Standard Supercapacitor Technologies

Design Brief
One charge cycle is required to have;

Since capacitance is the ratio of charge to potential difference;

As a capacitor is charged the potential difference will vary with time, as will current.

Energy stored can be expressed as;

The charge will vary from no charge to maximum charge;

NB:

Also;

NB: Therefore, a lower voltage is preferred to reduce losses through internal resistance but the voltage must be high enough to have a feasible capacitance. Overview of Supercapacitor Technology Batteries store energy as chemical energy and release it through electrochemical reactions. The rate of the cell reaction determines the power density of the battery. Although a battery can have a large energy density, the rate at which this energy can be used is restricted by the cell kinetics. Conventional capacitors have relatively high power densities, but relatively low energy densities when compared to electrochemical batteries and to fuel cells. That is, a battery can store more total energy than a capacitor, but it cannot deliver it very quickly, which means its power density is low. Capacitors, on the other hand, store relatively less energy per unit mass or volume, but what electrical energy they do store can be discharged rapidly to produce a lot of power, so their power density is usually high. For this reason capacitors are looked to as a potential solution to the low power density of batteries. As there is little or no chemical activity within a capacitor they can be charged and discharged hundreds of thousands before they fatigue.[1] Capacitors differ from batteries in that they store energy as charge separation rather than chemically. They traditionally use a solid dielectric between two metal electrodes. The amount of energy they store is limited by the dielectric dimensions, permittivity and dielectric strength. Capacitors are able to provide much larger power densities than batteries but for much shorter times due to their low energy density. Supercapacitors are electrochemical capacitors that instead of using a solid dielectric separate charge using an electrical double-layer or pseudocapacitance. A supercapacitor (or ultracapacitor) has an unusually high energy density when compared to common capacitors, typically on the order of thousands of times greater than a high capacity electrolytic capacitor. In general, supercapacitors improve storage density through the use of a nano-porous material. Two very high surface area porous electrodes are soaked in electrolyte. The charge is stored in electrochemical double layers. Double Layer Theory An electrical double layer (EDL) is formed on a surface in an electrolyte when there is a charge difference between the surface and the adjacent electrolyte layer. The surface can be a solid-liquid, liquid-liquid or liquid-gas interface.

The first layer, the surface charge, consists of ions directly adsorbed to the surface. The adsorption mechanisms are complicated and varied; such as Van der Waals interactions or pseudo-covalent bonding. The second layer, the diffuse layer, is made up of ions which are attracted to the surface charge layer by the coulomb force. The diffuse layer is only loosely associated with the surface because the ions are free moving rather than bonded. The motion of these diffuse ions is affected by the electrostatic attraction of the charge layer and the their own thermal motion. The double layer itself can be thought of as a simple capacitor. Allowing it to be modelled mathematically. Various models (Guoy, Stern and Chapman models) have been derived though with several assumptions;

ions are effectively modelled as point charges the only significant interactions in the diffuse layer are coulombic dielectric permittivity is assumed constant throughout the double layer the viscosity of fluid is constant above slipping plane.

All the models describe electrical potential as decreasing exponentially away from the surface to the bulk fluid. Jong U. Kim [2] developed a model of the double layer interaction in which he used a triple layer model and did not make the assumption that charge density at the outer diffuse plane is zero as an improvement on the standard Guoy-Stern-Chapman models. In forming the double layer on a surface by capacitive charging, energy is stored electrostatically in proportion to the area and charge density of the double layers. Though in pseudocapacitive supercapacitors the dominant charge separation method is not in double-layer formation but in the charge transfer from faradic reactions where energy is stored, much like a battery, electrochemically. If the electrode is a carbon nanotube which contains a functional group on its surface then an electron transfer reaction (a Faradic reaction) occurs at the surface of the electrode. This type of capacitance is called pseudocapacitance. If no Faradic reaction takes place charges, (ions), can only be physically absorbed into the double layer and without electron transfer, this is a pure double layer capacitance.

In reality both a double-layer and a pseudocapacitance will exist but one is usually dominant and characterises that particular supercapacitor. When both processes are important the capacitor is said to be a hybrid supercapacitor. In early EDLC supercapacitor technologies porous carbon electrodes saturated in an electrolyte and divided by a permeable membrane were used. Increasing surface area increases the capacitance so new supercapacitor technologies incorporate carbon nanotube structures to allow greater energy densities. Supercapacitors are governed by the same basic principles as conventional capacitors. However, they incorporate electrodes with much higher surface areas A and much thinner dielectrics that decrease the distance D between the electrodes. Specifically, owning to their properties of high electrical conductivity, high specific surface area, high charge transport capability, high mesoporosity, and high electrolyte accessibility, CNTs are attractive electrode materials for developing high-performance supercapacitors.[3] Like a conventional activated carbon-based supercapacitor, electrodes and electrolyte are two important components for a CNT supercapacitor. As mentioned previously, increasing voltage of the capacitor will increase the internal resistance. For application in electric vehicles it is required to increase surface area of the capacitor packing while also decreasing the internal resistance of the capacitor. The latter is achieved through selection of electrolyte and the optimising the shape of the carbon packing. Ionic liquids are one option for efficient ionic transport medium. The performance characteristics of an EDLC can be adjusted by changing the nature of its electrolyte. An EDLC can utilize either an aqueous or organic electrolyte. Aqueous electrolytes, such as H2SO4 and KOH, generally have lower internal resistance and lower minimum pore size requirements compared to organic electrolytes, such as acetonitrile. However, aqueous electrolytes also have lower breakdown voltages. Therefore, in choosing between an aqueous or organic electrolyte, one must consider the tradeoffs between capacitance, internal resistance, and voltage.[4] In table 1 is a list of current Supercapacitor technologies in development or on sale. The capacitor voltages are limited to below 3V as higher voltages would cause dielectric breakdown in the packing. Manufacturer EPCOS Maxwell Nesscap Evans Corp. Montena SAFT Elit Packing Carbon Carbon Carbon Powder Carbon Carbon Carbon Carbon/ NiO2 Electrolyte Organic Organic V 2.3 2.7 2.7 2.7 1.4 2.5 1.2 C 2700 3000 5000 65 1400 3500 470 3.0 11.0 5.2 2.5 3.5 3 9.5 9864 19,872 20,880 1260 15,624 16,920 13,824 Development Status On Sale On Sale On Sale On Sale On Sale Development Development

H2SO4 Organic Organic Aqueous

[1] C. Ashtiani, R. Wright, G. Hunt. (2006) Ultracapacitors for Automotive Applications Journal of Power Sources 154(2006), 561-566 [2] Jong U. Kim. (2005) "Electrical double layer: revisit based on boundary conditions" Ph.D. Thesis. Texas A&M University: U.S. [3] R. H. Baughman, A. A. Zakhidov, W. A. de Heer, (2002) "Carbon Nanotubes--the Route Toward Applications". Science, 297 (5582), 787 792 [4] M. S. Halper, J. C. Ellenbogen, (2006) "Supercapacitors - A Brief Overview" MITRE Nanosystems Group - McLean. Virginia: U.S.