Although lithium-sulfur batteries possess the highest theoretical capacity and lowest cost among all known rechargeable batteries, their commercialization is still hampered by the intrinsic disadvantages of low conductivity of sulfur and polysulfide shuttle effect, which is most critical. Considerable research efforts have been dedicated to solving these difficulties for every part of Li-S batteries. Separator modification with metal electrocatalysts is a promising approach to overcome the major part of these disadvantages. This work focuses on the development of Ni nanoparticles encapsulated in a few-layer nitrogen-doped graphene supported by nitrogen-doped graphitic carbon (Ni@NGC) with different metal loadings as separator modifications. The effect of metal loading on the Li-S electrochemical reaction kinetics and performance of Li-S batteries was investigated. Controlling the Ni loading allowed for the modulation of the surface area-to-metal content ratio, which influenced the reaction kinetics and cycling performance of Li-S cells. Among the separators with different Ni loadings, the one with 9 wt% Ni exhibited the most efficient acceleration of the polysulfide redox reaction and minimized the polysulfide shuttling effect. Batteries with this separator retained 77.2% capacity after 200 cycles at 0.5C, with a high sulfur loading of ∼4.0 mg cm -2, while a bare separator showed 51.3% capacity retention after 200 cycles under the same conditions. This work reveals that there is a vast utility space for carbon-encapsulated Ni nanoparticles in electrochemical energy storage devices with optimal selection and rational design.