Dual-functional Separators Regulating Ion Transport Enabled by 3D-Reinforced Polyimide Microspheres Protective Layer for Dendrite-Free and High-Temperature Lithium Metal Batteries

High-energy-density lithium metal batteries (LMBs) are confronted with crucial concerns of security and a short cycle lifespan caused by the uncontrollable formation of lithium (Li) dendrites. The poor thermal stability and heterogeneous Li deposition of conventional polyolefin separators often cause battery short circuiting and thermal runaway in LMBs. Herein, a novel dual-functional PE composite separator (PI-COOH/PE) coated by carboxyl polyimide (PI) microspheres is fabricated by an etching-acidification method. The three-dimensional (3D) high-temp PI microsphere with rich carboxyl groups on the surface improve the security of LMBs at extremely high temperatures and facilitate the formation of a stable and uniform SEI layer, which contributes to accelerating the Li+ transport and stabilizing the formation of the SEI layer. Consequently, the Li symmetric cell assembled with the (PI-COOH)/PE separator exhibits stable overpotential over 3000 h, and the corresponding Li//NCM811 full cells also show a high-level discharge capacity of 146.6 mAh g–1 at 5 C. Meanwhile, it also demonstrates outstanding cycling stability and thermal safety, which can survive continuously over 160 min at 140 °C (vs 21 min for PE). The above results indicate the (PI-COOH)/PE separator constructed by a low-cost and industrial-friendly strategy simultaneously addresses high-temperature stability and dendrite resistance.