Intramolecular Polarization‐Mediated Solvation and Interphase Engineering for Low‐Temperature High‐Voltage Lithium Metal Batteries

ABSTRACT Simultaneously achieving stable lithium metal batteries (LMBs) under cryogenic and high‐voltage conditions remains a fundamental challenge due to uncontrolled interfacial chemistry at lithium anodes and nickel‐rich cathodes. Here, we report an intramolecular polarization strategy that jointly regulates Li + solvation dynamics, solid electrolyte interphase (SEI) formation, and cathode electrolyte interphase (CEI) stress dissipation. An intramolecularly polarized electrolyte featuring orthogonally arranged electron donor–acceptor moieties with a dipole moment (∼4.2 D) establishes a potential–dependent solvation screening effect, reducing Li + desolvation energy to 38.1 kJ mol −1 , while enabling anodic stability beyond 5.3 V. The tailored solvation chemistry induces spontaneous formation of dual–gradient interphases composed of a LiF–rich SEI and a boroxane–incorporated CEI with an interface modulus ∼20 nN. Consequently, Li||Li symmetric cells exhibit stable cycling over 16 000 h with a minimal polarization of 8.3 mV. Full cells employing LiNi 0.8 Co 0.1 Mn 0.1 O 2 cathodes retain 90% capacity after 1000 cycles at 4.5 V and maintain 80% at 4.9 V. 3 Ah pouch cells achieve a high energy density of 509 Wh kg −1 at 30°C with 96.8% capacity retention after 80 cycles, while delivering 439.1 Wh kg −1 at −30°C. This work establishes a molecular polarization paradigm for electrolyte and interphase engineering toward high–energy–density LMBs under extreme conditions.