The increasing energy demand requires high-performance energy storage devices (ESD), which depend on their power density (PD), energy density (ED), operating temperature ranges, and life-cycle. PD, ED, and lifetime of supercapacitors rarely fulfill needs. The high density of ESD can be attained by using nanomaterials. Morphological advantages of graphene can be utilized to improve the device performance. This chapter discusses about the modifications that can be brought about in the currently used batteries which paves a way towards implementation of next-generation sustainable storage devices. It gives an in-depth review of the use of graphene-based nanomaterials in lithium-ion batteries and thermal-driven supercapacitors. Graphene modified by transition metals/metal oxides and sulfides/hetero-atoms/polymers can greatly enhance the device performance. Analysis of how morphology, structure, porosity, defects, functionalization, and synergy influence the performance is discussed. The low-temperature failure of supercapacitors, solar energy intermittency, and conversion efficiency issues can be over-turned by employing thermal-driven supercapacitors. This inspires to new-concept devices and to a sustainable future. This chapter gives an in-depth review of graphene-based nano-material utilization for high-performance ESDs.