Supercapacitor layer

Another type of supercapacitor has been developed in whieh instead of ideally polarizable electrodes, electrodes consisting of disperse platinum metals are used at which thin oxide films are formed by anodic polarization. Film formation is a faradaic process which in certain cases, such as the further partial oxidation and reduction of these layers, occurs under conditions close to reversibility. 

A classic definition of electrochemical ultracapacitors or supercapacitors summarizes them as devices, which store electrical energy via charge in the electrical double layer, mainly by electrostatic forces, without phase transformation in the electrode materials. Most commercially available capacitors consist of two high surface area carbon electrodes with graphitic or soot-like material as electrical conductivity enhancement additives. Chapter 1 of this volume contains seven papers with overview presentations, and development reports, as related to new carbon materials for this emerging segment of the energy market. 

Qu D., Studies of the activated carbons used in double-layer supercapacitors, J. Power Sourc. 2002 109 403-411. 

The contribution by Rouzaud et al. teaches to apply a modified version of high resolution Transmission Electron Microscopy (TEM) as an efficient technique of quantitative investigation of the mechanism of irreversible capacity loss in various carbon candidates for application in lithium-ion batteries. The authors introduce the Corridor model , which is interesting and is likely to stimulate active discussion within the lithium-ion battery community. Besides carbon fibers coated with polycarbon (a candidate anode material for lithium-ion technology), authors study carbon aerogels, a known material for supercapacitor application. Besides the capability to form an efficient double electric layer in these aerogels, authors... 

Fig. 12.3 Fabrication of the nanocomposite paper units for battery, (a) Schematic of the battery assembled by using nanocomposite film units. The nanocomposite unit comprises LiPF6 electrolyte and multiwalled carbon nanotube (MWNT) embedded inside cellulose paper. A thin extra layer of cellulose covers the top of the MWNT array. Ti/Au thin film deposited on the exposed MWNT acts as a current collector. In the battery, a thin Li electrode film is added onto the nanocomposite, (b) Cross-sectional SEM image of the nanocomposite paper showing MWNT protruding from the cel-lulose-RTIL ([bmlm] [Cl]) thin films (scale bar, 2pm). The schematic displays the partial exposure of MWNT. A supercapacitor is prepared by putting two sheets of nanocomposite paper together at the cellulose exposed side and using the MWNTs on the external surfaces as electrodes, (c) Photographs of the nanocomposite units demonstrating mechanical flexibility. Flat sheet (top), partially rolled (middle), and completely rolled up inside a capillary (bottom) are shown (See Color Plates)...

Electrostatic interactions have recently been exploited for the synthesis of gra-phene-CNT hybrids. For example, poly(ethyleneimine) (PEI) coated graphene has been mixed with acid treated CNTs in a layer-by-layer method to form high surface area electrodes for supercapacitors [90]. Furthermore, Lu et al. prepared a supercapacitor electrode by mixing PDDA coated CNT-Mn02 hybrid with RGO [91]. 

Li, Z., et al., Electrostatic layer-by-layer self-assembly multilayer films based on graphene and manganese dioxide sheets as novel electrode materials for supercapacitors. Journal of Materials Chemistry, 2011. 21(10) p. 3397-3403. 

Figure 2. Representation of (A, top) an electrochemical capacitor (supercapacitor), illustrating the energy storage in the electric double layers at the electrode—electrolyte interfaces, and (B, bottom) a fuel cell showing the continuous supply of reactants (hydrogen at the anode and oxygen at the cathode) and redox reactions in the cell.

In electrochemical capacitors (or supercapacitors), energy may not be delivered via redox reactions and, thus the use of the terms anode and cathode may not be appropriate but are in common usage. By orientation of electrolyte ions at the electrolyte/electrolyte interface, so-called electrical double layers (EDLs) are formed and released, which results in a parallel movement of electrons in the external wire, that is, in the energy-delivering process. 

An electrochemical capacitor is a device that stores electrical energy in the electrical double layer that forms at the interface between an electrolytic solution and an electronic conductor. The term applies to charged carbon—carbon systems as well as carbon-battery electrode and conducting polymer electrode combinations sometimes called ultracapacitors, supercapacitors, or hybrid capacitors. 

Figure 7. (A, top) Simple battery circuit diagram, where Cdl represents the capacitance of the electrical double layer at the electrode—solution interface (cf. discussion of supercapacitors below), W depicts the Warburg impedance for diffusion processes, Rj is the internal resistance, and Zanode and Zcathode are the impedances of the electrode reactions. These are sometimes represented as a series resistance capacitance network with values derived from the Argand diagram. This reaction capacitance can be 10 times the size of the double-layer capacitance. The reaction resistance component of Z is related to the exchange current for the kinetics of the reaction. (B, bottom) Corresponding Argand diagram of the behavior of impedance with frequency, f, for an idealized battery system, where the characteristic behaviors of ohmic, activation, and diffusion or concentration polarizations are depicted.

Recently supercapacitors are attracting much attention as new power sources complementary to secondary batteries. The term supercapacitors is used for both electrochemical double-layer capacitors (EDLCs) and pseudocapacitors. The EDLCs are based on the double-layer capacitance at carbon electrodes of high specific areas, while the pseudocapacitors are based on the pseudocapacitance of the films of redox oxides (Ru02, Ir02, etc.) or redox polymers (polypyrrole, polythiophene, etc.). 

Fig. 9.27 shows the variation of capacitance as a function of the surface area from which it may be concluded that in principle it is possible to obtain double-layer supercapacitors having specific capacitance of the order of 100 F/g so that values of practical capacitance density as high as 30 F/g can be predicted. 

A typical configuration of a double-layer supercapacitor involves two metallic collectors which hold in place the carbon powder electrodes, which in turn are separated by an electrolyte, in most of the cases formed by liquid solutions (Fig. 9.28.) A layer of porous, non-conductive material acts as a separator. 

Fig. 9.27 Specific capacitance of a double-layer supercapacitor as a function of surface area. (By permission of Chim Ind . E. Spila et al., 1995, 77, 333.)...

Solid ionic conductors can also be used in the fabrication of solid state double-layer supercapacitors. An example is the device developed in the late 1960s by Gould Ionics which adopted a cell system using a silver-carbon electrode couple separated by the highly ionically conducting solid electrolyte RbAg4I5 (see Section 9.1) ... 

Fig. 9.29 Power and energy densities of double-layer and electrochemical supercapacitors in comparison wiLh typical rechargeable batteries and fuel cells...

In this respect, this review provides a comprehensive survey of synthetic methods and physicochemical properties of the porous carbon materials. Furthermore, as electrochemical applications of the porous carbons to electrode materials for supercapacitor, the effects of geometric heterogeneity and surface inhomogeneity on ion penetration into the pores during double-layer charging/ discharging are discussed in detail by using ac-impedance spectroscopy, current transient technique, and cyclic voltammetry. 

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