Cross-linked cellulose/carboxylated polyimide nanofiber separator for lithium-ion battery application

•H-bond cross-linked Cellulose/PI-COOH composite separator is first prepared.•Cellulose/PI-COOH separator has 3D interconnected network from H-bond crosslinking.•Cellulose/PI-COOH separator possesses superior mechanical and thermal properties.•H-bond enhances the affinity and wettability of the separator toward electrolyte.•Cellulose/PI-COOH separator shows excellent cycle and rate performance in LIBs. Polyimide (PI) membranes with superior chemical resistance, insulation and self-extinguishing are attracting numerous attentions as the separators of lithium-ion batteries (LIBs), but significant challenges of low mechanical strength and poor electrolyte affinity still remain. Herein, a new kind of environmentally friendly hydrogen-bond (H-bond) cross-linked cellulose/carboxylated PI (Cellulose/PI-COOH) nanofiber composite separator is prepared via electrospinning followed by imidization and alkaline hydrolysis. Besides inheriting the high porosity of the pristine PI separator to absorb the electrolyte, the three-dimensional interconnected structure resulting from H-bond cross-linking is beneficial to improving the mechanical properties of the composite separator, and thereby delivers a tensile strength of 34.2 MPa, 5 times higher than that of the pristine PI separator (6.8 MPa). Meanwhile, the exposed hydroxyl groups on the cellulose, and carboxyl and imino groups on the carboxylated PI can also enhance the electrolyte affinity and wettability of the Cellulose/PI-COOH separator, which plays an important role in increasing the ionic conductivity (0.51 mS cm−1) and widening the electrochemical stability window (∼5.1 V). Consequently, compared with the polypropylene separator and PI separator, the H-bond cross-linked Cellulose/PI-COOH separators show better cycle performance and rate performance when adopted in lithium iron phosphate (LiFePO4) and lithium cobaltate (LiCoO2) half-cells. For example, the Cellulose/PI-COOH-based LiFePO4 half-cell demonstrates the highest initial discharge capacity of 166.2 mAh g−1 and capacity retention rate of 90%, much higher than the pristine PI-based LiFePO4 half-cell (114.6 mAh g−1, 86%). Furthermore, the much enhanced tensile strength, flexibility, thermal stability and flame-resistance of the Cellulose/PI-COOH separator are believed to greatly enhance the safety performance of the obtained LIBs.