Double-Layer Electrode Materials

Carbonaceous materials are almost exclusively utilized as active materials of double-layer electrodes due to their high conductivity, electrochemical stability, and porosity. Activated carbons still constitute the most practical active carbon-based electrode materials. They have high surface areas, are inexpensive to produce, and can be fabricated using a variety of readily available precursor materials. 

It is desirable to develop active carbon materials with higher capacitances by increasing both surface areas and porosities. The common belief was that increasing pore volumes to sizes that are accessible to solvated ion species would directly increase capacitance. However, it was proposed recently that the presence of micropores ( 2 nm) could increase the capacitances of these materials [14]. This indicates that some sort of ion desolvation mechanism occurring at the molecular scale allows ion transport and adsorption in these micropores. 

A significant dependence on ion size was also observed. This suggests that designing active carbon materials with tunable pore sizes that could be optimized for specific types of ion species will be a challenge. With these methods, it will be possible to develop electrode materials with significantly improved capacitances through trial and error investigations supplemented by molecular scale computational methods. 

Despite the widespread applicability and high capacitance values of activated carbon materials, other electrolyte and ion transport issues may arise and limit the performances of electrodes fabricated from these materials. Fabricating ordered electrode structures seems promising for overcoming this limitation. For example, CNTs have been extensively investigated due to their one-dimensional structures that result in porous electrode networks. 

Further investigations are required to develop active carbon-based materials with higher capacitances and electrode arrangements favorable to mass transport. Moreover, inexpensive, upscalable fabrication techniques for these materials are also required to render them commercially viable. 

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Nickel batteries use P-Ni(OH)2 as electrode material. This material converts to P-NiOOH during the charging process and this rearranges to y-NiOOH when it is overcharged. This last process is accompanied by a significant expansion, because of the difference in density between P-NiOOH and y-NiOOH, which may result in poor electric contact between the current collector and P-Ni(OH)2/p-NiOOH, with concomitant decrease in the discharge capacity of the battery. Among others, layered double hydroxides of Ni and other metals, often termed stabilized a-Ni(()H), or doped Ni(0H)2, have been tested as electrode materials (Bernard et al., 1996). The effect of the interlayer anions on the electrochemical performance of layered double hydroxide electrode materials has been recently studied by Lei et al. (2008) (see Chapter 6). 

Carbons act as excellent conductors, are chemically stable, and have high surface areas, making them the preferred materials for double-layer electrodes in modem ESs. Carbon, however, comes in many varieties and not all are applicable to electrode materials. The industrial standard and most basic high surface area carbon material is achvated carbon (AC). It is widely used because of moderate cost and easy preparahon. 

Dangler, C. et al. 2011. Role of conducting carbon in electrodes for electric double-layer capacitors. Materials Letters, 65, 300-303. 

Alternatives for MCFC cathodes have been found in doped lithium oxide materials such as LiFeOi, Li2Mn03, and LiCo02 and also in combination with NiO materials to form double-layered electrodes. A tape casting of a NiO/LiCo02 double layer electrode improved the stability tremendously. The oxygen reduction reaction is improved at these double layer cathodes and the resistance is reduced [21]. 

Electrically, the electrical double layer may be viewed as a capacitor with the charges separated by a distance of the order of molecular dimensions. The measured capacitance ranges from about two to several hundred microfarads per square centimeter depending on the stmcture of the double layer, the potential, and the composition of the electrode materials. Figure 4 illustrates the behavior of the capacitance and potential for a mercury electrode where the double layer capacitance is about 16 p.F/cm when cations occupy the OHP and about 38 p.F/cm when anions occupy the IHP. The behavior of other electrode materials is judged to be similar. 

In electrode kinetics a relationship is sought between the current density and the composition of the electrolyte, surface overpotential, and the electrode material. This microscopic description of the double layer indicates how stmcture and chemistry affect the rate of charge-transfer reactions. Generally in electrode kinetics the double layer is regarded as part of the interface, and a macroscopic relationship is sought. For the general reaction... 

The electrical double layer is the array of charged particles and/or oriented dipoles that exists at every material interface. In electrochemistry, such a layer reflects the ionic zones formed in the solution to compensate for the excess of charge on the electrode (qe). A positively charged electrode thus attracts a layer of negative ions (and vice versa). Since the interface must be neutral. qe + qs = 0 (where qs is the charge of the ions in the nearby solution). Accordingly, such a counterlayer is made... 

In recent years, many types of double-layer capacitors have been built with porous or extremely rough carbon electrodes. Activated carbon or materials produced by carbonization and partial activation of textile cloth can be used for these purposes. At carbon materials, the specific capacity is on the order of 10 J,F/cm of trae surface area in the region of ideal polarizability. Activated carbons have specific surface areas attaining thousands of mVg. The double-layer capacity can thus attain several tens of farads per gram of electrode material at the surfaces of such carbons. 

These measurements have verified that the work function of an electrode, emersed with the double layer intact, depends only on the electrode potential and not on the electrode material or the state of the electrode (oxidized or covered with submonolayer amounts of a metal) [20]. Work function measurements on emersed electrodes do not serve the same purpose as in surface science investigations of the solid vacuum interface. At the electrochemical interface, any change of the work function by adsorption is compensated by a rearrangement of the electrochemical double layer in order to keep the applied potential i.e. overall work function, constant. Work function measurements, however, could well be used as a probe for the quality of the emersion process. Provided the accuracy of the measurement is good enough, a combination of electrochemical and UPS measurements may lead to a determination of the components of equation (4). 

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. 

The pores of the silica template can be filled by carbon from a gas or a liquid phase. One may consider an insertion of pyrolytic carbon from the thermal decomposition of propylene or by an aqueous solution of sucrose, which after elimination of water requires a carbonization step at 900°C. The carbon infiltration is followed by the dissolution of silica by HF. The main attribute of template carbons is their well sized pores defined by the wall thickness of the silica matrix. Application of such highly ordered materials allows an exact screening of pores adapted for efficient charging of the electrical double layer. The electrochemical performance of capacitor electrodes prepared from the various template carbons have been determined and are tentatively correlated with their structural and microtextural characteristics. 

Carbonaceous materials play a key role in achieving the necessary performance parameters of electrochemical capacitors (EC). In fact, various forms of carbon constitute more than 95% of electrode composition [1], Double layer capacity and energy storage capacity of the capacitor is directly proportional to the accessible electrode surface, which is defined as surface that is wetted with electrolyte and participating in the electrochemical process. 

High porosity carbons ranging from typically microporous solids of narrow pore size distribution to materials with over 30% of mesopore contribution were produced by the treatment of various polymeric-type (coal) and carbonaceous (mesophase, semi-cokes, commercial active carbon) precursors with an excess of KOH. The effects related to parent material nature, KOH/precursor ratio and reaction temperature and time on the porosity characteristics and surface chemistry is described. The results are discussed in terms of suitability of produced carbons as an electrode material in electric double-layer capacitors. 

Porous carbons are among the most attractive electrode materials for electric double layer capacitors (EDLC), where the charge accumulation occurs mainly by electrostatic attraction forces at the clcctrode/electrolyte interface [1-3]. Advantages of this class of materials include high surface... 

The air gas-diffusion electrode developed in this laboratory [5] is a double-layer tablet (thickness ca.1.5 mm), which separates the electrolyte in the cell from the surrounding air. The electrode comprises two layers a porous, from highly hydrophobic, electrically conductive gas layer (from the side of the air) and a catalytic layer (from the side of the electrolyte). The gas layer consists of a carbon-based hydrophobic material produced from acetylene black and PTFE by a special technology [6], The high porosity of the gas layer ensures effective oxygen supply into the reaction zone of the electrode simultaneously the leakage of the electrolyte through the electrode... 

No investigation of a solid, such as the electrode in its interface with the electrolyte, can be considered complete without information on the physical structure of that solid, i.e. the arrangement of the atoms in the material with respect to each other. STM provides some information of this kind, with respect to the 2-dimensional array of the surface atoms, but what of the 3-dimensional structure of the electrode surface or the structure of a thick layer on an electrode, such as an under-potential deposited (upd) metal At the beginning of this chapter, electrocapillarity was employed to test and prove the theories of the double layer, a role it fulfilled admirably within its limitations as a somewhat indirect probe. The question arises, is it possible to see the double layer, to determine the location of the ions in solution with respect to the electrode, and to probe the double layer as the techniques above have probed adsorption Can the crystal structure of a upd metal layer be determined In essence, a technique is required that is able to investigate long- and short-range order in matter. 

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