Diffusion layer electricity conductivity

Overbeek and Booth [284] have extended the Henry model to include the effects of double-layer distortion by the relaxation effect. Since the double-layer charge is opposite to the particle charge, the fluid in the layer tends to move in the direction opposite to the particle. This distorts the symmetry of the flow and concentration profiles around the particle. Diffusion and electrical conductance tend to restore this symmetry however, it takes time for this to occur. This is known as the relaxation effect. The relaxation effect is not significant for zeta-potentials of less than 25 mV i.e., the Overbeek and Booth equations reduce to the Henry equation for zeta-potentials less than 25 mV [284]. For an electrophoretic mobility of approximately 10 X 10 " cm A -sec, the corresponding zeta potential is 20 mV at 25°C. Mobilities of up to 20 X 10 " cmW-s, i.e., zeta-potentials of 40 mV, are not uncommon for proteins at temperatures of 20-30°C, and thus relaxation may be important for some proteins. 

Why this large difference Well, whenever you consider an alloy rather than a pure material, the oxide layer - whatever its nature (NiO, Cr203, etc.) - has foreign elements contained in it, too. Some of these will greatly increase either the diffusion coefficients in, or electrical conductivity of, the layer, and make the rate of oxidation through the layer much more than it would be in the absence of foreign element contamination. 

Tafel slope (Napieran loop) transfer coefficient diffusion layer thickness dielectric constant, relative electric field constant = 8.85 x 10 F cm overvoltage, polarization ohmic voltage drop, resistance polarization specific conductance, conductivity electrochemical potential of material X,... 

The adsorption of ions at insulator surfaces or ionization of surface groups can lead to the formation of an electrical double layer with the diffuse layer present in solution. The ions contained in the diffuse layer are mobile while the layer of adsorbed ions is immobile. The presence of this mobile space charge is the source of the electrokinetic phenomena.t Electrokinetic phenomena are typical for insulator systems or for a poorly conductive electrolyte containing a suspension or an emulsion, but they can also occur at metal-electrolyte solution interfaces. 

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... 

The main components of a PEM fuel cell are the flow channels, gas diffusion layers, catalyst layers, and the electrolyte membrane. The respective electrodes are attached on opposing sides of the electrolyte membrane. Both electrodes are covered with diffusion layers, and the flow channels/current collectors. The flow channels collect current from the electrodes while providing the fuel or oxidant with access to the electrodes. The gas diffusion layer allows gases to diffuse to the electro-catalysts and provides electrical contact throughout the catalyst layers. Within the anode catalyst layer, the fuel (typically H2) is oxidized to produce electrons and protons. The electrons travel through an external circuit to produce electricity, while the protons pass through the proton conducting electrolyte membrane. Within the cathode catalyst layer, the electrons and protons recombine with the oxidant (usually 02) to produce water. 

A PEFC consists of two electrodes in contact with an electrolyte membrane (Fig. 14.7). The membrane is designed as an electronic insulator material separating the reactants (H2 and 02/air) and allowing only the transport of protons towards the electrodes. The electrodes are constituted of a porous gas diffusion layer (GDL) and a catalyst (usually platinum supported on high surface area carbon) containing active layer. This assembly is sandwiched between two electrically conducting bipolar plates within which gas distribution channels are integrated [96]. 

Due to their high electrical and thermal conductivity, materials made out of metal have been considered for fuel cells, especially for components such as current collectors, flow field bipolar plates, and diffusion layers. Only a very small amount of work has been presented on the use of metal materials as diffusion layers in PEM and DLFCs because most of the research has been focused on using metal plates as bipolar plates [24] and current collectors. The diffusion layers have to be thin and porous and have high thermal and electrical conductivity. They also have to be strong enough to be able to support the catalyst layers and the membrane. In addition, the fibers of these metal materials cannot puncture the thin proton electrolyte membrane. Thus, any possible metal materials to be considered for use as DLs must have an advantage over other conventional materials. 

Similar metal sheets have also been used as DLs in the cathode of PEMFCs. Wilkinson et al. [37,38] presented the idea of using fluid distribution layers made out of metal meshes with electrically conductive fillers inside the holes of the meshes. A very similar idea was also presented by Fiamada and Nakato [39]. Eosfeld and Eleven [40] presented another example of fuel cells that use metal meshes as diffusion layers along with metal FF plates. 

The catalyst layer usually consists of carbon-supported catalyst or carbon black mixed with PIPE and/or proton-conducting ionomer (e.g.. Nation iono-mer). Because the sizes of the pores in a t) ical DL are in the range of 1-100 pm and the average pore size of the CL is just a few hundred nanometers, the risk of having low electrical contact between both layers is high [129]. Thus, the MPL is also used to block the catalyst particles and does not let them clog the pores within the diffusion layer [57,90,132,133]. 

Passalacqua ef al. [143] were able to prove fhaf when an MPL is interposed befween fhe DL and fhe CL, fhe performance of fhe cell improves subsfan-tially. They concluded that the MPL reduced the size of fhe wafer droplefs, thus enhancing the oxygen diffusion. This layer also prevented fhe cafalysf particles from entering too far info fhe DL. Park ef al. [102] concluded fhaf wifh fhe addition of an MPL, bofh water management and electrical conductivity improved. 

To design the optimal diffusion layer for a specific fuel cell system, it is important to be able to measure and understand all the parameters and characteristics that have a direct influence on the performance of the diffusion layers. This section will discuss in detail some of the most important properties that affect the diffusion layers, such as thickness, hydrophobicity and hydrophilicity, porosity and permeability (for both gas and liquids), electrical and thermal conductivity, mechanical properties, durability, and flow... 

The thickness of the diffusion layer is directly related to the mass transport of gases and liquid within the material because it determines the length of the flow path. The electrical conductivity and resistance of the DL are also affected substantially by the thickness of the material. Therefore, to choose an optimal DL, there has to be a compromise between the thickness of the material and the properties mentioned before. 

Electrical and thermal conductivity are important diffusion layer properties that affect the fuel cell s overall performance. The maferial chosen to be the DL in a fuel cell must have a good electrical conductivity in order for the electron flow from the FF plates to the CLs (and vice versa) to have the least possible resistance. Similarly, the DL material must have good thermal properties so that heat generated in the active zones can be removed efficiently. Therefore, in order to choose an optimal material it is critical to be able to measure the electrical and thermal conductivity. In this section, a number of procedures used fo measure fhese paramefers will be discussed. 

The following subsection will briefly discuss the main methods used to measure in-plane and through-plane electrical conductivity for diffusion layer materials. This parameter is critical for optimal fuel cell performance. 

The most typical way to measure the in-plane electrical conductivity of a diffusion layer is through the use of the four-point probe method. A small current is applied across the sample material a separate set of voltage measuring probes that are in touch with the material are used to measure the resulting voltage drop in order to calculate the resistance. With these values, the in-plane resistivity, p, can be calculated with the following equation [9,233] ... 

Therefore, if is necessary to have good interaction between the diffusion layers and fhe FF plafes—nof only from a mass transport standpoint but also to maintain optimal electrical and thermal conductivity between them. Section 4.4.4 explained in detail measurement techniques to determine the electrical resistance in diffusion layers. It is important to note that most of fhose methods can also be implemented in order to calculate the contact resistance between the DLs and the FF plates. In this subsection, we will focus mostly on mass transport interactions between these two components. 

Diffusion medium properties for the PEFC system were most recently reviewed by Mathias et al. The primary purpose of a diffusion medium or gas diffusion layer (GDL) is to provide lateral current collection from the catalyst layer to the current collecting lands as well as uniform gas distribution to the catalyst layer through diffusion. It must also facilitate the transport of water out of the catalyst layer. The latter function is usually fulfilled by adding a coating of hydrophobic polymer such as poly(tet-rafluoroethylene) (PTFE) to the GDL. The hydrophobic polymer allows the excess water in the cathode catalyst layer to be expelled from the cell by gas flow in the channels, thereby alleviating flooding. It is known that the electric conductivity of GDL is... 

The remaining concentration of electron holes and, therefore, the electrical conductivity are functions of the water vapor pressure. This function can be derived by applying the formula (15a) of the exhaustion boundary layer. There we have, however, to substitute for Using the law of mass action of (21), we obtain for the diffusion potential... 

In a typical spectroelectrochemical measurement, an optically transparent electrode (OTE) is used and the UV/vis absorption spectrum (or absorbance) of the substance participating in the reaction is measured. Various types of OTE exist, for example (i) a plate (glass, quartz or plastic) coated either with an optically transparent vapor-deposited metal (Pt or Au) film or with an optically transparent conductive tin oxide film (Fig. 5.26), and (ii) a fine micromesh (40-800 wires/cm) of electrically conductive material (Pt or Au). The electrochemical cell may be either a thin-layer cell with a solution-layer thickness of less than 0.2 mm (Fig. 9.2(a)) or a cell with a solution layer of conventional thickness ( 1 cm, Fig. 9.2(b)). The advantage of the thin-layer cell is that the electrolysis is complete within a short time ( 30 s). On the other hand, the cell with conventional solution thickness has the advantage that mass transport in the solution near the electrode surface can be treated mathematically by the theory of semi-infinite linear diffusion. 

Arrhenius plots of conductivity for the four components of the elementary cell are shown in Fig. 34. They indicate that electrolyte and interconnection materials are responsible of the main part of ohmic losses. Furthermore, both must be gas tight. Therefore, it is necessary to use them as thin and dense layers with a minimum of microcracks. It has to be said that in the literature not much attention has been paid to electrode overpotentials in evaluating polarization losses. These parameters greatly depend on composition, porosity and current density. Their study must be developed in parallel with the physical properties such as electrical conductivity, thermal expansion coefficient, density, atomic diffusion, etc. 

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