Solid-state electrochemical double-layer capacitor (SEDLC) forms excellent energy storage device for high-power applications. They are highly reliable, with no electrolyte leaks, and can be packaged to suit various applications. The electrode material can be activated carbon to graphene. These can have a range of particle size, surface area, pore size and pore distribution for charge storage. The emphasis will be to optimize the graphene to carbon blend in the electrodes which would provide appreciable storage density of the SEDLC. We can use perfluorosulfonic acid polymer as the solid electrolyte in the SEDLC assembly. They have high ionic conductivity, good thermal stability, and mechanical strength. They also have excellent long-term chemical stability. Carbon is widely used for many practical applications, especially for the adsorption of ions and molecules, as it is possible to synthesize one-, two- or three-dimensional (1-, 2-, or 3-D) carbons. Some of the problems in activated carbon like varying micro or mesopores, poor ion mobility due to varying pore distribution, low electrical conductivity, can be overcome using graphene and blends of graphene with carbon of the right pore dimension and distribution. Graphene in various structural nomenclatures have been used by various groups for charge storage. Graphene nanoplates (GNP), with narrow mesopore distributions have been effectively used for SEDLCs. SEDLCs assembled with GNP and blends of GNP with Vulcan XC and solid polymer electrolyte like Nafion show exceptional performance. The cyclic voltammetric studies show that they support high scan rates with substantial smaller capacitance drop as we increase scan rates. Optimization of the electrode structure in terms of blend percentage, binder content and interface character in the frequency and time domain provides excellent insight into the double-layer interface. © 2014 Springer-Verlag Berlin Heidelberg.