Though the energy density of lithium-ion batteries continues to increase, safety issues related to the internal short circuit and the resulting combustion of highly flammable electrolytes impede the further development of lithium-ion batteries. It has been well-accepted that a thermal stable separator is important to postpone the entire battery short circuit and thermal runaway. Traditional methods to improve the thermal stability of separators include surface modification and/or developing alternate material systems for separators, which may affect the battery performance negatively. Herein, a thermostable and shrink-free separator with little compromise in battery performance was prepared by coaxial electrospinning and tested. The separator consisted of core-shell fiber networks where poly (vinylidene fluoride-hexafluoropropylene) (PVDF-HFP) layer served as shell and polyacrylonitrile (PAN) as the core. This core-shell fiber network exhibited little or even no shrinking/melting at elevated temperature over 250 °C. Meanwhile, it showed excellent electrolyte wettability and could take large amounts of liquid electrolyte, three times more than that of conventional Celgard 2400 separator. In addition, the half-cell using LiNi1/3
as cathode and the aforementioned electrospun core-shell fiber network as separator demonstrated superior electrochemical behavior, stably cycling for 200 cycles at 1 C with a reversible capacity of 130 mA·h·g−1
and little capacity decay.
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