This thesis discusses the role of initial particle size on the mechanisms of surface area loss of carbon-supported platinum (Pt) electrocatalysts in the cathode of proton exchange membrane fuel cells. Electrocatalyst decay protocols were used to accelerate cathode performance loss for Pt catalysts. Four cathodes with mean platinum particle sizes of 2.1, 3.5, 6.7 and 11.3 nm were evaluated to elucidate the impact of particle size on initial performance and subsequent degradation, when subjected to identical potential cycles. The degradation of Pt electrochemically active surface area (ECA) was significantly greater for 2.1 and 3.5 nm initial sizes compared to 6.7 and 11.3 nm initial sizes. As expected, the ECA loss of the cathodes shows an inverse proportionality with initial particle size. However, the initial performance of the 11.3 nm initial particle size electrode was significantly lower than the three smaller sizes. Thus, an initial Pt particle size of 6.7 nm was identified to offer the ideal balance performance and durability. The current state of standardization in characterizing particle size by transmission electron microscopy (TEM) is also investigated. The result is a standardized protocol for image acquisition and analysis. / text

The electrochemical oxygen reduction reaction (ORR) steps on a noble metal catalyst in an acidic aqueous electrolyte depend on the nature of the catalytic surface with which the O₂ molecule interacts. It has been assumed that the O₂ molecules interact directly with a bare noble-metal surface. By studying the nature of chemisorbed species on the surface of a metal catalyst as a function of the voltage on the anodic and cathodic sweeps, it is shown here that the O₂ reacts with a surface covered with oxide species extracted from the aqueous electrolyte and not from the O₂ molecules; the ORR is more active when the surface species are OH rather than O. Moreover, the strength of the chemical bond of the adsorbed species was shown to depend on the relative strengths of the metal-metal versus metal-oxide bonds. The Pt-Pt bonds are stronger than the Pd-Pd bonds, and the relative Pd-O bonds are stronger than the relative Pt-O bonds. As a result, the chemisorbed O species is stable to lower anodic potentials on Pd. CO oxidation to CO₂ occurs at a higher potential on Pd than on Pt, which is why Pd (not Pt) is tolerant to methanol. Experiments with alloys show the following: (1) methanol tolerance decreases with the increase of Pt in the Pd-Pt alloys with Pd₃Pt/C showing an initial tolerance that decreases with cycling; (2) OH is formed on Pt₃Co/C and core-shell Pt-Cu/C, which results in a higher activity and durability for the ORR on these catalysts; (3) a 300°C anneal is needed to stabilize the Pd₃Au/C catalyst that forms an O adsorbate; and (4) OH is formed on Pd₃Co/C and Pd₃CoNi/C. These studies provide a perspective on possible pathways of the ORR on oxide-coated noble-metal alloy catalysts. / text

In this dissertation, we present two major lines of numerical investigation based on a control-volume approach to solve coupled, nonlinear differential equations. The first model is developed to provide better understanding of the water management in PEMFC operating at less than 100ºC, under transient conditions. The model provides explanations for the observed differences between hydration and dehydration time constants during load change. When there is liquid water at the cathode catalyst layer, the time constant of the water content in the membrane is closely tied to that of liquid water saturation in the cathode catalyst layer, as the vapor is already saturated. The water content in the membrane will not reach steady state as long as the liquid water flow in the cathode catalyst layer is not at steady state. The second model is to optimize the morphological properties of HT-PEMFCs components so as to keep water generated as close as possible to the membrane to help reduce ionic resistance and thereby increase cell performance. Humidification of the feed gas at room temperature is shown to have minimal effects on the ionic resistance of the membrane used in the HT-PEMFC. Feed gases must be humidified at higher temperature to have effects on the ionic resistance. However, humidification at such higher temperatures will require complex system design and additional power consumption. It is, therefore, important to keep the water generated by the electrochemical reaction as close as possible to the membrane to hydration the membrane so as to reduce the ionic resistance and thereby increase cell performance. The use of cathode MPL helps keep the water generated close to the membrane and decreasing the MPL porosity and pore size will increase the effectiveness of the MPL in keep the water generated close to the membrane. The optimum value of the MPL porosity depends on the operating conditions of the cell. Similarly, decreasing the GDL porosity helps keep water close to the membrane and the optimum value of the GDL porosity depends on the operating conditions of the cell. / text

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Σκοπός της παρούσας διπλωματικής εργασίας είναι η μελέτη ενός υβριδικού συστήματος, το οποίο αποτελείται από μια κυψέλη καυσίμου και μπαταρίες, για την τροφοδοσία ενός μεταβαλλόμενου AC φορτίου. Επίσης, μελετώνται οι διατάξεις των ηλεκτρονικών ισχύος που απαιτούνται για να γίνει εφικτή η διασύνδεση της κυψέλης καυσίμου και των μπαταριών με το AC φορτίο. Αρχικά, γίνεται αναφορά στα βασικά χαρακτηριστικά του υδρογόνου και τους λογους που οδήγησαν στην αύξηση της χρήσης του τα τελευταία κυρίως χρόνια. Ακόμα, παρουσιάζονται οι διάφορες μέθοδοι παράγωγης του υδρογόνου, το οποίο αποτελεί το καύσιμο των περισοστέρων τύπων κυψελών καυσίμου. Στη συνέχεια, ακολουθεί η δομή και η ανάλυση του τρόπου λειτουργίας των διάφορων τύπων κυψελών καυσίμου. Έπειτα, παρουσιάζονται συνοπτικά οι διακοπτικοί μετατροπείς συνεχούς ρεύματος, διατάξεις των ηλεκτρονικών ισχύος, τις οποίες χρειαζόμαστε για την εξομάλυνση και τη σταθεροποίηση σε μια επιθυμητή τιμή της τάσης εξόδου των κυψελών καυσίμου, καθώς και τη μετατροπή της συνεχούς τάσης σε εναλλασσόμενη. Ακόμα, γίνεται περιγραφή της πειραματικής διάταξης κυψελών καυσίμου 1.2kW της εταιρίας Ballard Power Systems. Η διάταξη αυτή χρησιμοποιήθηκε για τη λήψη μετρήσεων και την εξαγωγή συμπερασμάτων σχετικά με τη λειτουργία μίας κυψέλης καυσίμου τύπου PEM, τόσο στη μόνιμη όσο και τη μεταβατική κατάσταση. Επίσης, αναπτύσσεται ένα μοντέλο του υβριδικού συστήματος στο Simulink, όπου προσομοιώνονται η κυψέλη καυσίμου 1.2kW της εταιρίας Nexa και οι μπαταρίες WP18-12I της εταιρίας LONG, ως πηγές τάσης. Ως μεταβλητό AC φορτίο χρησιμοποιείται μια θερμάστρα αλογόνου, με κατανάλωση ισχύος από 450W έως 1800W. Μελετάται η συμπεριφορά τόσο της κυψέλης καυσίμου όσο και των μπαταριών στις διάφορες αυξομειώσεις του φορτίου, καθώς και η απόκριση των μετατροπέων συνεχούς ρεύματος και του αντιστροφέα. Τέλος, παρουσιάζονται τα αποτελέσματα που προέκυψαν από την προσομοίωση στο Simulink. Από τα αποτελέσματα εξάγονται συμπεράσματα για τη λειτουργία του μοντέλου και προκύπτουν πιθανές προτάσεις για τη βελτίωση της απόδοσης του συστήματος. / The purpose of the present thesis is the study of a hybrid system, that consists of a fuel cell and batteries, in order to supply a changing AC load with power. The power electronics, that are required to make possible the interconnection of the fuel cell and the batteries with the AC load, are also being studied. To begin with, there is a reference to the essential features of hydrogen and the reasons that led to its increased use, mainly in recent years. In addition to this, the different methods for hydrogen production are being displayed. Hydrogen is the fuel for most fuel cell types. Moreover, the structure and the analysis on how the various types of fuel cells operate is considered. Furthermore, there is a brief presentation on DC-DC converters, power electronic devices, that are necessary in order to normalize and stabilize at a desired value the output of the fuel cell and convert DC voltage into AC. What is more, there is a description of the experimental arrangement of the fuel cell 1.2kW of the Ballard Power Systems company. The aforementioned device was used for taking measurements and draw conclusions on the operation of a PEM type fuel cell, in both the permanent and the transitory state. Afterwards, a model of the hybrid system is being developed in Simulink. As far as the voltage sources are concerned, the 1.2kW fuel cell of the Ballard Power Systems company along with the batteries WP18-12I of the LONG company are being simulated. A halogen stove with power consumption varying from 450W to 1800W is being used as the variable AC load. The behavior of both the fuel cell and the batteries to the various load fluctuations is being studied, as well as the response of the DC converters and the inverter. Finally, the results obtained from the simulation in Simulink are being presented. From them, conclusions are drawn on the functioning of the model and possible proposals arise to improve the overall performance of the system.

No description available.

Το αντικείμενο της παρούσας διατριβής ήταν η σύνθεση και ο χαρακτηρισμός νανοσύνθετων πολυμερικών μεμβρανών για την εφαρμογή τους σε κυψελίδες καυσίμου. Τα κελιά καυσίμου είναι ηλεκτροχημικές διατάξεις που μετατρέπουν με συνεχή τρόπο τη χημική ενέργεια ενός καυσίμου και ενός οξειδωτικού σε ηλεκτρική με ταυτόχρονη παραγωγή νερού. Μια πολύ σημαντική κατηγορία κελίων, είναι τα κελιά καυσίμου μεμβράνης πολυμερούς (PEMFC, Polymer Exchange Membrane Fuel Cell) τα οποία χρησιμοποιούν ως ηλεκτρολύτη μια πολυμερική μεμβράνη. Ανάλογα με τη θερμοκρασία λειτουργίας τα PEMFCs χωρίζονται σε αυτά που λειτουργούν σε θερμοκρασίες μέχρι 80ºC και στα υψηλής θερμοκρασίας που λειτουργούν στους 120-200ºC. Λειτουργία σε θερμοκρασίες πάνω από 100ºC έχει διάφορα πλεονεκτήματα, όπως αύξηση της κινητικής των αντιδράσεων, δυνατότητα χρησιμοποίησης άλλων καυσίμων εκτός από υδρογόνο, η χρήση όχι υψηλής καθαρότητας υδρογόνου και/ή χαμηλότερης ποσότητας του ακριβού καταλύτη Pt στα ηλεκτρόδια. Ένας από τους ηλεκτρολύτες για εφαρμογές σε PEMFC υψηλών θερμοκρασιών είναι το συμπολυμερές αρωματικού πολυαιθέρα με ομάδες πυριδίνης Advent TPS. Το συμπολυμερές Advent TPS έχει εξαιρετική ικανότητα σχηματισμού φιλμ, υψηλό Tg (>280ºC), υψηλή θερμική σταθερότητα (Τd>400ºC), υψηλή οξειδωτική σταθερότητα, ενώ μετά από εμποτισμό με Η3ΡΟ4 85% η ιοντική αγωγιμότητα είναι επίσης της τάξης του 10-2 S/cm. Στη παρούσα εργασία παρασκευάστηκαν νανοσύνθετες μεμβράνες, με την εισαγωγή υδρόφιλων, ανοργάνων προσθέτων στην υδρόφοβη πολυμερική μήτρα του Advent TPS με απώτερο σκοπό τη παρασκευή ενός νανοσύνθετου πολυμερικού ηλεκτρολύτη ο οποίος έχει την ικανότητα να εμποτίζεται με νερό βελτιώνοντας έτσι την αγωγιμότητα του συστήματος TPS/H3PO4.Τα ανόργανα εγκλείσματα που χρησιμοποιήθηκαν ήταν ο τροποποιημένος μοντμοριλλονίτης (H+-MMT), το οξείδιο του τιτανίου (ΤiΟ2) και το TiO2-P2O5. Οι νανοσύνθετες μεμβράνες εμφάνισαν ικανότητα εμποτισμού στο Η2Ο, οξειδωτική σταθερότητα και η ιοντική τους αγωγιμότητα ύστερα από τον εμποτισμό τους με Η3ΡΟ4 πλησίασε τη τιμή του Advent TPS. Επιπλέον στη περίπτωση των μεμβρανών με τον Η+-ΜΜΤ το H3PO4 συγκρατείται ισχυρότερα στη μεμβράνη, λόγω της μορφολογίας του ΜΜΤ, μειώνοντας έτσι το πρόβλημα διάχυσης του H3PO4 από τον ηλεκτρολύτη κατά τη διαδικασία της ψύξης του κελιού. / The objective of this thesis was the synthesis and characterization of nanocomposite membranes for use in fuel cells. Fuel cells are devices that convert the chemical energy of a fuel and an oxidant to electrical with simultaneous production of water. Polymer Exchange Membrane Fuel Cell (PEMFC) represents an important class of fuel cells, which uses a polymer membrane as its electrolyte. Operating above 150ºC has many advantages such as increased reaction rate, flexibility to use not so pure hydrogen as fuel and/or lower loading of the expensive metal (Pt) on the electrode. Advent TPS is an electrolyte for high temperature PEMFC that exhibits excellent film-forming properties, mechanical integrity, high glass transition temperature (2800C) as well as high thermal stability up to 4000 C. In addition to the above properties, Advent TPS shows high oxidative stability and acid doping ability, enabling proton conductivity in the range of 10-2 S/cm. The main goal of this thesis was to synthesize a nanocomposite electrolyte by adding inorganic, hydrophilic fillers in Advent TPS polymer matrix in order to fabricate a membrane that reveals ability to absorb water. The hydration of electrolyte can increase the proton conductivity. Inorganic fillers such as modified montmorillonite (H+-MMT), TiO2, TiO2-P2O5 were used. The nanocomposite membranes showed doping water ability, oxidative stability and proton conductivity in the range of 10-2 S/cm. Furthermore, the nanocomposite membranes with H+-MMT can retain the acid into the membrane, reducing the leaching problem during the cooling process of the cell. Finally the hybrid membranes were characterized with conventional techniques and showed thermal and mechanical stability.

Solid oxide fuel cells (SOFCs) are electrochemical devices that can convert a variety of fuels directly into electricity. Their commercialization requires efficient operation of its components. The sluggish kinetics for the oxygen reduction reaction (ORR) at the SOFC cathode contributes to the loss in the fuel cell efficiency. In this work, the ORR was investigated for the strontium-doped lanthanum manganite cathode (LSM) and yttria-stabilized zirconia electrolyte (YSZ) system. A combined mathematical modelling and experimental framework was developed to estimate, for the first time, the kinetics of the elementary processes of the ORR for porous LSM cathodes. The kinetics of each process was then analyzed to identify the contribution to the cathode resistance. The steady state and impedance response for polarized and unpolarized LSM cathodes was collected over a temperature range between 750C and 850C and two different oxygen partial pressure (pO2) ranges: (i) between 0.0001atm and 0.001atm, where LSM is considered to be stoichiometric with respect to oxygen and (ii) between 0.01atm and 0.21atm, where LSM is considered to be superstoichiometric with respect to oxygen. A mathematical model was developed to analyze both the steady state and impedance data. Two pathways for the ORR were considered: one where oxygen is transported in the gas phase and one where oxygen is transported along the surface of the LSM cathode. Rate constants, transport coefficients and their respective activation energies were obtained for the adsorption/desorption, surface diffusion and charge transfer processes. The experimental results indicated different polarization behavior between low and high pO2. It is hypothesized that the concentration of cation vacancies on the LSM surface changes with both pO2 and extent of polarization and that cation vacancies on the LSM surface can promote the ORR. Modelling results at low pO2 suggested that the adsorption reaction was slow and that thermodynamic limitations resulting in low equilibrium oxygen surface coverage can play an important role at both low and high polarizations. Modelling in high pO2 was complicated by the nature of the LSM surface in these conditions and suggests an electrochemical reaction at the gas/LSM interface and the transport of charged adsorbed oxygen atoms. / Thesis (Ph.D, Chemical Engineering) -- Queen's University, 2009-12-31 11:53:23.535

A steady-state simulation of a diesel-fuelled SOFC system was developed using a process simulation software package (VMGSim). The system was studied by conducting a sensitivity analysis of six independent variables (steam to carbon ratio, oxygen to carbon ratio, fuel utilization, air utilization, reformer pre-heater approach temperature and cathode temperature to the SOFC) and their effect on three response variables (net system efficiency, stack efficiency, system exhaust temperature). The steam to carbon ratio, fuel utilization and air utilization were the most influential independent variables and thus affected the greatest change in the performance metrics. Secondly, a multi-variable study was carried out on the most influential variables and constrained optima for the efficiencies (45% net system, 47% stack) and system exhaust temperature (78 degrees Celsius) were obtained. For the second part of this work, a steam reforming heat-exchange reactor was modeled using COMSOL. The reactor performance was assessed on the basis of selectivity and residence time for a given conversion. Both the kinetic models of Parmar et al. (2010) and Shi et al. (2009) for catalytic diesel steam reforming were applied and compared. Differences in performance were attributed to differences in the catalyst support and the reaction mechanisms used for deriving the reforming rate expressions. Finally, a proof of concept multi-scale modeling and design tool was developed by integrating the CFD model with the process simulation. Two-way communication between four different software components; COMSOL, VMGSim, Matlab and Microsoft Excel was achieved. / Thesis (Master, Chemical Engineering) -- Queen's University, 2012-04-18 01:12:27.072