Diffusion layers, electrolyte

Water produced by electrochemical reactions in a fuel cell needs to be removed for efficient operation of the cell. Water transport in electrode-gas diffusion layers, electrolyte, and gas flow channels plays a critical role in the design of a fuel cell. Figure 7.8 shows water generation at the electrodeelectrolyte interface and mechanisms of water transport in a fuel cell. 

IHP) (the Helmholtz condenser formula is used in connection with it), located at the surface of the layer of Stem adsorbed ions, and an outer Helmholtz plane (OHP), located on the plane of centers of the next layer of ions marking the beginning of the diffuse layer. These planes, marked IHP and OHP in Fig. V-3 are merely planes of average electrical property the actual local potentials, if they could be measured, must vary wildly between locations where there is an adsorbed ion and places where only water resides on the surface. For liquid surfaces, discussed in Section V-7C, the interface will not be smooth due to thermal waves (Section IV-3). Sweeney and co-workers applied gradient theory (see Chapter III) to model the electric double layer and interfacial tension of a hydrocarbon-aqueous electrolyte interface [27]. 

The interaction of an electrolyte with an adsorbent may take one of several forms. Several of these are discussed, albeit briefly, in what follows. The electrolyte may be adsorbed in toto, in which case the situation is similar to that for molecular adsorption. It is more often true, however, that ions of one sign are held more strongly, with those of the opposite sign forming a diffuse or secondary layer. The surface may be polar, with a potential l/, so that primary adsorption can be treated in terms of the Stem model (Section V-3), or the adsorption of interest may involve exchange of ions in the diffuse layer. 

The repulsion between oil droplets will be more effective in preventing flocculation Ae greater the thickness of the diffuse layer and the greater the value of 0. the surface potential. These two quantities depend oppositely on the electrolyte concentration, however. The total surface potential should increase with electrolyte concentration, since the absolute excess of anions over cations in the oil phase should increase. On the other hand, the half-thickness of the double layer decreases with increasing electrolyte concentration. The plot of emulsion stability versus electrolyte concentration may thus go through a maximum. 

The diffusion layer widtli is very much dependent on tire degree of agitation of tire electrolyte. Thus, via tire parameter 5, tire hydrodynamics of tire solution can be considered. Experimentally, defined hydrodynamic conditions are achieved by a rotating cylinder, disc or ring-disc electrodes, for which analytical solutions for tire diffusion equation are available [37, 4T, 42 and 43]. 

Pt/Ru Catalyst Polymer Pt Catalyst Porous Gas Layer Electrolyte Layer Diffusion Membrane Electrode... 

The region of the gradual potential drop from the Helmholtz layer into the bulk of the solution is called the Gouy or diffuse layer (29,30). The Gouy layer has similar characteristics to the ion atmosphere from electrolyte theory. This layer has an almost exponential decay of potential with increasing distance. The thickness of the diffuse layer may be approximated by the Debye length of the electrolyte. 

Fig. 20.1 Potential and concentration gradients in the electrolytic cell CU/CUSO4/CU. (a) The electrodes are unpolarised the potential dilference is the equilibrium potential and there is no concentration gradient in the diffusion layer. (f>) The electrodes are polarised Ep of the anode is now more positive than E. whilst E of the cathode is more negative and concentration gradients exist across the diffusion layer c, C), are the concentrations at the electrode...

The conductivity of liquid and glass membranes is determined by ion-migration (absence of an excess of supporting electrolyte is assumed) in the diffusion layer. Equation (25) should then be written as ... 

In the thin-layer cavity cell technique, a cell is constructed to give a thin cavity on one wall of which the metal-plate working electrode is mounted. This wall is separated by a Teflon sheet in which a central aperture has been cut out, from the opposite wall of the cavity this wall contains entry and exit tubes for the test solution which is caused to flow past the working electrode provision is made for connections to the other electrodes. If the Teflon sheet is thin enough (about 0.05 mm), the distance between the two walls of the cavity is less than the normal thickness of the diffusion layer of the electrolyte when undergoing electrolysis, and so electrolysis within the cavity is rapid.26... 

Figure 1-13 displays the experimental dependence of the double-layer capacitance upon the applied potential and electrolyte concentration. As expected for the parallel-plate model, the capacitance is nearly independent of the potential or concentration over several hundreds of millivolts. Nevertheless, a sharp dip in the capacitance is observed (around —0.5 V i.e., the Ep/C) with dilute solutions, reflecting the contribution of the diffuse layer. Comparison of the double layer witii die parallel-plate capacitor is dius most appropriate at high electrolyte concentrations (i.e., when C CH). 

The model more generally accepted for metal/electrolyte interfaces envisages the electrical double layer as split into two parts the inner layer and the diffuse layer, which can be represented by two capacitances in series.1,3-7,10,15,32 Thus, the total differential capacitance C is equal to... 

For pc-Au/electrolyte interfaces, Clavilier and Nguyen Van Huong256 also concluded that the crystallographic inhomogeneity factor depends on ce. Later, the influence of the crystallographic inhomogeneity of pc and monocrystalline electrodes (with various surface defects) was discussed in many papers.75,152,154 156 247-259 It has been shown that the potential of the diffuse-layer capacitance minimum for a polycrystalline electrode does not correspond to Ea=Q of the whole surface, i.e., 2J 0,< 0 at E n. 

The division of the interface into an inner layer and a diffuse layer has been a matter of discussion in view of the molecular dimensions of the inner layer.122-126,279-285 However, the contribution of a constant capacitance is an experimental fact. Furthermore, molecular theories for electrolytes near a charged hard wall282 as well as phenomenological nonlocal electrostatic theories283 predict such a component without artificial introduction of any inner layers. This turns out to be an effect of the short-range structure of the solvent.279-285... 

The electrical double-layer structure at Ga/DMF, In(Ga)/DMF, and Tl(Ga)/DMF interfaces upon the addition of various amounts of NaC104 as a surface-inactive electrolyte has been investigated by differential capacitance, as well as by the streaming electrode method.358 The capacitance of all the systems was found to be independent of the ac frequency, v. The potential of the diffuse layer minimum was independent of... 

Figure 18 shows the dependence of the activation barrier for film nucleation on the electrode potential. The activation barrier, which at the equilibrium film-formation potential E, depends only on the surface tension and electric field, is seen to decrease with increasing anodic potential, and an overpotential of a few tenths of a volt is required for the activation energy to decrease to the order of kBT. However, for some metals such as iron,30,31 in the passivation process metal dissolution takes place simultaneously with film formation, and kinetic factors such as the rate of metal dissolution and the accumulation of ions in the diffusion layer of the electrolyte on the metal surface have to be taken into account, requiring a more refined treatment. 

Figure 4a. Electrochemical cells for microwave conductivity measurements. Cell above microwave conduit (1) electrochemical cell (plastic tube, placed on working electrode material), (2) counter-electrode, (3) reference electrode, (4) electrolyte, (5) space charge layer, (6) diffusion layer, (7) contact to working electrode, (8) waveguide.

Diffnsion finxes develop as a result of these concentration gradients. The layer of electrolyte where the concentration changes occur and within which the substances are transported by diffnsion is called the diffusion layer. Its thickness, 5 (the diffusion path length), depends on cell design features and on the intensity of convechve... 

It must be pointed out that in a diffusion layer where the ions are transported not only by migration but also by diffusion, the effective transport numbers t of the ions (the ratios between partial currents ij and total current t) will differ from the parameter tj [defined by Eq. (1.13)], which is the transport number of ion j in the bulk electrolyte, where concentration gradients and diffusional transport of substances are absent. In fact, in our case the effective transport number of the reacting ions in the diffusion layer is unity and that of the nonreacting ions is zero. 

It follows from Eqs. (4.37) and (4.38) that the diffusion-layer thickness will increase without limits and the diffusion flux will decrease to zero when the electrolyte is not stirred (v = 0) or the electrode not rotated (co = 0). This implies that a steady electric cnrrent cannot flow in such cells. But this conclusion is at variance with the experimental data. 

Natural convection can be eliminated entirely when electrolytes held in a matrix or porous support are used instead of free liquids. Natural convection will not develop in a pore space when the individual pores are sufficiently narrow. When such electrolytes are used, the diffusion layer propagates across the entire matrix (i.e., across the full electrode gap). 

The trends of behavior described above are found in solutions containing an excess of foreign electrolyte, which by definition is not involved in the electrode reaction. Without this excess of foreign electrolyte, additional effects arise that are most distinct in binary solutions. An appreciable diffusion potential q) arises in the diffusion layer because of the gradient of overall electrolyte concentration that is present there. Moreover, the conductivity of the solution will decrease and an additional ohmic potential drop will arise when an electrolyte ion is the reactant and the overall concentration decreases. Both of these potential differences are associated with the diffusion layer in the solution, and strictly speaking, are not a part of electrode polarization. But in polarization measurements, the potential of the electrode usually is defined relative to a point in the solution which, although not far from the electrode, is outside the diffusion layer. Hence, in addition to the true polarization AE, the overall potential drop across the diffusion layer, 9 = 9 + 9ohm is included in the measured value of polarization, AE. ... 

A considerable decrease in platinum consumption without performance loss was attained when a certain amount (30 to 40% by mass) of the proton-conducting polymer was introduced into the catalytically active layer of the electrode. To this end a mixture of platinized carbon black and a solution of (low-equivalent-weight ionomeric ) Nafion is homogenized by ultrasonic treatment, applied to the diffusion layer, and freed of its solvent by exposure to a temperature of about 100°C. The part of the catalyst s surface area that is in contact with the electrolyte (which in the case of solid electrolytes is always quite small) increases considerably, due to the ionomer present in the active layer. 

This book seeks essentially to provide a rigorous, yet lucid and comprehensible outline of the basic concepts (phenomena, processes, and laws) that form the subject matter of modem theoretical and applied electrochemistry. Particular attention is given to electrochemical problems of fundamental significance, yet those often treated in an obscure or even incorrect way in monographs and texts. Among these problems are some, that appear elementary at first glance, such as the mechanism of current flow in electrolyte solutions, the nature of electrode potentials, and the values of the transport numbers in diffusion layers. 

At present it is impossible to formulate an exact theory of the structure of the electrical double layer, even in the simple case where no specific adsorption occurs. This is partly because of the lack of experimental data (e.g. on the permittivity in electric fields of up to 109 V m"1) and partly because even the largest computers are incapable of carrying out such a task. The analysis of a system where an electrically charged metal in which the positions of the ions in the lattice are known (the situation is more complicated with liquid metals) is in contact with an electrolyte solution should include the effect of the electrical field on the permittivity of the solvent, its structure and electrolyte ion concentrations in the vicinity of the interface, and, at the same time, the effect of varying ion concentrations on the structure and the permittivity of the solvent. Because of the unsolved difficulties in the solution of this problem, simplifying models must be employed the electrical double layer is divided into three regions that interact only electrostatically, i.e. the electrode itself, the compact layer and the diffuse layer. 

It is assumed that the quantity Cc is not a function of the electrolyte concentration c, and changes only with the charge cr, while Cd depends both on o and on c, according to the diffuse layer theory (see below). The validity of this relationship is a necessary condition for the case where the adsorption of ions in the double layer is purely electrostatic in nature. Experiments have demonstrated that the concept of the electrical double layer without specific adsorption is applicable to a very limited number of systems. Specific adsorption apparently does not occur in LiF, NaF and KF solutions (except at high concentrations, where anomalous phenomena occur). At potentials that are appropriately more negative than Epzc, where adsorption of anions is absent, no specific adsorption occurs for the salts of... 

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