Real time adaptive efficient cold start strategy for proton exchange membrane fuel cells

Cold start of proton exchange membrane fuel cells (PEMFCs) at sub-zero temperatures is perceived as one of the obstacles in their commercialization way in automotive application. This paper proposes a novel internal-based adaptive strategy for the cold start of PEMFC to control its operating current in real time in a way to maximize the generated heat flux and electrical power in a short time span. In this respect, firstly, an online parameter identification method is integrated into a semi-empirical model to cope with the PEMFC performances drifts during cold start. Subsequently, an optimization algorithm is launched to find the best operating points from the updated model. Finally, the determined operating point, which is the current corresponding to the maximum power, is applied to PEMFC to achieve a rapid cold start. It should be noted that the utilization of adaptive filters has escaped the attention of previous PEMFC cold start studies. The ultimate results of the proposed strategy are experimentally validated and compared to the most commonly used cold start strategies based on Potentiostatic and Galvanostatic modes. The experimental outcomes of the comparative study indicate the striking superior performance of the proposed strategy in terms of heating time and energy requirement. © 2018 Elsevier Lt

Membraneless Electrolyzers for Solar Fuels Production

Solar energy has the potential to meet all of society’s energy demands, but challenges remain in storing it for times when the sun is not shining. Electrolysis is a promising means of energy storage which applies solar-derived electricity to drive the production of chemical fuels. These so-called solar fuels, such as hydrogen gas produced from water electrolysis, can be fed back to the grid for electricity generation or used directly as a fuel in the transportation sector. Solar fuels can be generated by coupling a photovoltaic (PV) cell to an electrolyzer, or by directly converting light to chemical energy using a photoelectrochemical cell (PEC). Presently, both PV-electrolyzers and PECs have prohibitively high capital costs which prevent them from generating hydrogen at competitive prices. This dissertation explores the design of membraneless electrolyzers and PECs in order to simplify their design and decrease their overall capital costs. A membraneless water electrolyzer can operate with as few as three components: A cathode for the hydrogen evolution reaction, an anode for the oxygen evolution reaction, and a chassis for managing the flows of a liquid electrolyte and the product gas streams. Absent from this device is an ionically conducting membrane, a key component in a conventional polymer electrolyte membrane (PEM) electrolyzer that typically serves as a physical barrier for separating product gases generated at the anode and cathode. These membranes can allow for compact and efficient electrolyzer designs, but are prone to degradation and failure if exposed to impurities in the electrolyte. A membraneless electrolyzer has the opportunity to reduce capital costs and operate in non-pristine environments, but little is known about the performance limitations and design rules that govern operation of membraneless electrolyzers. These design rules require a thorough understanding of the thermodynamics, kinetics, and transport processes in electrochemical systems. In Chapter 2, these concepts are reviewed and a framework is provided to guide the continuum scale modeling of the performance of membraneless electrochemical cells. Afterwards, three different studies are presented which combine experiment and theory to demonstrate the mechanisms of product transport and efficiency loss. Chapter 3 investigates the dynamics of hydrogen bubbles during operation of a membraneless electrolyzer, which can strongly affect the product purity of the collected hydrogen. High-speed video imaging was implemented to quantify the size and position of hydrogen gas bubbles as they detach from porous mesh electrodes. The total hydrogen detected was compared to the theoretical value predicted by Faraday’s law. This analysis confirmed that not all electrochemically generated hydrogen enters the gas phase at the cathode surface. In fact, significant quantities of hydrogen remain dissolved in solution, and can result in lower product collection efficiencies. Differences in bubble volume fraction evolved along the length of the cathode reflect differences in the local current densities, and were found to be in agreement with the primary current distribution. Overall, this study demonstrates the ability to use in-situ HSV to quantitatively evaluate key performance metrics of membraneless electrolyzers in a non-invasive manner. This technique can be of great value for future experiments, where statistical analysis of bubble sizes and positions can provide information on how to collect hydrogen at maximum purity. Chapter 4 presents an electrode design where selective placement of the electrocatalyst is shown to enhance the purity of hydrogen collected. These “asymmetric electrodes” were prepared by coating only one planar face of a porous titanium mesh electrode with platinum electrocatalyst. For an opposing pair of electrodes, the platinum coated surface faces outwards such that the electrochemically generated bubbles nucleate and grow on the outside while ions conduct through the void spacing in the mesh and across the inter-electrode gap. A key metric used in evaluating the performance of membraneless electrolyzers is the hydrogen cross-over percentage, which is defined as the fraction of electrochemically generated hydrogen that is collected in the headspace over the oxygen-evolving anode. When compared to the performance of symmetric electrodes – electrodes coated on both faces with platinum – the asymmetric electrodes demonstrated significantly lower rates of cross-over. With optimization, asymmetric electrodes were able to achieve hydrogen cross-over values as low as 1%. These electrodes were then incorporated into a floating photovoltaic electrolysis device for a direct demonstration of solar driven electrolysis. The assembled “solar fuels rig” was allowed to float in a reservoir of 0.5 M sulfuric acid under a light source calibrated to simulate sunlight, and a solar to hydrogen efficiency of 5.3% was observed. In Chapter 5, the design principles for membraneless electrolyzers were applied to a photoelectrochemical (PEC) cell. Whereas an electrolyzer is externally powered by electricity, a PEC cell can directly harvest light to drive an electrochemical reaction. The PEC reactor was based on a parallel plate design, where the current was demonstrated to be limited by the intensity of light and the concentration of the electrolyte. By increasing the average flow rate of the electrolyte, mass transport limitations could be alleviated. The limiting current density was compared to theoretical values based off of the solution to a convection-diffusion problem. This modeled solution was used to predict the limitations to PEC performance in scaled up designs, where solar concentration mirrors could increase the total current density. The mass transport limitations of a PEC flow cell are also highly relevant to the study of CO2 reduction, where the solubility limit of CO2 in aqueous electrolyte can also limit performance

Obstacles, Interfacial Forms, and Turbulence: A Numerical Analysis of Soil–Water Evaporation Across Different Interfaces

AbstractExchange processes between a turbulent free flow and a porous media flow are sensitive to the flow dynamics in both flow regimes, as well as to the interface that separates them. Resolving these complex exchange processes across irregular interfaces is key in understanding many natural and engineered systems. With soil–water evaporation as the natural application of interest, the coupled behavior and exchange between flow regimes are investigated numerically, considering a turbulent free flow as well as interfacial forms and obstacles. Interfacial forms and obstacles will alter the flow conditions at the interface, creating flow structures that either enhance or reduce exchange rates based on their velocity conditions and their mixing with the main flow. To evaluate how these interfacial forms change the exchange rates, interfacial conditions are isolated and investigated numerically. First, different flow speeds are compared for a flat surface. Second, a porous obstacle of varied height is introduced at the interface, and the effects the flow structures that develop have on the interface are analyzed. The flow parameters of this obstacle are then varied and the interfacial exchange rates investigated. Next, to evaluate the interaction of flow structures between obstacles, a second obstacle is introduced, separated by a varied distance. Finally, the shape of these obstacles is modified to create different wave forms. Each of these interfacial forms and obstacles is shown to create different flow structures adjacent to the surface which alter the mass, momentum, and energy conditions at the interface. These changes will enhance the exchange rate in locations where higher velocity gradients and more mixing with the main flow develop, but will reduce the exchange rate in locations where low velocity gradients and limited mixing with the main flow occur

Physical modelling of DMFC performance heterogeneities and the recovery of reversible cathode degradation

In this work, a transient multiphase DMFC model in 2D has been developed with the aim to describe the physical processes inside a DMFC single cell with a focus on performance heterogeneities along the channel. The model featured the spatial discretisation of the ACL and CCL, which proved essential for the investigation of local inhomogeneities in the cell as well as for understanding transient phenomena during the recovery of reversible cathode degradation. The model has been thoroughly validated against experimental performance data from a macro-segmented cell, which also included impedance spectra as well as the overall methanol and water crossover. The local resolution of the cell performance helped to verify the modelling of physical processes for mass and charge transport on the global as well as on the local scale. Such a locally resolved model validation can hardly be found in literature. A very good agreement of the model prediction with the experimental data regarding humidity-related phenomena inside the DMFC cathode as well as general mass transport phenomena and their effect on the cell performance under various operating conditions has been achieved with just one set of model parameters. The simulation study has highlighted the complex interplay of gas and liquid phase inside the DMFC and its impact on material properties and transport processes inside the cell. Furthermore, the importance of interface processes at the PEM boundaries to the catalyst layers as well as inside the catalyst layer on the local cell behaviour could be shown. For the species transport inside the compositional fuel cell structure, the formation and presence of liquid water plays a dominant role. It could be shown that phase-dependent sorption processes at the DMFC membrane interface fundamentally determine the water transfer from anode to cathode and consequently the distribution of liquid water inside the cell. The impact of the individual humidity-related transport mechanisms has been evaluated step by step in this work. The ionomer phases in the cell, i.e the bulk membrane as well as the ionomer thin-film in the CL, proved to be highly sensitive to the local water activity and phase conditions and exhibit a strong resistance to proton transport in the areas of the DMFC with poor humidification. Mass transport resistances in the heterogeneous CL microstructure due to liquid water accumulation could be successfully modelled on the continuum scale by integrating an ionomer-film model. The validated cell model also proved fit to describe the transient processes within the cell during the recovery of reversible cathode degradation during a refresh cycle. Without any adjustments in the model, the dynamics in the local potential for electrons and ions as well as in the membrane in dependence on the conditions inside the DMFC were predicted with a very good accuracy in anode and cathode. With its spatial resolution of the CCL, the model rendered a visualisation of the heterogeneous distribution of species and reactions in the course of the refresh sequence. Also the local formation of H2 in the DMFC anode during the absence of oxygen in the CCL could be successfully described with the model. The simulation study showed that the methanol crossover through the DMFC membrane and the resulting methanol oxidation reactions in the CCL play an essential role during the refresh cycle. Especially the secondary, H2O-activated MOR reaction path in the CCL under oxygen-depleted conditions was identified as relevant for the achievement of low local potentials in the DMFC cathode and thus for the full recovery of the cathode ECSA during the air break. A variation of air stop scenarios was simulated with the model and the impact of the local species distribution on the electrochemical processes within the cell was studied. The variations included settings where the PtOx-surface species in the CCL would get entirely or only partially reduced. In a simulation of a longer air stop, the effect of methanol accumulation during the air stop period could be visualised and its impact on the heterogeneities in the local cell voltage could be explained. Also the processes during an incomplete air stop, where oxygen is only partially depleted in the cathode catalyst layer, could be shown with the model. Two air stop variants resulting in a full recovery of the cathode ECSA were identified and examined. The simulation showed that while a flush with pure nitrogen on the one hand swiftly enables a full reduction of the platinum oxides in the CCL, it on the other hand limits the re-humidification of the membrane. By improving the model’s refresh boundary conditions, i.e. further limiting the diffusion of oxygen into the cell from external during the air stop period (and thus presumably approximating the experimental conditions more closely), the best results in terms of platinum oxide reduction and ionomer rehydration were achieved

On the Mass Transport Phenomena in Proton Exchange Membrane Electrolyzers

Proton exchange membrane (PEM) water electrolysis is a technology designed to produce H2 using only water and electricity as inputs; it has gained increased attention in industry and academia due to its advantages over incumbent H2 generation processes (of which the most widely used are steam reforming and coal gasification) namely, low temperature, carbon-neutral and intermittent operation. PEM electrolysis can be instrumental for creating a hydrogen economy, although still much research needs to be carried out before widespread industrial adoption is achieved. PEM water electrolyzers suffer energy losses associated with the chemical reactions and the transport of charge and mass; of these phenomena, mass transport in PEM electrolyzers is the least understood subject, given the complex nature of the interaction of multiphase flows (mainly consisting of liquid water and evolved gases) through micrometric pores. The subject of multiphase flow in water electrolysis and its relationship with the mass transport phenomena in PEM water electrolysis has been a prevalent subject in the literature. Despite numerous attempts at pinpointing the relationship between mass transport overpotential and the operating parameters, there is no clear consensus about which transport mechanisms dominate, nor about how the component design of PEM electrolyzers affects the mass transport. While the effect of temperature and current density on mass transport losses has been extensively studied and is well understood, there are significantly fewer studies that focus on the effect of water flow and pressure. Both water flow and pressure have a direct effect on mechanisms such as bubble nucleation and two-phase flows that occur in the porous structures within a PEM electrolyzer (electrodes and porous transport layers, PTLs). In this work, I studied the effect of water flow and pressure on the mass transport phenomena in PEM electrolyzers. Chapters 1 and 2 provide an introduction to the topic as well as a description of the materials and experimental setups used. Chapter 3 of this thesis depicts the visualization and modeling of bubble nucleation in an operating PEM electrolyzer. I discovered that bubble detachment radii are largely independent of water flow and I identified two types of bubbles: bubbles that detach after reaching a critical size, and bubbles that fill up the pores of a PTL before detaching. Chapter 3 consists of the measurements I carried out regarding the transport of evolved gas through the water-filled pores of a PTL, where I observed that water flow severely impedes the gas transport through the pores and that such impediment is related to a shear stress exerted by the water flow on the pores. Chapter 5 shows the measuring of mass transport losses using electrochemical impedance spectroscopy (EIS) on an operating PEM electrolyzer; the results indicate that pressure and water flow affect the diffusion of gas in the electrode and that the mass transport overpotential depends on design parameters of the PEM electrolyzer, such as electrode thickness and hydrophobicity. Overall, I derived a theoretical framework based on the assumption that the evolved gas in a PEM electrolyzer permeates through the PTL after diffusing from the active sites to the bubble nucleation sites. Such framework, constructed on the basis of the models regarding gas transport in porous media, can be used to explain the mass transport loses in a PEM electrolyzer that arise from operating with increased water flows and pressures. The model I derived can be used in future work as a guideline to optimize the components of a PEM electrolyzer, in particular regarding the hydrophobicity and pore size distribution of PTLs as well as the composition of the catalyst ink to produce the electrodes. Moreover, this work can also be used to further understand the mass transport losses and optimize the operation of PEM electrolyzers to decrease the energy consumption of H2 generation