Single‐Molecule Dual‐Anchor Design Enables Extreme‐Condition Lithium Metal Batteries Through Solvation Reconstruction and Cathode Polymerization

Lithium metal batteries (LMBs) have emerged as the most promising candidate for next-generation high-energy-density energy storage systems. However, their practical implementation is hindered by the inability of conventional carbonate electrolytes to simultaneously stabilize the lithium metal anode and LiNi_0.8Co_0.1Mn_0.1O₂ (NCM811) cathode interfaces, particularly under extreme operating conditions. Herein, we present a transformative molecular design using 3,5-difluorophenylboronic acid neopentyl glycol ester (DNE), which uniquely integrates dual interfacial stabilization mechanisms in a single molecule. Unlike conventional additives, DNE's Lewis acidic B─O bonds chemically anchor PF₆ ^- anions, reconstructing the Li⁺ solvation sheath to enable a lithium fluoride-rich solid electrolyte interphase that suppresses dendrites and lithium dendrite growth. Simultaneously, its cyclic borate ester undergoes in situ polymerization on the cathode surface, forming a transition metal ion-trapping network that optimizes the cathode electrolyte interphase and mitigates structural degradation in NCM811 cathodes. This synergistic dual-action mechanism endows Li||NCM811 cells with exceptional cycling stability under extreme conditions (4.7 V, 60 °C, and 5 C). Furthermore, a 1 Ah pouch cell with an energy density of 331 Wh kg^-1 maintains 98.8% capacity retention after 100 cycles. This dual-interface molecular anchoring strategy establishes a design paradigm for developing high-performance LMBs suitable for operations in extreme conditions.