On a Pioneering Polymer Electrolyte Fuel Cell Model

"Polymer Electrolyte Fuel Cell Model" is a seminal work that continues to form the basis for modern modeling efforts, especially models concerning the membrane and its behavior at the continuum level. The paper is complete with experimental data, modeling equations, model validation, and optimization scenarios. While the treatment of the underlying phenomena is limited to isothermal, single-phase conditions, and one-dimensional flow, it represents the key interactions within the membrane at the center of the PEFC. It focuses on analyzing the water balance within the cell and clearly demonstrates the complex interactions of water diffusion and electro-osmotic flux. Cell-level and system-level water balance are key to the development of efficient PEFCs going forward, particularly as researchers address the need to simplify humidification and recycle configurations while increasing the operating temperature of the stack to minimize radiator requirements

Impact of Energy Crops on Soil Management and Erosion

Energy crops are perennials that require less cultivation and inputs than conventional crops, and are low maintenance harvest crops used for biofuels

Water Uptake in PEMFC Catalyst Layers

Water uptake profiles of proton-exchange-membrane fuel-cell catalyst layers are characterized in the form of capillary-pressure saturation (Pc-S) curves. The curves indicate that the catalyst layers tested are highly hydrophilic and require capillary pressures as low as -80 kPa to eject imbibed water. Comparison of materials made with and without Pt indicates a difference in water ejection and uptake phenomena due to the presence of Pt. The addition of Pt increases the tendency of the catalyst layer to retain water. Dynamic vapor sorption (DVS) is used to characterize the water-vapor sorption onto Nafion, Pt/C, and C surfaces. The DVS results align with the trends found from the Pc-S curves and show an increased propensity for water uptake in the presence of Pt. The effect of the ion in Nafion, sodium or protonated form, is also compared and demonstrates that although the protonation of the Nafion in the catalyst layer also increases hydrophilicity, the effect is not as great as that caused by Pt

Modeling Water Management in Polymer-Electrolyte Fuel Cells

Fuel cells may become the energy-delivery devices of the 21st century with realization of a carbon-neutral energy economy. Although there are many types of fuel cells, polymerelectrolyte fuel cells (PEFCs) are receiving the most attention for automotive and small stationary applications. In a PEFC, hydrogen and oxygen are combined electrochemically to produce water, electricity, and waste heat. During the operation of a PEFC, many interrelated and complex phenomena occur. These processes include mass and heat transfer, electrochemical reactions, and ionic and electronic transport. Most of these processes occur in the through-plane direction in what we term the PEFC sandwich as shown in Figure 1. This sandwich comprises multiple layers including diffusion media that can be composite structures containing a macroporous gas-diffusion layer (GDL) and microporous layer (MPL), catalyst layers (CLs), flow fields or bipolar plates, and a membrane. During operation fuel is fed into the anode flow field, moves through the diffusion medium, and reacts electrochemically at the anode CL to form hydrogen ions and electrons. The oxidant, usually oxygen in air, is fed into the cathode flow field, moves through the diffusion medium, and is electrochemically reduced at the cathode CL by combination with the generated protons and electrons. The water, either liquid or vapor, produced by the reduction of oxygen at the cathode exits the PEFC through either the cathode or anode flow field. The electrons generated at the anode pass through an external circuit and may be used to perform work before they are consumed at the cathode. The performance of a PEFC is most often reported in the form of a polarization curve, as shown in Figure 2. Roughly speaking, the polarization curve can be broken down into various regions. First, it should be noted that the equilibrium potential differs from the open-circuit voltage due mainly to hydrogen crossover through the membrane (i.e., a mixed potential on the cathode) and the resulting effects of the kinetic reactions. Next, at low currents, the behavior of a PEFC is dominated by kinetic losses. These losses mainly stem from the high overpotential of the oxygen-reduction reaction (ORR). As the current is increased, ohmic losses become a factor in lowering the overall cell potential. These ohmic losses are mainly from ionic losses in the electrodes and separator. At high currents, mass-transport limitations become increasingly important. These losses are due to reactants not being able to reach the electrocatalytic sites. Key among the issues facing PEFCs today is water management. Due to their low operating temperature (< 100 C), water exists in both liquid and vapor phases. Furthermore, state-of-the-art membranes require the use of water to provide high conductivity and fast proton transport. Thus, there is a tradeoff between having enough water for proton conduction (ohmic losses), but not too much or else the buildup of liquid water will cause a situation in which the reactant-gas-transport pathways are flooded (mass-transfer limitations). Figure 3 displays experimental evidence of the effects of water management on performance. In Figure 3(a), a neutron image of water content displays flooding near the outlet of the cell due to accumulation of liquid water and a decrease in the gas flowrates. The serpentine flow field is clearly visible with the water mainly underneath the ribs. Figure 3(b) shows polarization performance at 0.4 and 0.8 V and high-frequency resistance at 0.8 V as a function of cathode humidification temperature. At low current densities, as the inlet air becomes more humid, the membrane resistance decreases, and the performance increases. At higher current densities, the same effect occurs; however, the higher temperatures and more humid air also results in a lower inlet oxygen partial pressure

Kinetic Heterogeneities in a Highly Supercooled Liquid

We study a highly supercooled two-dimensional fluid mixture via molecular dynamics simulation. We follow bond breakage events among particle pairs, which occur on the scale of the $\alpha$ relaxation time $\tau_{\alpha}$. Large scale heterogeneities analogous to the critical fluctuations in Ising systems are found in the spatial distribution of bonds which are broken in a time interval with a width of order $0.05\tau_{\alpha}$. The structure factor of the broken bond density is well approximated by the Ornstein-Zernike form. The correlation length is of order $100 \sigma_1$ at the lowest temperature studied, $\sigma_1$ being the particle size. The weakly bonded regions thus identified evolve in time with strong spatial correlations.Comment: 3 pages, 6 figure

Femtosecond photodissociation dynamics of 1,4-diiodobenzene by gas-phase X-ray scattering and photoelectron spectroscopy

We present a multifaceted investigation into the initial photodissociation dynamics of 1,4-diiodobenzene (DIB) following absorption of 267 nm radiation. We combine ultrafast time-resolved photoelectron spectroscopy and X-ray scattering experiments performed at the Linac Coherent Light Source (LCLS) to study the initial electronic excitation and subsequent rotational alignment, and interpret the experiments in light of Complete Active Space Self-Consistent Field (CASSCF) calculations of the excited electronic landscape. The initially excited state is found to be a bound 1B1 surface, which undergoes ultrafast population transfer to a nearby state in 35 ± 10 fs. The internal conversion most likely leads to one or more singlet repulsive surfaces that initiate the dissociation. This initial study is an essential and prerequisite component of a comprehensive study of the complete photodissociation pathway(s) of DIB at 267 nm. Assignment of the initially excited electronic state as a bound state identifies the mechanism as predissociative, and measurement of its lifetime establishes the time between excitation and initiation of dissociation, which is crucial for direct comparison of photoelectron and scattering experiments.</p

The potential energy landscape of a model glass former: thermodynamics, anharmonicities, and finite size effects

It is possible to formulate the thermodynamics of a glass forming system in terms of the properties of inherent structures, which correspond to the minima of the potential energy and build up the potential energy landscape in the high-dimensional configuration space. In this work we quantitatively apply this general approach to a simulated model glass-forming system. We systematically vary the system size between N=20 and N=160. This analysis enables us to determine for which temperature range the properties of the glass former are governed by the regions of the configuration space, close to the inherent structures. Furthermore, we obtain detailed information about the nature of anharmonic contributions. Moreover, we can explain the presence of finite size effects in terms of specific properties of the energy landscape. Finally, determination of the total number of inherent structures for very small systems enables us to estimate the Kauzmann temperature

Water Uptake in PEMFC Catalyst Layers

Water uptake profiles of proton-exchange-membrane fuel-cell catalyst layers are characterized in the form of capillary-pressure saturation (Pc-S) curves. The curves indicate that the catalyst layers tested are highly hydrophilic and require capillary pressures as low as -80 kPa to eject imbibed water. Comparison of materials made with and without Pt indicates a difference in water ejection and uptake phenomena due to the presence of Pt. The addition of Pt increases the tendency of the catalyst layer to retain water. Dynamic vapor sorption (DVS) is used to characterize the water-vapor sorption onto Nafion, Pt/C, and C surfaces. The DVS results align with the trends found from the Pc-S curves and show an increased propensity for water uptake in the presence of Pt. The effect of the ion in Nafion, sodium or protonated form, is also compared and demonstrates that although the protonation of the Nafion in the catalyst layer also increases hydrophilicity, the effect is not as great as that caused by Pt