Effect of Commercial Gas Diffusion Layers on Catalyst Durability of Polymer Electrolyte Fuel Cells in Varied Cathode Gas Environment.

Gas diffusion layers (GDLs) play a crucial role in heat transfer and water management of cathode catalyst layers in polymer electrolyte fuel cells (PEFCs). Thermal and water gradients can accelerate electrocatalyst degradation and therefore the selection of GDLs can have a major influence on PEFC durability. Currently, the role of GDLs in electrocatalyst degradation is poorly studied. In this study, electrocatalyst accelerated stress test studies are performed on membrane electrode assemblies (MEAs) prepared using three most commonly used GDLs. The effect of GDLs on electrocatalyst degradation is evaluated in both nitrogen (non-reactive) and air (reactive) gas environments at 100% relative humidity. In situ electrochemical characterization and extensive physical characterization is performed to understand the subtle differences in electrocatalyst degradation and correlated to the use of different GDLs. Overall, no difference is observed in the electrocatalyst degradation due to GDLs based on polarization curves at the end of life. But interestingly, MEA with a cracked microporous layer (MPL) in the GDL exhibited a higher electrocatalyst loading loss, which resulted in a lower and more heterogeneous increase in the average electrocatalyst nanoparticle size.

Insights into Interfacial and Bulk Transport Phenomena Affecting Proton Exchange Membrane Water Electrolyzer Performance at Ultra-Low Iridium Loadings.

Interfacial and bulk properties between the catalyst layer and the porous transport layer (PTL) restrict the iridium loading reduction for proton exchange membrane water electrolyzers (PEMWEs), by limiting their mass and charge transport. Using titanium fiber PTLs of varying thickness and porosity, the bulk and interface transport properties are investigated, correlating them to PEMWEs cell performance at ultra-low Ir loadings of ≈0.05 mgIr cm-2 . Electrochemical experiments, tomography, and modeling are combined to study the bulk and interfacial impacts of PTLs on PEMWE performance. It is found that the PEMWE performance is largely dependent on the PTL properties at ultra-low Ir loadings; bulk structural properties are critical to determine the mass transport and Ohmic resistance of PEMWEs while the surface properties of PTLs are critical to govern the catalyst layer utilization and electrode kinetics. The PTL-induced variation in kinetic and mass transport overpotential are on the order of ≈40 and 60 mV (at 80 A mgIr -1 ), respectively, while a nonnegligible 35 mV (at 3 A cm-2 ) difference in Ohmic overpotential. Thus at least 150 mV improvement in PEMWE performance can be achieved through PTL structural optimization without membrane thickness reduction or advent of new electrocatalysts.

Measurement of Contact Angles at Carbon Fiber-Water-Air Triple-Phase Boundaries Inside Gas Diffusion Layers Using X-ray Computed Tomography.

Gas diffusion layers (GDLs) are porous carbonaceous layers that are widely used in energy conversion and storage devices. Simulation of water transport through GDLs, in a polymer electrolyte fuel cell (PEFC), for example, typically uses goniometer-measured external contact angles. Until now, there is no well-developed method to obtain contact angles inside the GDLs. AlRatrout et al. developed an open-source code to compute local contact angles at triple-phase contact points from segmented micro-X-ray computed tomography (X-ray CT) images of porous rocks. We apply it, for the first time, to micro-X-ray CT images of water-filled commercial GDLs and compute local contact angles at internal GDL fiber-water-air triple-phase contact points. We obtain a state of mixed wettability (hydrophilic and hydrophobic) inside all GDL samples, with a broad range of contact angles, instead of one hydrophobic contact angle found from goniometer experiments. Lattice Boltzmann water transport simulations performed with these distributed contact angles produce results that are in better agreement with experimental data. We also obtain high-resolution X-ray photoelectron spectroscopy (XPS) data of the GDL samples and find that the concentration of oxide species correlates strongly with the measured hydrophilicity. The method introduced here can help rationally design GDLs and directly quantify their internal surface wettability that is needed for accurate predictions of their functionality in energy technology devices.

Observation of Preferential Pathways for Oxygen Removal through Porous Transport Layers of Polymer Electrolyte Water Electrolyzers.

Understanding the relationships between porous transport layer (PTL) morphology and oxygen removal is essential to improve the polymer electrolyte water electrolyzer (PEWE) performance. Operando X-ray computed tomography and machine learning were performed on a model electrolyzer at different water flow rates and current densities to determine how these operating conditions alter oxygen transport in the PTLs. We report a direct observation of oxygen taking preferential pathways through the PTL, regardless of the water flow rate or current density (1-4 A/cm2). Oxygen distribution in the PTL had a periodic behavior with period of 400 µm. A computational fluid dynamics model was used to predict oxygen distribution in the PTL showing periodic oxygen front. Observed oxygen distribution is due to low in-plane PTL tortuosity and high porosity enabling merging of oxygen bubbles in the middle of the PTL and also due to aerophobicity of the layer.

Convenient non-invasive electrochemical techniques to monitor microbial processes: current state and perspectives.

Real-time electrochemical monitoring in bioprocesses is an improvement over existing systems because it is versatile and provides more information to the user than periodic measurements of cell density or metabolic activity. Real-time electrochemical monitoring provides the ability to monitor the physiological status of actively growing cells related to electron transfer activity and potential changes in the proton gradient of the cells. Voltammetric and amperometric techniques offer opportunities to monitor electron transfer reactions when electrogenic microbes are used in microbial fuel cells or bioelectrochemical synthesis. Impedance techniques provide the ability to monitor the physiological status of a wide range of microorganisms in conventional bioprocesses. Impedance techniques involve scanning a range of frequencies to define physiological activity in terms of equivalent electrical circuits, thereby enabling the use of computer modeling to evaluate specific growth parameters. Electrochemical monitoring of microbial activity has applications throughout the biotechnology industry for generating real-time data and offers the potential for automated process controls for specific bioprocesses.

In-situ electrochemical analysis of microbial activity.

Microbes have a wide range of metabolic capabilities available that makes them industrially useful organisms. Monitoring these metabolic processes is a crucial component in efficient industrial application. Unfortunately, monitoring these metabolic processes can often be invasive and time consuming and expensive, especially within an anaerobic environment. Electrochemical techniques, such as cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) offer a non-invasive approach to monitor microbial activity and growth. EIS and CV were used to monitor Clostridium phytofermentans, an anaerobic and endospore-forming bacterium. C. phytofermentans ferments a wide range of sugars into hydrogen, acetate, and ethanol as fermentation by-products. For this study, both traditional microbiological and electrochemical techniques were used to monitor the growth of C. phytofermentans and the formation of fermentation products. An irreversible reduction peak was observed using CV beginning at mid-logarithmic phase of growth. This peak was associated with C. phytofermentans and not the spent medium and was indicative of a decrease in carbon and energy sources to the cells. Additionally, EIS analysis during growth provided information related to increased charge transfer resistance of the culture also as a function of carbon and energy source depletion. Results demonstrate that CV and EIS are useful tools in the monitoring the physiological status of bioprocesses.