Unlocking the Potential of MOFs Anodes via Solid‐State Corrosion Prelithiation for High‐Energy Li‐Ion Batteries

Abstract Pristine metal‐organic frameworks (MOFs) with their excellent cycling stability and high capacity are considered as promising next‐generation anode materials for advanced high‐performance lithium‐ion batteries. Despite extensive efforts to improve initial Coulombic efficiency (ICE) via electrochemical prelithiation, the fundamental processes governing transition metals (TMs) dissolution and associated degradation mechanisms in MOFs‐based full cells remain unclear. In this study, crystalline cobalt‐nickel bimetallic metal‐organic frameworks CoNi x ‐MOF (CoNi x ‐Benzene dicarboxylic MOFs), specifically derived from benzene dicarboxylic (BDC) ligands, are selected as the target material for investigation. A solid‐state corrosion (SSC) strategy for prelithiating MOFs anodes with corrosion of lithium metal is proposed for the first time. The full cell with prelithiated MOFs anode achieves an energy density of 493 Wh kg −1 and demonstrates superior cycling stability with 83.3% capacity retention after 240 cycles at 0.2 C. The SSC prelithiation strategy effectively passivates Co/Ni nanoparticles, reducing Ni dissolution percentage by an order of magnitude (from 15.32% to 1.16%), which is identified as the key factor underpinning the enhanced full cell performance. This study underscores the practical applicability of MOFs‐based anodes prelithiated by the SSC strategy for achieving high‐energy‐density and long‐cycling lithium‐ion batteries.