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 LiNi_1/3Co_1/3Mn_1/3O₂ 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.

Lithium-ion batteries have attracted enormous interests recently as promising power sources. However, the safety issue associated with the employment of highly flammable liquid electrolyte impedes the further development of next-generation lithium-ion batteries. Recently, researchers reported the use of electrospun core-shell fiber as the battery separator consisting of polymer layer as protective shell and flame retardants loaded inside as core. In case of a typical battery shorting, the protective polymer shell melts during thermal-runaway and the flame retardants inside would be released to suppress the combustion of the electrolyte. Due to the use of a single precursor solution for electrospinning containing both polymer and flame retardants, the weight ratio of flame retardants is limited and dependent. Herein, we developed a dual-nozzle, coaxial electrospinning approach to fabricate the core-shell nanofiber with a greatly enhanced flame retardants weight percentage in the final fibers. The weight ratio of flame retardants of triphenyl phosphate in the final composite reaches over 60 wt.%. The LiFePO4-based cell using this composite nanofiber as battery separator exhibits excellent flame-retardant property without compromising the cycling stability or rate performances. In addition, this functional nanofiber can also be coated onto commercial separators instead of being used directly as separators.