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High-temperature Co-electrolysis of H2O and CO2 in a solid-oxide electrolyser (Co-SOE) for syngas production is a high-efficiency renewable electricity conversion and storage method part of the Power-to-X technologies. Syngas, a mixture of H2, CO and CO2, is a critical building block to make several chemical and synthesis fuels. The thesis aimed to model the Co-electrolysis process in a steady-state process modelling tool called Aspen Plus. The model was designed at thermoneutral mode and four cases with electrolysis temperatures of 700 °C, 750 °C, 800 °C and 850°C. The results from the model were used to perform an economic assessment and check the feasibility of Co-SOE. The analysis included calculation of Net Present Value (NPV), Internal Rate of Return (IRR) and the Levelised cost of Syngas (LCOS). The LCOS from Co-SOE was compared to the benchmark technology of syngas production in a Reverse Water Gas Shift (RWGS) reactor. The H2 feed to the RWGS reactor was assumed to be obtained from a Proton Exchange Membrane Electrolyser(PEME). A sensitivity analysis was performed to check the effect of electricity price, electrolyser stack price, electrolyser lifetime, CO2 feed price, by-product O2 revenue and discount rate on the LCOS. The LCOS was calculated to be 0.697, 0.727, 0.752 and 0.783 €/kg at 700 °C, 750 °C, 800 °C and 850 °C, respectively, increased with temperature due to increased electricity consumption at thermoneutral mode. The average LCOS from Co-SOE was 18.5% cheaper than the benchmark technology due to the high investment in the PEME and low conversion efficiency of the RWGS process. There was a trade-off between LCOS and system efficiency due to the effect of internal methanation occurring on the cathode side of the SOE. 750 °C was found to be the optimum design temperature to minimise the LCOS and maximise the efficiency. LCOS was most sensitive to electricity price, followed by O2 revenue and discount rate, while other parameters were less significant. The thesis also discussed key challenges to overcome in the future development of the Co-SOE technology. Co-SOE was found to be a promising technology for green syngas production. However, challenges concerning low stack lifetime, high capital investment and high cost of electricity have yet to be overcome to demonstrate it at a commercial scale.

<p>The introduction of metal supported cells may be a key innovation in the development of solid oxide fuel cell (SOFC) technology. The objective of this study was to develop a process of co-firing the ceramic layers of a solid oxide fuel cell attached to their porous metal support. This is a major departure from the traditional fuel cell architecture where the support layer is a ceramic composite made of YSZ and NiO.</p> <p>The problems to be eliminated during the fabrication process include the warping, cracking and delamination of the cell during the co-sintering process.</p> <p>In this study, the porous metal layer was produced by the freeze tape casting process. During co-sintering, it is necessary to match the relative shrinkage between the metal and ceramic layers. Different parameters which can influence the relative shrinkage were explored, including the heating rate, sintering temperature, sintering time, cell thickness, solid loading of the green tapes, applications of wet and dry hydrogen in the sintering atmosphere, as well as a change of the electrolyte material. Specifically, GDC was tested as an alternative electrolyte to YSZ.</p> <p>Since the porous metal substrate is exposed to air during fuel cell operation, it must be protected from oxidation. Therefore, the pack cementation method was used to apply a layer of aluminum onto the metal substrate. Variables such as temperature and exposure time of the coating materials were investigated in this thesis.</p> / Master of Applied Science (MASc)

This dissertation aims to present a detailed analysis of the grid voltage disturbance in frequency domain for the current control design in the grid-tie inverter applications and to propose current control techniques in order to minimize its impact and maximize feasibility of the power conditioning system in distributed generations. Because the grid voltage is constantly changing, the inverter must be able to response to it. If the inverter is unable to respond properly, then the grid voltage power comes back to the system and damages the fuel cell power conditioning systems. A closed-loop dynamic model for the current control loop of the grid-tie inverter has been developed. The model explains the structure of the inverter admittance terms. The disturbance of the grid voltages has been analyzed in frequency domain. The admittance compensator has been proposed to prevent the grid voltage effect. The proposed lead-lag current control with admittance compensator transfers current properly without system failure. In order to get rid of the steady-state error of the feedback current, a proportional-resonant controller (PR) has been adopted. A PR control with admittance compensation provides great performance from zero power to full power operation. In addition, active and reactive power flow controller has been proposed based on the PR controller with admittance compensation. The proposed active and reactive power flow control scheme shows a wide range power flow control from pure leading power to pure lagging power. Finally, the proposed controller scheme has been verified its feasibility in three phase grid-tie inverter applications. First of all, a half-bridge grid-tie inverter has been designed with PR controller and admittance compensation. Then three individual grid-tie inverters has been combined and produced three phase current to the three phase grid in either balanced condition or unbalanced condition. The proposed control scheme can be applied not only single phase grid-tie inverter application, but also three phase grid-tie inverter application. This research can be applicable to the photovoltaic PCS as well. This technology makes renewable energy source more plausible for distributed generations. / Ph. D.

Widespread use of solid oxide fuel cells is hindered by a lack of long-term durability of seals between metallic and ceramic components caused by thermal expansion mismatch induced cracking. A novel gas seal design incorporating an engineered thermal expansion gradient in a SrO-La₂O₃-A₂O₃-B₂O₃-SiO₂ glass matrix with a TiNiHf shape memory alloy mesh for active stress relief and crack healing is being developed. Coefficient of thermal expansion (CTE) measurements of the seal and fuel cell components shows the possibility for a thermal expansion gradient. Differential scanning calorimetry and microscopy have shown that the TiNiHf alloy has a shape memory transition in the desired range of 200-250ºC. The oxide glass partially crystallizes during thermal cycling which has been observed through X-ray diffraction and dilatometry. The CTE decreases from 9.3Ã 10-6/°C to 6.6Ã 10-6/°C after thermal cycling. Neutron diffraction data from TiNiHf /glass composite samples reveals that the TiNiHf alloy has the ability of absorbing residual stresses from a glass matrix during martensitic phase transition. There is evidence from microscopy that the glass composition is important in determining if reaction will occur with the TiNiHf alloy. The TiNiHf alloy mesh structures can be created using the 3D printing process. This process has been adapted to allow for printing of very thin wire mesh structures of Ni and NiTi powders with a more suitable binder solution. A bi-layer test fixture has been developed which will be useful for assessing leak rate through seal materials. / Master of Science

The work in this thesis mainly focuses on the preparation and characterization of several phosphates and solid oxide systems with the aim of developing new proton conducting materials for intermediate temperature fuel cells (ITFCs). Soft chemical methods such as sol-gel methods and conventional solid state methods were applied for the synthesis of these materials. Aluminum phosphate obtained by a solution method is single phase and belongs to one of the Al(H₂PO₄)₃ allotropies with hexagonal symmetry. The material is stable up to 200°C and decomposes into Al(PO₃)₃ at a higher temperature. The electrical conductivity of pure Al(H₂PO₄)₃ is on the order of 10⁻⁶-10⁻⁷ S/cm, very close to the value for the known proton conductors AlH₃(PO₄)₂•3H₂O and AlH₂P₃O₁₀•2H₂O. Much higher conductivity is observed for samples containing even a trace amount of excess H₃PO₄. It is likely that the conduction path gradually changes from grain interior to the surface as the acid content increases. The conductivity of Al(H₂PO₄)₃-0.5H₃PO₄ exhibited a good stability over the measured 110 hours. Although tin pyrophosphate (SnP₂O₇) has been reported to show a significantly high conductivity (~10⁻² S/cm) at 250°C in various atmospheres, we observed large discrepancies in the electrical properties of SnP₂O₇ prepared by different methods. Using an excess amount of phosphorous in the synthetic procedure generally produces SnP₂O₇ with much higher conductivity (several orders of magnitude higher) than samples with stoichiometric Sn:P ratios in their synthetic procedure. Solid state ³¹P NMR confirmed the presence of residual phosphoric acid for samples with excess starting phosphorous. Transmission Electron Microscope (TEM) confirmed an amorphous layer covered the SnP₂O₇ granules which was probably phosphoric acid or condensed phases. Thereby, it is quite likely that the high conductivity of SnP₂O₇ results mainly from the contribution of the residual acid. The conductivity of these samples exhibited a good stability over the measured 80 hours. Based on the observations for SnP₂O₇, we developed a nano core-shell structure based on BPO₄ and P₂O₅ synthesised by solid state methods. The particle size of BPO₄ using this method varied between 10-20 nm depending on the content of P₂O₅. TEM confirmed the existence of an amorphous layer that is homogeneously distributed. The composite exhibits the highest conductivity of 8.8×10⁻² S/cm at 300°C in air for 20% extra P₂O₅ and demonstrates a good stability during the whole measured 110 hours. Polytetrafluoroethylene (PTFE) was introduced into the composites in order to increase malleability for fabrication. The conductivity and mechanical strength were optimized by adjusting the PTFE and P₂O₅ content. These organic-inorganic composites demonstrate much better stability at elevated temperature (250°C) over conventional SiC-H₃PO₄-PTFE composites which are common electrolytes for phosphoric acid fuel cells (PAFCs). Fuel cells based on BPO₄-H₃PO₄-PTFE composite as the electrolyte were investigated using pure H₂ and methanol as fuels. A maximum power density of 320 mW/cm² at a voltage of 0.31 V and a maximum current density of 1.9 A/cm² at 200°C were observed for H₂/O₂ fuel cells. A maximum power density of 40 mW/cm² and maximum current of 300 mA/cm² 275°C were observed when 3M methanol was used in the cell. Phosphoric acid was also introduced into materials with internal open structures such as phosphotungstic acid (H₃PW₁₂O₄₀) and heteropolyacid salt ((NH₄)₃PW₁₂O₄₀), for the purpose of acquiring additional connections. The hybrids obtained have a cubic symmetry with enlarged unit cell volume, probably due to the incorporation of phosphoric acid into the internal structures. Solid state ³¹P NMR performed on H₃PW₁₂O₄₀-xH₃PO₄ (x = 0-3) showed additional peaks at high acid content which could not assigned to phosphorus from the starting materials, suggesting a strong interaction between H₃PW₁₂O₄₀ and H₃PO₄. The conductivity of hybrids was improved significantly compared with samples without phosphoric acid. Fourier transform infrared spectra (FT-IR) suggest the existence of large amount of hydrogen bonds (OH••••O) that may responsible for the high conductivity. A H₂/O₂ fuel cell based on H₃PW₁₂O₄₀-H₃PO₄-PTFE exhibited a peak power density of 2.7 mW/cm² at 0.3 V in ambient temperature. Solid oxide proton conductors based on yttrium doped BaZrO₃ were investigated by introducing potassium or lanthanum at the A-sites. The materials were prepared by different methods and were obtained as a single phase with space group Pm-3m (221). The unit cell of these samples is slightly smaller than the undoped one. The upper limit of solid solution formation on the A-sites for potassium is between 5 ~ 10% as introducing more K results in the occurrence of a second phase or impurities such as YSZ (yttrium stabilized zirconium). K doped Barium zirconates showed an improved water uptake capability even with 5% K doping, whereas for La doped ones, water uptake is strongly dependent on particle size and synthetic history. The conductivity of K doped BaZrO₃ was improved by a factor of two (2×10⁻³ S/cm) at 600°C compared with undoped material. Fuel cells based on Pt/Ba₀₋₉₅K₀₋₀₅Zr₀₋₈₅Y₀₋₁₁Zn₀₋₀₄O[subscript(3-δ)]/Pt under humidified 5% H₂/air conditions gave a maximum power density 7.7 mWcm⁻² at 718°C and an interfacial resistance 4 Ωcm⁻². While for La doped samples, the conductivity was comparable with undoped ones; the benefits of introducing lanthanum at A-sites may not be so obvious as deficiency of barium is one factor that leads to the diminishing conductivity.

The research presented is based on alternative anode materials for high temperature steam electrolysis. The key to commercially viable renewable energy economy is based on energy storage of intermittent sources. Hydrogen is the preferred form of energy storage for solid oxide electrolysis cells. However, conventional anode material lanthanum strontium manganite (LSM), suffers from poor ionic conductivity, thus prohibiting much of the bulk electrode from providing an enhanced electrochemical performance. This study explores the use of a double-layered perovskite system with mixed electronic and ionic conductivity for use as anode material. Specifically, the SmBa₁₋ₓSrₓCo₂O[sub](5+δ) system (SBSCO) is analyzed for characteristics that may enhance the performance and feasibility of SBSCO as an alternative anode material to LSM. Previous in-house work showed SmBa₀.₅Sr₀.₅Co₂O[sub](5+δ) had the lowest area specific resistance of any double- layered material reported. Here the system is further explored by studying the full range of compositions. From X-ray diffraction analysis, increased Sr substitution leads to a tetragonal phase change in SBSCO. High temperature x-ray diffraction of compositions showed thermal stability of structure. Magnetization measurements are reported for selected compositions. The stability of SBSCO was examined in CO₂ containing atmospheres. Despite containing alkaline earth metals, the system offers limited CO₂ tolerance. A set of thermodynamic parameters is presented based on CO₂ partial pressure and temperature. Model indicates SBSCO is a stable electrode material for both electrolysis and fuel cell modes. Compositions were tested for steam electrolysis performance with the use of YSZ electrolyte, and Ni-YSZ and La₀.₄Sr₀.₄Ni₀.₀₆Ti₀.₉₄O₂.₉₄ cathodes. SmBa₀.₃Sr₀.₇Co₂O[sub](5+δ) had the highest performance for compositions (0≤x≤1) based on I-V curves and impedance measurements. Stability tests were conducted in potentiostatic mode and no delamination was observed for SBSCO in microstructural analysis after testing. From these studies, SBSCO is demonstrated to be a suitable for application in electrolysis and an alternative for LSM as anode material.

A numerical model was developed to evaluate the performance of detailed solid oxide fuel cell (SOFC) anode microstructures obtained from experimental reconstruction techniques or generated from synthetic computational techniques. The model is also capable of identifying the linear triple phase boundary (TPB) reaction sites and evaluating the effective transport within the detailed structures, allowing a comparison between the structural properties and performance to be conducted. To simulate the cell performance, a novel numerical coupling technique was developed in OpenFOAM and validated. The computational grid type and mesh properties were also evaluated to establish appropriate mesh resolutions to employ when studying the performance. The performance of a baseline synthetic electrode structure was evaluated using the model and under the applied conditions it was observed that the ionic potential had the largest influence over the performance. The model was used in conjunction with a computational synthetic electrode manufacturing algorithm to conduct a numerical powder to power parametric study investigating the effects of the manufacturing properties on the performance. An improvement in the overall performance was observed in structures which maximized the number of reaction sites and had well established transport networks in the ion phase. From the manufacturing parameters studied a performance increase was observed in structures with low porosity and ionic solid volume fractions near the percolation threshold, and when the anodes were manufactured from small monosized particles or binary mixtures comprising of smaller oxygen ion conductive particles. Insight into the anode thickness was also provided and it was observed that the current distribution within the anode was a function of the applied overpotential and an increase in the overpotential resulted in the majority of the current production to increase and shift closer to the electrode-electrolyte interface. / Thesis (Master, Mechanical and Materials Engineering) -- Queen's University, 2013-10-01 09:41:47.617

Un outil de diagnostic in situ pour l'étude des électrolyseurs à oxyde solide, fondé sur la spectroscopie d'impédance électrochimique, a été mis en place à travers une analyse systématique de l'influence de plusieurs paramètres (densité de courant, température, composition et débit des gaz) sur les performances et le comportement d'une monocellule commerciale dans une configuration à 2 électrodes. Les principaux phénomènes régissant le fonctionnement de la cellule ont été identifiés. Une analyse de son comportement après apparition et évolution dans le temps d'une dégradation prématurée, suite à une modification sur le banc d'essai, a été réalisée. Un mécanisme expliquant l'origine et les conséquences de cette dégradation prématurée a été proposé. Une étude sur l'influence de l'épaisseur d'une des deux électrodes de la cellule a par ailleurs permis de distinguer deux des phénomènes principaux liés à la diffusion de H2O à l'électrode Ni-YSZ. Enfin, l'étude du comportement de la cellule après dégradation par conduction électronique de l'électrolyte YSZ a mis en évidence la formation de porosités entrainant notamment des délaminations à l'interface YSZ/YDC. Un état de dégradation plus avancé que pour les tests précédents a été observé pour les couches YDC et Ni-YSZ. Ce phénomène se manifeste par un déplacement en fréquence de l'ensemble du diagramme d'impédance mesuré vers les plus basses fréquences, formant une boucle négative. Rp finit par disparaitre, le courant circulant alors majoritairement via la conduction électronique de l'électrolyte YSZ. / An in situ diagnosis tool, based on electrochemical impedance spectroscopy, for the study of solid oxide electrolyzer cells was established through the analysis of the influence of several parameters (current density, temperature, gas composition and gas flow rate) on the performances and the behavior of a commercial single cell studied in a two-electrode configuration. The main phenomena governing the cell were identified. An analysis of its behavior after appearance and evolution with time of a premature degradation was carried out. A mechanism explaining the origin and the consequences of such degradation was suggested. Furthermore, studying the influence of the cathode thickness allowed distinguishing two of the main phenomena associated to H2O diffusion at the Ni-YSZ electrode. In addition, a study of the cell behavior after degradation by electronic conduction of the YSZ electrolyte showed formation of numerous porosities leading to delaminations at the YSZ/YDC interface. This phenomenon was characterized by a shift of the overall impedance diagram to the lowest frequencies, with appearance of a negative loop which finally leads to the disappearance of Rp as the current circulates mostly via electronic conduction of the YSZ electrolyte.