University, Jinju 52828, Republic of Korea; Present Address: ; ? orcid.org

In this work, electrospun PBI separators with a highly porous structure and nanofiber diameter of about 90-150 nm are prepared using a multi-nozzle under controlled conditions for lithium metal batteries. Cross-linking with alpha, alpha-dibromo-p-xylene and surface treatment using 4-(chloromethyl) benzoic acid successfully improve the electrochemical as well as mechanical properties of the separators. The resulting separator is endowed with high thermal stability and excellent wettability (1080 to 1150%) with commercial liquid electrolyte than PE and PP (Celgard 2400) separators. Besides, attractive cycling stability and rate capability in LiFePO4/Li cells are attained with the modified separators. Prominently, CROSSLINK PBI exhibits a stable Coulombic efficiency of more than 99% over 100 charge-discharge cycles at 0.5 C, which is superior to the value of cells using commercial PE and PP (Celgard 2400) separators. The half cells assembled using the CROSSLINK PBI separator can deliver a discharge capacity of 150.3 mAh g-1 at 0.2 C after 50 cycles corresponding to 88.4% of the theoretical value of LiFePO4 (170 mAh g-1). This work offers a worthwhile method to produce thermally stable separators with noteworthy electrochemical performances which opens new possibilities to improve the safe operation of batteries.