Increasing environmental concerns as well as diminishing fossil fuel reserves call for a new generation of energy conversion technologies. Fuel cells, which convert the chemical energy of a fuel directly to electrical energy, have been identified as one of the leading alternative energy conversion technologies. Fuel cells are more efficient than conventional heat engines with minimal pollutant emissions and superior scalability. Proton Exchange Membrane Fuel Cells (PEMFCs) which produce electricity from hydrogen have been widely investigated for transportation and stationary applications. The focus of this study is on the Direct Propane Fuel Cell (DPFC), which belongs to the PEMFC family, but consumes propane instead of hydrogen as feedstock. A drawback associated with DPFCs is that the propane reaction rate is much slower than that of hydrogen. Two ideas were suggested to overcome this issue: (i) operating at high temperatures (150-230oC), and (ii) keeping the propane partial pressure at the maximum possible value. An electrolyte material composed of zirconium phosphate (ZrP) and polytetrafluoroethylene (PTFE) was suggested because it is an acceptable proton conductor at high temperatures. In order to keep the propane partial pressure at the maximum value, interdigitated flow-fields were chosen to distribute propane through the anode catalyst layer. In order to evaluate the performance of a DPFC which operates at high temperature and uses interdigitated flow-fields, a computational approach was chosen. Computational Fluid Dynamics (CFD) was used to create two 2-D mathematical models for DPFCs based on differential conservation equations. Two different approaches were investigated to model species transport in the electrolyte phase of the anode and cathode catalyst layers and the membrane layer. In the first approach, the migration phenomenon was assumed to be the only mechanism of proton transport. However, both migration and diffusion phenomena were considered as mechanisms of species transport in the second approach. Therefore, Ohm's law was used in the first approach and concentrated solution theory (Generalized Stefan-Maxwell equations) was used for the second one. Both models are isothermal. The models were solved numerically by implementing the partial differential equations and the boundary conditions in FreeFEM++ software which is based on Finite Element Methods. Programming in the C++ language was performed and the existing library of C++ classes and tools in FreeFEM++ were used. The final model contained 60 pages of original code, written specifically for this thesis. The models were used to predict the performance of a DPFC with different operating conditions and equipment design parameters. The results showed that using a specific combination of interdigitated flow-fields, ZrP-PTFE electrolyte having a proton conductivity of 0.05 S/cm, and operating at 230oC and 1 atm produced a performance (polarization curve) that was (a) far superior to anything in the DPFC published literature, and (b) competitive with the performance of direct methanol fuel cells. In addition, it was equivalent to that of hydrogen fuel cells at low current densities (30 mA/cm2).

Gegenstand der Arbeit ist die Untersuchung der kollektiven Diffusion von Wasser und Ionen in wässrigen Elektrolytlösungen. Dabei wird insbesondere die Dynamik der Wassermoleküle innerhalb der Hydratationshüllen der Ionen und der Einfluss poröser Materialien untersucht. Nach einer Einführung zur Dynamik der Hydratationshülle folgen Grundlagen der NMR-Diffusometrie, welche genutzt wurde um die Selbstdiffusionskoefifizienten der Wassermoleküle und der Ionen der Lösungen zu messen. Daraus wurden die dynamischen Hydratationszahlen der Ionen bestimmt, welche die Anzahl an Wassermolekülen angeben, die durch die Diffusion des Ions in ihrer translatorischen Bewegung beeinflusst sind. Der Einfluss poröser Materialien auf die Dynamik wird am Beispiel nanoporöser Glasmonolithe und mikroporöser Li-LSX Kristalle untersucht.

Electrolyte and pyrotechnic pellets are two important components of thermal batteries. Both electrolyte and pyrotechnic pellets are produced by cold compaction of constituent powders. These compacts are integrated in the battery as pellets with sufficient green density, green strength, calorific energy and burning rate (for pyrotechnic only) to provide high performance batteries. In this study, effects of physical properties of the used powders such as particle size distribution, average particle size, particle shape and composition of components and applied compression pressure and their interactions on green density and green strength of electrolyte pellets and in addition, calorific energy and burning rate of pyrotechnic pellets were examined. Statistical experimental designs were constructed to investigate the main and interaction effects of studied variables. 24 two factorial statistically designed experiments&rsquo / results for pyrotechnic pellets exhibited that the compression pressure and iron powder morphology were the most significant factors improving green density and break strength of pyrotechnic pellets. It was shown that the compression pressure had a negative effect on burning rate. Both calorific output and burning rate were increased significantly by increasing KClO4 fraction. In addition, decreasing particle size of KClO4 had also a positive effect on burning rate. The maximum calorific output was obtained at maximum KClO4 fraction. 23 two factorial statistically designed green strength and green density experiments&rsquo / results of electrolyte pellets revealed that, compression pressure was again the dominating factor. Moreover, there was a tendency for higher green density with lower MgO fraction and electrolyte powder average particle size. Besides, the positive effect of decreasing average particle size on green strength was investigated distinctly at low green density values. From the thermal battery perspective, main and interaction effects of variables on the characteristics of electrolyte and pyrotechnic pellets were successfully examined.

L'apparition des électrolytes solides dans le domaine du stockage de l'énergie ouvre la voie à un véritable bouleversement dans la conception et la fabrication des générateurs électrochimiques. Leur champ d'application est extrêmement vaste : réalisation de piles et d'accumulateurs légers pour équiper les véhicules électriques, élaboration de micropiles utilisées à des fins médicales et horlogères par exemple...

This thesis studies the performance of solid polymer lithium batteries from room temperature to elevated temperatures using mainly electrochemical techniques, with emphasis on the bulk properties of the polymer electrolyte and the electrode-electrolyte interfaces. Its contributions include: 1) Demonstrated the relationship between polymer segmental motion and ionic conductivity indeed has a Vogel-Tammann-Fulcher (VTF) dependence, and improved the conductivity of the graft copolymer electrolyte (GCE) by almost an order of magnitude by changing the ion-conducting block from poly(oxyethylene) methacrylate (POEM) to a block with a lower glass transition temperature \((T_g)\) poly(oxyethylene) acrylate (POEA). 2) Identified the rate-limiting step in the battery occurs at the cathode-electrolyte interface using both full cell and symmetric cell electrochemical impedance spectroscopy (EIS), improved the battery rate capability by using the GCE as both the electrolyte and the cathode binder to reduce the resistance at the cathode-electrolyte interface, and used TEM and SEM to visualize the polymer-particle interface (full cells with \(LiFePO_4\) as the cathode active material and lithium metal as the anode were assembled and tested). 3) Applied the solid polymer battery to oil and gas drilling application, performed high temperature (up to 210°C) cycling (both isothermal and thermal cycling), and demonstrated for the first time, current exchange between a solid polymer electrolyte and a liquid lithium metal. Both the cell open-circuit-voltage (OCV) and the overall GCE mass remained stable up to 200°C, suggesting that the GCE is electrochemically and gravimetrically stable at high temperatures. Used full cell EIS to study the behavior of the various battery parameters as a function of cycling and temperature. 4) Identified the thermal instability of the cell was due to the reactivity of lithium metal and its passivation film at high temperatures, and used Li/GCE/Li symmetric cell EIS to study the thermal stability of the anode-electrolyte interface, which was responsible for the fast capacity fade observed at high temperatures. 5) Proposed a new electrolyte material and a new battery design called polymer ionic liquid (PIL) battery that can dramatically improve the safety, energy density, and rate capability of rechargeable lithium batteries. / Engineering and Applied Sciences

Grätzel cells or Dye-Sensitized Solar Cells (DSSCs) are considered one of the most promising methods to convert the sun's energy into electricity due to their low cost and simple technology of production. The Grätzel cell is based on a photosensitizer adsorbed on a low band gap semiconductor. The photosensitizer can be a metal complex or an organic dye. Organic dyes can be produced on a large scale resulting in cheaper dyes than complexes based on rare elements. However, the performance of Grätzel cells based on metal-free, organic dyes is not high enough yet. The dye's performance depends primarily on the electron dynamics. The electron dynamics in Grätzel cells includes electron injection, recombination, and regeneration. Different deactivation processes affect the electron dynamics and the cells’ performance. In this thesis, the electron dynamics was explored by various time-resolved spectroscopic techniques, namely time-correlated single photon counting, streak camera, and femtosecond transient absorption. Using these techniques, new deactivation processes for organic dyes used in DSSCs were uncovered. These processes include photoisomerization, and quenching through complexation with the electrolyte. These deactivation processes affect the performance of organic dyes in Grätzel cells, and should be avoided. For instance, the photoisomerization can compete with the electron injection and produce isomers with unknown performance. Photoisomerization as a general phenomenon in DSSC dyes has not been shown before, but is shown to occur in several organic dyes, among them D149, D102, L0 and L0Br. In addition, D149 forms ground state complexes with the standard iodide/triiodide electrolyte, which directly affect the electron dynamics on TiO2. Also, new dyes were designed with the aim of using ferrocene(s) as intramolecular regenerators, and their dynamics was studied by transient absorption. This thesis provides deeper insights into some deactivation processes of organic dyes used in DSSCs. New rules for the design of organic dyes, based on these insights, can further improve the efficiency of DSSCs.

A procedure is presented to analyze select geometric and effective properties of the porous transport layer (PTL) of the polymer electrolyte membrane fuel cell (PEMFC) in com- pressed and uncompressed states using micro-computed X-ray tomography (Micro CT). A method of compression using a novel device design was employed to mimic the non-homogeneous compression conditions found in functioning fuel cells. The process also features open source image processing and CFD analysis through the use of software packages Fiji and OpenFOAM (proprietary software is also used such as Matlab). Tomographic images of a PTL sample in different compressive states are first analyzed by measuring local porosity values in the through-plane and both in- plane directions. The objective of this study was to develop a method for imaging the PTL structure to show directionality within its properties using relatively inexpensive and non-destructional means. Three different PTL types were tested, one without any additives, one with Polytetrafluoroethylene (PTFE) and one with PTFE and a microporous layer (MPL). Non-homogeneous porosity was shown to exist with the highest and least variable porosity values obtained from the in-plane direction that was in-line with the direction of fibres. Porosity values compared well with values obtained from the literature. The profile of the PTL with MPL added was unattainable using this procedure as the resolution of the Micro CT was too low to resolve its pore space. The next stage involved the effective properties analysis which included effective electronic conductivity and effective diffusivity. It was found that the through-plane values for the effective electronic conductivity study were higher than expected. The ratio between through-plane and in-plane was found to be much higher than expected from literature. Lack of sufficient resolution of fibre contacts has been shown to play a role in this discrepancy. These contact problems were shown not too affect measurements of diffusivity in the pore phase. The in-plane direction parallel to the direction of fibres was found to have the highest values of effective transport properties. Effective diffusivity ratios of between 0.1 and 0.37 were found to be reasonable with the limited experimental evidence found in literature. The it was found that the Bruggeman relation for calculating diffusivity and percolation theory by Tomadakis and Sotirchos over predicted the values for diffusion within the PTL and it is suggested that these theories are not suitable for predicting diffusivity for this material. / Thesis (Master, Mechanical and Materials Engineering) -- Queen's University, 2012-02-02 15:46:29.395

NMR experiments performed under the effect of electric fields, either continuous or pulsed, can provide quantitative parameters related to ion association and ion transport in solution.  Electrophoretic NMR (eNMR) is based on a diffusion pulse-sequence with electric fields applied in the form of pulses. Magnetic field gradients enable the measurement of the electrophoretic mobility of charged species, a parameter that can be related to ionic association. The effective charge of the tetramethylammonium cation ion in water, dimethylsulphoxide (DMSO), acetonitrile, methanol and ethanol was estimated by eNMR and diffusion measurements and compared to the value predicted by the Debye-Hückel-Onsager limiting law. The difference between the predicted and measured effective charge was attributed to ion pairing which was found to be especially significant in ethanol. The association of a large set of cations to polyethylene oxide (PEO) in methanol, through the ion-dipole interaction, was quantified by eNMR. The trends found were in good agreement with the scarce data from other methods. Significant association was found for cations that have a surface charge density below a critical value. For short PEO chains, the charge per monomer was found to be significantly higher than for longer PEO chains when binding to the same cations. This was attributed to the high entropy cost required to rearrange a long chain in order to optimize the ion-dipole interactions with the cations. Moreover, it was suggested that short PEO chains may exhibit distinct binding modes in the presence of different cations, as supported by diffusion measurements, relaxation measurements and chemical shift data. The protonation state of a uranium (VI)-adenosine monophosphate (AMP) complex in aqueous solution was measured by eNMR in the alkaline pH range. The question whether or not specific oxygens in the ligand were protonated was resolved by considering the possible association of other species present in the solution to the complex. The methodology of eNMR was developed through the introduction of a new pulse-sequence which suppresses artifactual flow effects in highly conductive samples. In another experimental setup, using NMR imaging, a constant current was applied to a lithium ion (Li ion) battery model. Here, 7Li spin-echo imaging was used to probe the spin density in the electrolyte and thus visualize the development of Li+ concentration gradients. The Li+ transport number and salt diffusivity were obtained within an electrochemical transport model. The parameters obtained were in good agreement with data for similar electrolytes. The use of an alternative imaging method based on CTI (Constant Time Imaging) was explored and implemented. / <p>QC 20140825</p>

Increasing environmental concerns as well as diminishing fossil fuel reserves call for a new generation of energy conversion technologies. Fuel cells, which convert the chemical energy of a fuel directly to electrical energy, have been identified as one of the leading alternative energy conversion technologies. Fuel cells are more efficient than conventional heat engines with minimal pollutant emissions and superior scalability. Proton Exchange Membrane Fuel Cells (PEMFCs) which produce electricity from hydrogen have been widely investigated for transportation and stationary applications. The focus of this study is on the Direct Propane Fuel Cell (DPFC), which belongs to the PEMFC family, but consumes propane instead of hydrogen as feedstock. A drawback associated with DPFCs is that the propane reaction rate is much slower than that of hydrogen. Two ideas were suggested to overcome this issue: (i) operating at high temperatures (150-230oC), and (ii) keeping the propane partial pressure at the maximum possible value. An electrolyte material composed of zirconium phosphate (ZrP) and polytetrafluoroethylene (PTFE) was suggested because it is an acceptable proton conductor at high temperatures. In order to keep the propane partial pressure at the maximum value, interdigitated flow-fields were chosen to distribute propane through the anode catalyst layer. In order to evaluate the performance of a DPFC which operates at high temperature and uses interdigitated flow-fields, a computational approach was chosen. Computational Fluid Dynamics (CFD) was used to create two 2-D mathematical models for DPFCs based on differential conservation equations. Two different approaches were investigated to model species transport in the electrolyte phase of the anode and cathode catalyst layers and the membrane layer. In the first approach, the migration phenomenon was assumed to be the only mechanism of proton transport. However, both migration and diffusion phenomena were considered as mechanisms of species transport in the second approach. Therefore, Ohm's law was used in the first approach and concentrated solution theory (Generalized Stefan-Maxwell equations) was used for the second one. Both models are isothermal. The models were solved numerically by implementing the partial differential equations and the boundary conditions in FreeFEM++ software which is based on Finite Element Methods. Programming in the C++ language was performed and the existing library of C++ classes and tools in FreeFEM++ were used. The final model contained 60 pages of original code, written specifically for this thesis. The models were used to predict the performance of a DPFC with different operating conditions and equipment design parameters. The results showed that using a specific combination of interdigitated flow-fields, ZrP-PTFE electrolyte having a proton conductivity of 0.05 S/cm, and operating at 230oC and 1 atm produced a performance (polarization curve) that was (a) far superior to anything in the DPFC published literature, and (b) competitive with the performance of direct methanol fuel cells. In addition, it was equivalent to that of hydrogen fuel cells at low current densities (30 mA/cm2).

Polymer electrolyte membrane fuel cells (PEMFCs) have been looked as potential alternative energy conversion devices to conventional energy conversion systems such as combustion engines. Proton conducting membranes (PEMs) are one critical component of PEMFCs. The development of novel electrolyte membranes with dense structure, good mechanical flexibility, and high proton conductivity, but with little or no dependence on humidity at temperatures above 100¡ãC remains an important challenge to the realization of practical PEM fuel cells. In this thesis, to solve the technical difficulties existing in current high temperature PEM systems based on phosphoric acid and imidazole, a new type of proton conducting species 1H-1,2,3-triazole has been explored, and proved to have high proton conductivity and also enough electrochemical stability for fuel cell applications. In further experiments, effective methods have been developed to synthesize triazole derivatives and polymers. The properties of the synthesized polymers have studied and reported in this thesis. Preliminary computational simulations have also been performed to study the proton conducting mechanism to provide intrinsic information of the proton conducting process in 1H-1,2,3-triazole. In the final part, research works on other proton conducting species including H3PO4 and other heterocycles have been reported.