Quasi-solid-state sodium-ion hybrid capacitors enabled by UiO-66@PVDF-HFP multifunctional separators: selective charge transfer and high safety

The practical application of sodium-ion hybrid capacitors is limited by their low energy densities resulted from the kinetics mismatch between cathodes and anodes, and the fire safety related to the flammable electrolyte-separator system. Hence, we report a rational design of metal-organic frameworks (MOFs, UiO-66) modified PVDF-HFP separator. High tensile strength and dimensional thermal stability of the separator reduce the risk of electrode short circuit caused by the separator deformation. MCC test demonstrates a reduction of 75% in peak heat release rate (pHRR), indicating an enhanced fire-resistant property of the separator. This is due to the transformation of UiO-66 into ZrO2 accompanied by the consumption of oxygen and the formation of the barrier char that suppresses further heat release. Quasi-solid-state electrolyte prepared based on this separator presents an enhanced ionic conductivity of 2.44 mS*cm-1 and Na-ion transference number of 0.55, which are related to the high porosity ( >70%) and electrolyte uptake (~ 320%) of the separator. Moreover, the open metal sites of UiO-66 can capture PF6- and consequently liberate the Na+ for faster migration, thus reducing the kinetics mismatch between cathodes and anodes. Such multifunctional separator enables the quasi-solid-state Na-ion hybrid capacitor to achieve high energy density (182 Wh*kg-1 @31 W*kg-1) and power density (5280 W*kg-1 @22 Wh*kg-1), as well as excellent cyclic stability (10000 cycles @1000 mA*g-1). Keywords: Quasi-solid-state; PVDF-HFP; Metal-organic frameworks; Dimensional thermal stability; Fire safety; Selective charge transfer