Porous electrodes conductive additive

Oxygen reduction can be accelerated by an application of electrodes with high surface area, e.g. the porous electrodes [9, 13]. The porous electrodes usually consist of catalysts, hydrophobic agent (polytetrafluoroethylene-PTFE) and conductive additive. Electrode kinetics on the porous electrodes is complicated by the mass and charge transfer in the pores and is called the macrokinetics of electrode processes . 

In this case a porous electrode has a maximal possible amount of the electrochemically active material and the minimal amount of the conductive additive, which is necessary for formation of closed cluster (the touch of the spheres at the Figure 5) and a good conductivity of electrode mass. 

In the paper from V. Matveyev of the Ukrainian State University of Chemical Engineering, an examination of the role of conductive carbon additives in a composite porous electrode is conducted. A model for calculation of the local electrochemical characteristics of an electrode is presented. A comparison on the polarization of the electrode as a function of the redox state of the electroactive species is emphasized in the model. The electrochemical reaction of chloranil (tetrachlorobenzoquinone) was measured and results compare favorably to calculations derived from the model. 

However, as we saw in section 3.3 for platinum on YSZ, the fact that i—rj data fits a Butler—Volmer expression does not necessarily indicate that the electrode is limited by interfacial electrochemical kinetics. Supporting this point is a series of papers published by Svensson et al., who modeled the current—overpotential i—rj) characteristics of porous mixed-conducting electrodes. As shown in Figure 28a, these models take a similar mechanistic approach as the Adler model but consider additional physics (surface adsorption and transport) and forego time dependence (required to predict impedance) in order to solve for the full nonlinear i—rj characteristics at steady state. 

Electrochemical Limitations of Porous Electrodes and the Consequences for the Conductive Additive... 

Our experiments, as well as analysis of the proposed theoretical model for a generalized system of porous electrode "active material - carbon additive" proved that thermally exfoliated graphite (TEG) can be one of the most effective conductive additive and structural support for the different new and existing active materials. The reason for such wide application of TEG is a following unique complex of TEG properties low density, relatively high conductivity and stability to electrochemical oxidation. 

In addition to a - compared with a diaphragm - better conductivity of the membrane, advanced electrocatalysis is applied for cell voltage reduction electrocatalyst particles (for instance platinum or Ni-Zn alloy) are deposited in the boundary layer adjacent to a porous electrode material [55]. Figure 23 shows the principle. 

Porous-electrode theory has been used to describe a variety of electrochemical devices including fuel cells, batteries, separation devices, and electrochemical capacitors. In many of these systems, the electrode contains a single solid phase and a single fluid phase. Newman and Tiedemann reviewed the behavior of these flooded porous electrodes [23]. Many fuel-cell electrodes, however, contain more than one fluid phase, which introduces additional complications. Typical fuel cell catalyst layers, for example, contain both an electrolytic phase and a gas phase in addition to the solid electronically conducting phase. An earher review of gas-diffusion electrodes for fuel cells is provided by Bockris and Srinivasan [24]. 

Batteries of this type have been developed with film, tablet, and cylindrical designs. In the first type, the electrolyte film is applied onto the metal anode or cathodic current collector by sputtering or vaporization. The tablet and cylindrical batteries designed for comparatively high drain rates employ porous electrodes manufactured by pressing a mixture of the powders of the active materials (silver or polyiodide), electrolyte, and conductive additive (carbon black, etc.). 

It is evident that a single-pore theory cannot describe more complex cases of real porous electrodes containing particles of different sizes that are randomly distributed. Nevertheless, numerical simulations demand some additional information about the electrode, particle size distribution, possible heterogeneity of the material, conductivity of different phases, etc., and the electrode studied should be composed of a uniform packing of the particles with their size being much smaller than the electrode thickness. 

The anode of a Ni-Cd battery typically consists of a mix of Cd and CdO powders with the addition of a conductive additive (acetylene black). The impedance of the anode-particle surface is determined by the activated adsorption of OH anions first on the metal surface, with subsequent conversion into Cd(OH)2 and hydrated CdO layers (Duhirel et al. [1992])). Reaction products are also present in a partly dissolved Cd(OH)3" state. The activated adsorption mechanism of the anode reaction, as well as porous structure of the electrode, makes it appropriate to use for its analysis the equivalent circuit shown in Figure 4.5.14. It was shown by Xiong et al. [1996], by separate impedance measurements on the anode and cathode, that most of the impedance decrease during discharge is due to the anode, as the initial formation of a Cd(OH)Jrate limiting step of the reaction. The... 

The cathode of a modem Ni-Cd battery consists of controlled particle size spherical NiO(OH)2 particles, mixed with a conductive additive (Zn or acetylene black) and binder and pressed onto a Ni-foam current collector. Nickel hydroxide cathode kinetics is determined by a sohd state proton insertion reaction (Huggins et al. [1994]). Its impedance can therefore be treated as that of intercalation material, e.g. considering H+ diffusion toward the center of sohd-state particles and specific conductivity of the porous material itself. The porous nature of the electrode can be accounted for by using the transmission line model (D.D. Macdonald et al. [1990]). The equivalent circuit considering both diffusion within particles and layer porosity is given in Figure 4.5.9. Using the diffusion equations derived for spherical boundary conditions, as in Eq. (30), appears most appropriate. 

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