Enabling Further Organic Electrolyte Infiltration of Cellulose-Based Separators via Defect-Rich Polypyrrole Modification for High Sodium Ion Transport in Sodium Metal Batteries

Sodium metal batteries (SMBs) have high-density and cost-effective characteristics as one of the energy storage systems, but uncontrollable dendrite growth and poor rate performance still hinder their practical applications. Herein, a nitrogen-rich modified cellulose separator with released abundant ion transport tunnels in organic electrolyte was synthesized by in situ polymerization of polypyrrole, which is based on the high permeability of cellulose in aqueous solution and the interfacial interaction between cellulose and polypyrrole. Meanwhile, the introduction of abundant structural defects such as branch chains, oxygen-containing functional groups, and imine-like structure to disrupt polypyrrole conjugation enables the utilization of conductive polymers in composite separator applications. With the electrolyte affinity surface on, the modified separator exhibits reinforced electrolyte uptake (254%) and extended electrolyte wettability, thereby leading to accelerated ionic conductivity (2.77 mS cm^-1) and homogeneous sodium deposition by facilitating the establishment of additional pathways for ion transport. Benefiting from nitrogen-rich groups, the polypyrrole-modified separator demonstrates selective Na⁺ transport by the data of improved Na⁺ transference number (0.62). Owing to the above advantages, the battery assembled with the modified separators exhibits outstanding rate performance and prominent capacity retention two times that of the pristine cellulose separator at a high current density under the condition of fluorine-free electrolyte.