Li<sup>+</sup> Ion-Dipole\nInteraction-Enabled a Dynamic\nSupramolecular Elastomer Interface Layer for Dendrite-Free Lithium\nMetal Anodes

The unstable lithium (Li)/electrolyte interface, causing\ninferior\ncycling efficiency and unrestrained dendrite growth, has severely\nhampered the practical deployment of Li metal batteries (LMBs), particularly\nin carbonate electrolytes. Herein, we present a robust approach capitalizing\non a dynamic supramolecular elastomer (DSE) interface layer, which\nis capable of being reduced with Li metal to spontaneously form strong\nLi<sup>+</sup> ion-dipole interaction, thereby enhancing interfacial\nstability in carbonate electrolytes. The soft phase in the DSE structure\nenables fast Li<sup>+</sup> transport via loosely coordinated Li<sup>+</sup>–O interaction, while the hard phase, rich in electronegative\nlithiophilic sites, drives the generation of fast-ion-conducting solid\nelectrolyte interface components, including Li<sub>3</sub>N and Li<sub>2</sub>S. Furthermore, the dynamically resilient DSE network composed\nof soft and hard phases protects Li anodes from electrolyte corrosion\nand accommodates volume changes during cycling. All features of the\nDSE layer synergistically facilitate uniform Li<sup>+</sup> deposition\nand suppress Li dendrite propagation, ensuring a stable and dendrite-free\nLi anode. Consequently, the symmetric Li||Li cell incorporating the\nDSE layer achieves cycling stability exceeding 6000 h under 1 mA cm<sup>–2</sup> and 1 mA h cm<sup>–2</sup> conditions. Furthermore,\nfull cell pairing DSE/Li anode with LiFePO<sub>4</sub> (LFP) or high-voltage\nLiNi<sub>0.8</sub>Mn<sub>0.1</sub>Co<sub>0.1</sub>O<sub>2</sub> (NMC811)\ncathodes exhibits high-efficiency Li deposition and cycling stability,\neven under constrained conditions of limited Li (40 μm) and\nultrahigh loading NMC811 cathode (21.5 mg cm<sup>–2</sup>).\nThis study underscores the effectiveness of the ion-dipole interaction-enabled\nDSE network in developing stable, high-energy-density LMBs.