Proton conductivity diffusion

Figure 9. Proton conductivity diffusion coefficient (mobility) and water self-diffusion coefficient of Nation 117 (EW = 1100 g/equiv), as a function of temperature and the degree of hydration n = [H20]/[—SOsH]). ...

Proton conductivity diffusion coefficients for hydrated samples and samples solvated with... 

Graduating now to the diamagnetic cation [H2N-NH3]+, one finds much of interest. NMR (of 1H, 2H, 7Li, 14N, 15N) and other measurements of (H2N-NH3) (HSO4) and similar salts, and especially of Li(H2N-NH3)(S04), reveal ferroelectric behaviour and substantial capability of proton conductivity/diffusion through the crystals (e.g. Refs. 70 and 71). 

Figure 23.7 Proton conductivity diffusion coefficient (DJ and self-diffusion coefRcient of phosphorous for poly-(diallyldimethylammonium-dihydrogenphosphate)-phosphoric acid ((PAMA+H2P04 )-n H3PO4) as a function of the phosphoric acid content [98]. Note that the ratio DJDp remains almost constant (see text).

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. 

Water proton self-diffusion exhibits a break point and begins to increase at a = 0.85. In the case of AOT self-diffusion, a breakpoint also occurs, but AOT self-diffusion continues to slow as a decreases further. These breakpoints in both water and AOT selfdiffusion behavior at a = 0.85 coincide with the breakpoint in electrical conductivity illustrated in Fig. 1, where the onset of electrical conductivity percolation occurs. At a = 0.7 two more breakpoints in the water proton and AOT self-diffusion are seen. Water proton self-diffusion increases more markedly and AOT self-diffusion beings to increase markedly. 

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. 

MeOH is transported through the membrane by two modes diffusion and electro-osmotic drag. ° When MeOH comes into contact with the membrane, it diffuses through the membrane from anode to cathode and is also dragged along with the hydrated protons under the influence of current flowing across the cell. Therefore, a correlation between the MeOH diffusion coefficient and proton conductivity is observed. The diffusive mode of MeOH transport dominates when the cell is idle, whereas the electro-osmotic drag... 

Colbow, Zhang, and Wilkinson [128] showed that the performance of liquid feed fuel cells could be increased by oxidizing the carbon diffusion layer. The DL was electrochemically oxidized in acidic aqueous solution (impregnated in some cases with proton-conducting ionomer) prior to application of the electrocatalyst. 

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]. 

A poorly balanced water distribution in the fuel cell can severely impair its performance and cause long-term effects due to structural degradation. If PEMs or CLs are too dry, proton conductivity will be poor, potentially leading to excessive joule heating, which could affect the structural integrity of the cell. Too much water in diffusion media (CLs and GDLs) blocks the gaseous supply of reactants. As these examples show, all processes in PEECs are linked to water distribution and the balance of water fluxes. 

A more recent view of proton transport is that of Kreuer, who, compared with the Zundel-based view, describes the process on different structural scales within phase separated morphologies. The smallest scale is molecular, which involves intermolecular proton transfer and the breaking and re-forming of hydrogen bonds. When the water content becomes low, the relative population of hydrogen bonds decreases so that proton conductance diminishes in a way that the elementary mechanism becomes that of the diffusion of hydrated protons, the so-called vehicle mechanism . 

The highest level, at structural scales >10 nm, is that over which long-range transport takes place and diffusion depends on the degree of connectivity of the water pockets, which involves the concept of percolation. The observed decrease in water permeation with decreasing water volume fraction is more pronounced in sulfonated poly(ether ketone) than in Nafion, owing to differences in the state of percolation. Proton conductivity decreases in the same order, as well. 

Allcock et al. also have investigated the use of phosphonated polyphosphazenes as potential membrane materials for use in direct methanol fuel cells (Figure A2) Membranes were found to have lEC values between 1.17 and 1.43 mequiv/g and proton conductivities between 10 and 10 S/cm. Methanol diffusion coefficients for these membranes were found to be at least 12 times lower than that for Nafion 117 and 6 times lower than that for a cross-linked sulfonated polyphosphazene membrane. 

X 10 cm /s at room temperature) and that the diffusion of protonated water molecules makes some contribution to the total proton conductivity (vehicle mechanism " ). This is --"22% when assuming that the diffusion coefficients of H2O and H3O+ (or H502 ) are identical. However, as suggested by Agmon, " the diffusion of H3O+ may be retarded, because of the strong hydrogen bonding in the first hydration shell. 

Figure 2. Conductivity diffusion coefficient (mobility) of protons and water self-diffusion coefficient of aqueous solutions of hydrochloric acid (HCl), as a function of acid concentration (molarity, M) (data are taken from ref 141).

Figure 4. Schematic illustration of correlated proton transfers in pure liquid imidazole leading to proton diffusion but not proton conductivity (see text).

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