Diffusion proton transport mechanisms

The main characteristic to consider for a PEM to be used in potential fuel cell is proton conductivity. To achieve good performance of a PEM fuel cell, high proton conductivity is essential, especially at a high current density. To understand proton transport at a molecular level in hydrated polymeric membranes, there are two principal proton transport mechanisms (1) the Grotthus mechanism or proton hopping mechanism, and (2) the vehicular mechanism or diffusion mechanism [243-245]. 

The membrane proeessing and morphology have also significant effects on the proton transport and eonduetivity. The NMR study by Jayakody et al. [140] showed that the proton diffusivity is about an order of magnitude higher in the PPA-cast membranes than in DMAe-east membranes. Apparently an additional proton transport mechanism exists involving rapid exchange between the phosphoric acid and... 

Choi et al. proposed a pore transport model to describe proton diffusion within Nafion." The diffusion coefficients are predicted. The surface diffusion coefficient is 1.01 X10 cm /s at room temperature the vehicular diffusion coefficient is 1.71x10 cm /s and the Grotthuss diffusion coefficient is 7x10 cm /s. The Grotthuss diffusion is the fastest proton transport mechanism within Nafion. The surface diffusion coefficient is much lower than the other two diffusion coefficients. The surface diffusion does not contribute significantly to the overall conductivity of protons except at low water levels. 

The total electro-osmotic coefficient = Whydr + mo includes a contribution of hydrodynamic coupling (Whydr) and a molecular contribution related to the diffusion of mobile protonated complexes—namely, H3O. The relative importance, n ydr and depends on the prevailing mode of proton transport in pores. If structural diffusion of protons prevails (see Section 6.7.1), is expected to be small and Whydr- If/ ori the other hand, proton mobility is mainly due to the diffusion of protonated water clusters via the so-called "vehicle mechanism," a significant molecular contribution to n can be expected. The value of is thus closely tied to the relative contributions to proton mobility of structural diffusion and vehicle mechanism. ... 

Structural diffusion is favored by conditions that enhance the stiffness of the hydrogen-bonded network between water molecules low temperatures and low acid concentration. The decrease in water content leads to an effective increase in the concentration of acid protons, which in turn suppresses the contribution of structural diffusion, as found in aqueous acidic solutions. This agrees with the finding of an enhanced contribution of vehicular transport in PEMs at low hydration. Such an observation is also supported by recent studies of molecular mechanisms of proton transport in PEMs at minimal hydration. ... 

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 . 

As shown by DFTB and CPMD simulations, the principal features of the transport mechanism are rotational diffusion of the protonic defect and proton transfer toward a neighboring oxide ion. That is, only the proton shows long-range diffusion, whereas the oxygens reside in their crystallographic positions. Both experiments " " and quantum-MD simulations, have revealed that rotational diffu-... 

Some attempts to inclnde structural diffusion exist. The mechanism of proton transport in bulk water has been studied by various molecular modeling techniques like the Car-Parinello ab initio molecnlar dynamics simnlations (CPAIMD), mixed quan-tnm and classical mechanics technique (QM/MM), E " ... 

The functional form of the triggers ate based on transition state, as determined by the quantum mechanical calculation and their numerical values are parameterized to satisfy the macroscopically determined rate constant and activation energy. Local equilibration at the end of the reaction helps in maintaining the correct heat of reaction and structure. For the vahdation of the algorithm, it has been implemented to study proton transport in bulk water. In bulk water the two components of the total diffusivity were found to be uncorrelated. 

Going beyond an atomistic description of the aqueous phase and the membrane, Paddison and coworkers [79-88] employed statistical mechanical models, incorporating solvent friction and spatially dependent dielectric properties, to the calculation of the proton diffusion coefficient in Nation and PEEKK membrane pores. They concluded from their studies that, in accordance with NMR based evidence [50], the mechanism of proton transport is more vehicular (classical ion transport) in the vicinity of the pore surface and more Grotthus-like in the center. 

Structural models emerge from the notion of membrane as a heterogenous porous medium characterized by a radius distribution of water-filled pores. This structural concept of a water-filled network embedded in the polymer host has already formed the basis for the discussion of proton conductivity mechanisms in previous sections. Its foundations have been discussed in Sect. 8.2.2.1. Clearly, this concept promotes hydraulic permeation (D Arcy flow [80]) as a vital mechanism of water transport, in addition to diffusion. Since larger water contents result in an increased number of pores used for water transport and in larger mean radii of these pores, corresponding D Arcy coefficients are expected to exhibit strong dependencies on w. 

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