmentalize Li Deposition Toward Anode‐Free Lithium Metal Batteries

Abstract As the promising next‐generation energy storage solution, lithium metal battery (LMB) has gained great attention but still suffers from troubles associated with the highly active metallic lithium. Herein, it is aimed to develop an anode‐free LMB engaging no Li disk or foil by modifying the Cu current collector with mercapto metal–organic frameworks (MOFs) impregnating Ag nanoparticles (NPs). While the polar mercapto groups facilitate and guide Li + transport, the highly lithiophilic Ag NPs help to enhance the electric conductivity and lower the energy barrier of Li nucleation. Furthermore, the MOF pores allow compartmentalizing bulk Li into a 3D matrix Li storage so that not only the local current density is reduced, but also is the plating/stripping reversibility greatly enhanced. As a result, full cells pairing the prelithiated Ag@Zr‐DMBD/Cu anodes with LiFePO 4 cathodes demonstrate a high initial specific capacity of 159.8 mAh g −1 , first‐cycle Coulombic efficiency of 96.6%, and long‐term cycling stability over 1000 cycles with 99.3% capacity retention at 1 C. This study underlines the multi‐aspect functionalization of MOFs to impart lithiophilicity, polarity, and porosity to achieve reversible Li plating/stripping and paves the way for realizing high‐performance anode‐free LMBs through exquisite modification of the Cu current collector.