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

Abstract 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 0.8 Co 0.1 Mn 0.1 O 2 (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 PF 6 − 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.