Grafting‐Engineered Interfacial Desolvation Dynamics: A Universal Strategy for Low‐Temperature Li‐Metal Batteries

Abstract Lithium metal batteries (LMBs) encounter significant performance degradation at low temperatures due to high desolvation energy barriers, sluggish Li‐ion transport kinetics, and non‐uniform deposition, all of which contribute to dendrite growth and serious polarization. Herein, a grafted layer which can simultaneously regulate Li + desolvation pathway and modulate lithium deposition behavior is developed. The grafted layer integrates an organic matrix for pre‐desolvation via selective Li⁺ sieving and solvation‐shell modulation, coupled with an electron‐blocking interphase and lithiophilic alloy layer to synergistically regulate Li⁺ flux uniformity and dendrite suppression. Symmetric cells with grafted Li exhibit a cycle life over 1000 h at −20 °C, representing a tenfold improvement compared with bare Li. PFG‐NMR reveals selective Li + transport within the engineered interface, with the Li + diffusion coefficient significantly exceeding those of anions and solvent molecules. Furthermore, theoretical calculations and simulations demonstrate a substantial reduction in the desolvation energy barrier. Explored as the anode in lithium–air batteries, it can also be cycled for more than 250 cycles at −20 °C which is far better than the bare Li anode. This study establishes pre‐desolvation engineering as a viable strategy for enhancing the stability of lithium anode, providing critical insights into the next‐generation LMBs operating under extreme conditions.