Use of active power filter to reduce the effects of harmonics in solid oxide fuel cells

The Solid Oxide Fuel Cell (SOFC) is a class of fuel cells that is capable of generating very high levels of power at high temperatures. SOFCs are used for stationary power generation and as Combined Heat and Power (CHP) systems. In spite of all the beneficial features of the SOFC, the propagation of ripple currents, due to nonlinear loads, is a challenging problem, as it interferes with the physical operation of the fuel cell. The purpose of this thesis is to identify the cause of ripples and attempt to eliminate or reduce the ripple propagation through the use of Active Power Filters (APF). To this end, a systematic approach to modeling the fuel cell to account for its nonlinear behavior in the presence of current ripples is presented. A model of a small fuel cell power system which consists of a fuel cell, a DC-DC converter, a single-phase inverter and a nonlinear load is developed in MATLAB/Simulink environment. The extent of ripple propagation, due to variations in load magnitude and frequency, are identified using frequency spectrum analysis. In order to reduce the effects of ripple propagation, an APF is modeled to remove ripples from the DC fuel cell current. The emphasis of this thesis is based on the idea that small fuel cell systems cannot implement large passive filters to cancel the effects of ripple propagation and hence, the compact APF topology effectively protects the fuel cell from propagating ripples and improves its electrical performance.

Evaluation of strontium-site-deficient Sr2Fe1.4Co0.1Mo0.5O6-δ-based perovskite oxides as intermediate temperature solid oxide fuel cell cathodes

In this paper strontium-site-deficient Sr₂Fe_1.4Co_0.1Mo_0.5O_6-δ-based perovskite oxides (S_xFCM) were prepared and evaluated as the cathode materials for intermediate temperature solid oxide fuel cells (IT-SOFCs). All samples exhibited a cubic phase structure and the lattice shrinked with increasing the Sr-deficiency as shown in XRD patterns. XPS results determined that the transition elements (Co/Fe/Mo) in S_xFCM oxides were in a mixed valence state, demonstrating the small polaron hopping conductivity mechanism existed. Among the samples, S_1.950FCM presented the lowest coefficient of thermal expansion of 15.62 × 10^-6 K^-1, the highest conductivity value of 28 S cm^-1 at 500 °C, and the lowest interfacial polarization resistance of 0.093 Ω cm² at 800 °C, respectively. Furthermore, an anode-supported single cell with a S_1.950FCM cathode was prepared, demonstrating a maximum power density of 1.16 W cm^-2 at 800 °C by using wet H₂ (3% H₂O) as the fuel and ambient air as the oxidant. These results indicate that the introduction of Sr-deficiency can dramatically improve the electrochemical performance of Sr₂Fe_1.4Co_0.1Mo_0.5O_6-δ, showing great promise as a novel cathode candidate material for IT-SOFCs.

Flash-Sintering and Characterization of La0.8Sr0.2Ga0.8Mg0.2O3-δ Electrolytes for Solid Oxide Fuel Cells

La_0.8Sr_0.2Ga_0.8Mg_0.2O_3-δ (LSGM), a promising electrolyte material for intermediate temperature solid oxide fuel cells, can be sintered to a fully dense state by a flash-sintering technique. In this work, LSGM is sintered by the current-limiting flash-sintering process at 690°C under an electric field of 100 V cm^-1, in comparison with up to 1400°C or even higher temperature in conventional furnace sintering. The resultant LSGM samples are investigated by scanning electron microscopy, X-ray diffraction, and electrochemical impedance spectroscopy. The SEM images exhibit well-densified microstructures while XRD results show that the perovskite structure after flash-sintering does not changed. EIS results show that the conductivity of LSGM sintered by the current-limiting flash-sintering process increases with sintering current density value. The conductivity of samples sintered at 120 mA mm^-2 reaches 0.049 σ cm^-1 at 800°C, which is approximate to the value of conventional sintered LSGM samples at 1400°C. Additionally, the flash-sintering process is interpreted by Joule heating theory. Therefore, the current-limiting flash-sintering technique is proved to be an energy-efficient and eligible approach for the densification of LSGM and other materials requiring high sintering temperature.

Fabrication and evaluation of NiO/Y2O3-stabilized-ZrO2 hollow fibers for anode-supported micro-tubular solid oxide fuel cells

In this work NiO/3mol% Y₂O₃-ZrO₂ (3YSZ) and NiO/8mol% Y₂O₃-ZrO₂ (8YSZ) hollow fibers were prepared by phase-inversion. The effect of different kinds of YSZ (3YSZ and 8YSZ) on the porosity, electrical conductivity, shrinkage and flexural strength of the hollow fibers were systematically evaluated. When compared with Ni-8YSZ the porosity and shrinkage of Ni-3YSZ hollow fibers increases while the electrical conductivity decreases, while at the same time also exhibiting enhanced flexural strength. Single cells with Ni-3YSZ and Ni-8YSZ hollow fibers as the supported anode were successfully fabricated showing maximum power densities of 0.53 and 0.67Wcm^-2 at 800°C, respectively. Furthermore, in order to improve the cell performance, a Ni-8YSZ anode functional layer was added between the electrolyte and Ni-YSZ hollow fiber. Here enhanced peak power densities of 0.79 and 0.73Wcm^-2 were achieved at 800°C for single cells with Ni-3YSZ and Ni-8YSZ hollow fibers, respectively.

High performance cobalt-free Cu1.4Mn1.6O4 spinel oxide as an intermediate temperature solid oxide fuel cell cathode

In this work Cu_1.4Mn_1.6O₄ (CMO) spinel oxide is prepared and evaluated as a novel cobalt-free cathode for intermediate temperature solid oxide fuel cells (IT-SOFCs). Single phase CMO powder with cubic structure is identified using XRD. XPS results confirm that mixed Cu⁺/Cu²⁺ and Mn³⁺/Mn⁴⁺ couples exist in the CMO sample, and a maximum conductivity of 78 S cm⁻¹ is achieved at 800 °C. Meanwhile, CMO oxide shows good thermal and chemical compatibility with a 10 mol% Sc₂O₃ stabilized ZrO₂ (ScSZ) electrolyte material. Impedance spectroscopy measurements reveals that CMO exhibits a low polarization resistance of 0.143 Ω cm² at 800 °C. Furthermore, a Ni-ScSZ/ScSZ/CMO single cell demonstrates a maximum power density of 1076 mW cm⁻² at 800 °C under H₂ (3% H₂O) as the fuel and ambient air as the oxidant. These results indicate that Cu_1.4Mn_1.6O₄ is a superior and promising cathode material for IT-SOFCs.

Fabrication and characterization of SSZ tape cast electrolyte-supported solid oxide fuel cells

A 10 mol%Sc₂O₃, 1 mol%CeO₂ stabilized-ZrO₂ (SSZ) powder was successfully prepared using the sol-gel method. Subsequent SSZ electrolyte pellets were prepared by tape casting technique and sintered at 1400 °C, 1450 °C, 1500 °C, 1550 °C and 1600 °C. These were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and electrochemical impedance spectroscopy (EIS). SSZ showed a pure cubic phase after sintering, the grain size of SSZ increased with the increase of sintering temperature. The SSZ sintered at 1550 °C showed the highest ion conductivity. The maximum power densities of Ni-SSZ/SSZ/La_0.8Sr_0.2MnO_3-δ (LSM)-SSZ single cells sintered at 1550 °C were 0.18, 0.36, 0.51 and 0.72 W cm^-2 at 650, 700, 750 and 800 °C, respectively. The polarization resistance (R_p) of the single cell attained 0.201 Ω cm² at 800 °C.

Improved electrochemical performance of Sr2Fe1.5Mo0.4Nb0.1O6-δ -Sm0.2Ce0.8O2-δ composite cathodes by a one-pot method for intermediate temperature solid oxide fuel cells

In this paper, Sr₂Fe_1.5Mo_0.4Nb_0.1O_6-δ (SFMNb)-xSm_0.2Ce_0.8O_2-δ (SDC) (x = 0, 20, 30, 40, 50 wt%) composite cathode materials were synthesized by a one-pot combustion method to improve the electrochemical performance of SFMNb cathode for intermediate temperature solid oxide fuel cells (IT-SOFCs). The fabrication of composite cathodes by adding SDC to SFMNb is conducive to providing extended electrochemical reaction zones for oxygen reduction reactions (ORR). X-ray diffraction (XRD) demonstrates that SFMNb is chemically compatible with SDC electrolytes at temperature up to 1100 °C. Scanning electron microscope (SEM) indicates that the SFMNb-SDC composite cathodes have a porous network nanostructure as well as the single phase SFMNb. The conductivity and thermal expansion coefficient of the composite cathodes decrease with the increased content of SDC, while the electrochemical impedance spectra (EIS) exhibits that SFMNb-40SDC composite cathode has optimal electrochemical performance with low polarization resistance (R_p) on the La_0.9Sr_0.1Ga_0.8Mg_0.2O₃ electrolyte. The R_p of the SFMNb-40SDC composite cathode is about 0.047 Ω cm² at 800 °C in air. A single cell with SFMNb-40SDC cathode also displays favorable discharge performance, whose maximum power density is 1.22 W cm^-2 at 800 °C. All results indicate that SFMNb-40SDC composite material is a promising cathode candidate for IT-SOFCs.

Synthesis of Pr0.6Sr0.4FeO 3-δ -xCe0.9Pr0.1O 2-δ cobalt-free composite cathodes by a one-pot method for intermediate-temperature solid oxide fuel cells

Cobalt-free composite cathodes consisting of Pr_0.6Sr_0.4FeO _3-δ -xCe_0.9Pr_0.1O _2-δ (PSFO-xCPO, x = 0-50 wt%) have been synthesized using a one-pot method. X-ray diffraction, scanning electron microscopy, thermal expansion coefficient, conductivity, and polarization resistance (R _P ) have been used to characterize the PSFO-xCPO cathodes. Furthermore the discharge performance of the Ni-SSZ/SSZ/GDC/PSFO-xCPO cells has been measured. The experimental results indicate that the PSFO-xCPO composite materials fully consist of PSFO and CPO phases and posses a porous microstructure. The conductivity of PSFO-xCPO decreases with the increase of CPO content, but R _P of PSFO-40CPO shows the smallest value amongst all the samples. The power density of single cells with a PSFO-40CPO composite cathode is significantly improved compared with that of the PSFO cathode, exhibiting 0.43, 0.75, 1.08 and 1.30 W cm^-2 at 650, 700, 750 and 800 °C, respectively. In addition, single cells with the PSFO-40CPO composite cathode show a stable performance with no obvious degradation over 100 h when operating at 750 °C.

Ceramic Materials Development for Intermediate Temperature Solid Oxide Fuel Cell (IT-SOFC)

Solid oxide fuel cell (SOFC) is an electrochemical device that converts chemical energy into electric power with high efficiency. Traditional SOFC has its disadvantages, such as redox cycling instability and carbon deposition while using hydrocarbon fuels. It is because traditional SOFC uses Ni-cermet as anode. In order to solve these problems, ceramic anode is a good candidate to replace Ni. However, the conductivity of most ceramic anode materials are much lower than Ni metal, and it introduces high ohmic resistance. How to increase the conductivity is a hot topic in this research field. Based on our proposed mechanism, several types of ceramic materials have been developed. Vanadium doped perovskite, Sr1-x/2VxTi1-xO3 (SVT) and Sr0.2Na0.8Nb1-xVxO3 (SNNV), achieved the conductivity as high as 300 S*cm-1 in hydrogen, without any high temperature reduction. GDC electrolyte supported cell was fabricated with Sr0.2Na0.8Nb0.9V0.1O3 and the performance was measured in hydrogen and methane respectively. Due to vanadium’s intrinsic problems, the anode supported cell is not easy. Fe doped double perovskite Sr2CoMoO6 (SFCM) was also developed. By carefully doping Fe, the conductivity was improved over one magnitude, without any vigorous reducing conditions. SFCM anode supported cell was successfully fabricated with GDC as the electrolyte. By impregnating Ni-GDC nano particles into the anode, the cell can be operated at lower temperatures while having higher performance than the traditional Ni-cermet cells. Meanwhile, this SFCM anode supported SOFC has long term stability in the reformate containing methane. During the anode development, cathode improvement caused by a thin Co-GDC layer was observed. By adding this Co-GDC layer between the electrolyte and the cathode, the interfacial resistance decreases due to fast oxygen ion transport. This mechanism was confirmed via isotope exchange. This Co-GDC layer works with multiple kinds of cathodes and the modified cell’s performance is 3 times as the traditional Ni-GDC cell. With this new method, lowering the SOFC operation temperature is feasible.