A single production of nitrogen-doped graphene nanosheets was developed in this present work from a spent Zn-C primary battery. The electrochemically exfoliated nitrogen-doped graphene nanosheets (EC-N-GNS) was applied in supercapacitor symmetric devices. As-prepared EC-N-GNS was utilized for a symmetric supercapacitor with natural seawater multivalent ion electrolyte. The recycling of graphite into nitrogen-doped graphene was characterized by X-ray diffraction and RAMAN spectroscopy. The few-layered morphological structures of EC-N-GNS were analyzed by field emission scanning electron microscope and field emission transmission electron microscope. The electrochemical analysis of the cyclic voltammetry curves observed an electrochemical double-layer capacitor (EDLC) behavior with a potential window of −0.8 V to +0.5 V. The electrochemical galvanostatic charge—discharge study was obtained to be maximum specific capacitance (Csp)—67.69 F/g and 43.07 F/g at a current density of 1 A/g. We promising the facile single-step electrochemically exfoliated EC-N-GNS was obtained from a waste zinc-carbon primary battery to recycle the graphite electrodes. The superior electrochemical performance comparatively bulk graphite and EC-N-GNS for potential energy storage supercapacitor applications.