LiNbO ₃ -Mediated Dielectric Polarization Tailoring at Polymer Electrolyte Interfaces for Dendrite-Free Lithium Metal Batteries

Lithium-metal batteries (LMBs) face critical challenges in interfacial instability and dendritic growth, despite their high theoretical capacity. To address these issues, we designed an interface layer containing LiNbO₃ crystals to modify the polymer electrolyte, achieving uniform deposition of lithium ions. This design innovatively integrates electrostatic screening and field-guided ion transport mechanisms─unique to LiNbO₃ dielectric polarization materials─achieving unprecedented homogeneous Li⁺ flux distribution while catalytically mediating the formation of a dual-functional LiF/Li₃N-rich solid electrolyte interphase (SEI). Notably, the Li₃N component synergistically enhances ion diffusion, while LiF mechanically suppresses dendrites, synergizing physicochemical stabilization where conventional SPEs fail. The optimized LN-SPE demonstrates exceptional ionic conductivity of 4.92 × 10^-4 S cm^-1 and Li⁺ transference number of 0.67 at RT, enabling an assembled SSLMB to deliver 138.1 mAh g^-1 at 0.5 C with ultrahigh capacity retention of 94.42% after 100 cycles, while maintaining 142.4 mAh g^-1 at 1 C. Crucially, the sustained dielectric polarization activity ensures long-term interfacial integrity, positioning this work as a paradigm-shifting approach for electroceramic-polymer hybrids with scalable manufacturing pathways, thus offering transformative solutions for next-generation high-energy-density batteries.