Graphene, a 2D carbon structure, due to its unique materials characteristics for energy storage applications has grasped the considerable attention of scientists. The highlighted properties of this material with a mechanically robust and highly conductive nature have opened new opportunities for different energy storage systems such as Li-S (lithium-sulfur), Li-ion batteries, and metal-air batteries. It is necessary to understand the intrinsic properties of graphene materials to widen its large-scale applications in energy storage systems. In this review, different routes of graphene synthesis were investigated using chemical, thermal, plasma, and other methods along with their advantages and disadvantages. Apart from this, the applications of N-doped graphene in energy storage devices were discussed.