Nanoporous Aramid Nanofiber Separators with High Modulus and Thermal Stability for Safe Lithium‐Ion Batteries

Abstract Developing high‐safety separators is a promising strategy to prevent thermal runaway in lithium‐ion batteries (LIBs), which stems from the low melting temperatures and inadequate modulus of commercial polyolefin separators. However, achieving high modulus and thermal stability, along with uniform nanopores in these separators, poses significant challenges. Herein, the study presents ultrathin nanoporous aramid nanofiber (ANF) separators with high modulus and excellent thermal stability, enhancing the safety of LIBs. These separators are produced using a microfluidic‐based continuous printing strategy, where the flow thickness can be meticulously controlled at the micrometer scale. This method allows for the continuous fabrication of nanoporous ANF separators with thicknesses ranging from 1.6 ± 0.1 µm to 2.7 ± 0.1 µm. Thanks to the double‐side solvent diffusion, the separators exhibit controllably uniform pore sizes with a narrow distribution, spanning from 40 ± 5 nm to 105 ± 9 nm, and a high modulus of 3.3 ± 0.5 GPa. These nanoporous ANF separators effectively inhibit lithium dendrite formation, resulting in a high‐capacity retention rate for the LIBs (80% after 240 cycles). Most notably, their robust structural and mechanical stability at elevated temperatures significantly enhances LIB safety under transient thermal abuse conditions, thus addressing critical safety concerns associated with LIBs.