Electro-spun nanofiber web is highly attractive as a separator for lithium ion batteries because of its high electrical properties. In moving toward wider battery applications of the nanofiber separators, a deeper understanding on the structure and property relationship is highly meaningful. In this regard, we prepared electro-spun poly(vinylidene fluoride) (PVdF) webs with various thicknesses (10.5~100 µm) and investigated their structures and electrochemical performances. As the thickness of the web is decreased, a decrease of porosity and an increase of pore size are resulted in. For the 10.5 µm-thick separator, a minor short-circuit was detected, stressing the importance of reducing pore-size on prevention of short-circuit. However, above the thickness of 21 µm, well-connected, submicron-sized pores are generated, and, with lowering the separator thickness, discharge capacity and rate capability are enhanced owing to the lowered area-specific resistance.
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