Three‐Dimensional Computational Fluid Dynamics Modeling of a Planar Solid Oxide Fuel Cell

A three‐dimensional computational fluid dynamics model was developed to study the performance of a planar solid oxide fuel cell (SOFC). The governing equations were solved with the finite volume method. The model was validated by comparing the simulation results with data from literature. Parametric simulations were performed to investigate the coupled heat/mass transfer and electrochemical reactions in a planar SOFC. Different from previous two‐dimensional studies the present three‐dimensional analyses revealed that the current density was higher at the center along the flow channel while lower under the interconnect ribs, due to slower diffusion of gas species under the ribs. The effects of inlet gas flow rate and electrode porosity on SOFC performance were examined as well. The analyses provide a better understanding of the working mechanisms of SOFCs. The model can serve as a useful tool for SOFC design optimization.     

Study of a Single‐Chamber Solid Oxide Fuel Cell Microstack with V‐Shaped Congener‐Electrode‐Facing Configuration

Single‐chamber solid oxide fuel cell (SC‐SOFC) microstacks with V‐Shaped congener‐electrode‐facing configuration were fabricated and operated successfully in a box‐like stainless steel chamber. Two gas channels with small gas inlets were used to transport the fuel and oxygen to the anodes and cathodes, respectively. The temperature of an anode‐facing‐anode two‐cell stack was higher than that of a cathode‐facing‐cathode two‐cell stack during the test procedure. For a three‐cell stack, the cell in the middle region presented the highest power output. The open circuit voltage (OCV) and maximum power output of the three‐cell stack in a gas mixture of 100 sccm N₂, 120 sccm CH₄, and 80 sccm O₂ were 3.0 V and 413 mW, respectively.     

In Situ X‐Ray Diffraction and Stress Analysis of Solid Oxide Fuel Cells

To increase the long term stability and performance of solid oxide fuel cell (SOFC) materials, it is important to understand the main degradation processes in their functional layers. In this work, the interface between electrolyte and anode material was investigated by in situ X‐ray diffraction (XRD) stress and phase analysis. It has been found that the determining process for the initial degradation of SOFC is the reduction of the anode material with hydrogen. During this process a tensile strength of 600–700 MPa is measured. These stresses are induced in the electrolyte material and produce crack networks. The reduction from nickel oxide to pure nickel was monitored by in situ phase analysis. This reaction induces tensile stress at the interface between electrolyte and anode. The stress produced in the electrolyte material was also confirmed by the observation of crack networks detected using scanning electron microscopy (SEM). Finally, the reducing process was optimized using different process gases, decreasing the destructive tensile stress level.     

Degradation Mechanism of Anode‐Supported Solid Oxide Fuel Cell In Planar‐Cell Channel‐Type Setup

The degradation mechanism of anode‐supported planar solid oxide fuel cells is investigated in the present work. We fabricate a large‐area (10 cm × 10 cm) cell and carry out a long‐term test with the assembly components. A constant current of ∼0.4 A cm^–2 is applied to the cell for ∼3,100 h, and the furnace temperature is controlled in the sequence 750–800–750 °C to investigate the effect of operating temperature and thermal cycling on the degradation rate. Impedance spectra and current–voltage characteristics are measured during the operation in order to trace any increase in Ohmic and non‐Ohmic resistance as a function of time. The degradation rate is rapid during the operation at the higher temperature of ∼800 °C compared to that during the operation at ∼750 °C. Even after cooling down to ∼750 °C, that rate is still accelerated. The main contribution to the cell degradation is from an increase in the Ohmic resistance. Postmaterial analyses indicate that the cathode is delaminated at the electrolyte/cathode interface, which is attributed to the difference in thermal expansion coefficient (TEC). Thus, the present results emphasize the importance of matching the TEC between cell layers, especially under severe operating conditions such as long duration and complex thermal cycling.     

Fabrication of a Flat Tubular Segmented‐in‐series Solid Oxide Fuel Cell Using Decalcomania Paper

A flat tubular segmented‐in‐series (SIS) solid oxide fuel cell (SOFC) was fabricated using decalcomania paper. The performance of a two‐cell stack with 4.5‐mm‐wide electrodes was investigated in a temperature range of 650–800 °C. The decalcomania paper allowed fabrication of the SIS‐SOFC on all sides of the flat tubular support and achieve an effective electrode area larger than that obtained using typical SOFC fabrication techniques such as screen printing or slurry coating. SEM observations revealed that each component layer was flat, uniformly thick, and well adherent to adjacent layers. Measured values of open circuit voltages were very close to the theoretical values; confirming that the processing technique utilizing decalcomania paper is suitable for SIS‐SOFC fabrication. The power densities of the two‐cell‐stack were 437.4, 375.6, 324.6, and 257.1 mW cm⁻² at 800, 750, 700 and 650 °C, respectively.     

Development of an In Situ Surface Deformation and Temperature Measurement Technique for a Solid Oxide Fuel Cell Button Cell

A novel experimental technique is developed to measure the in situ surface deformation and temperature of a solid oxide fuel cell (SOFC) anode surface along with the cell electrochemical performance. The experimental setup consists of a NexTech Probostat^™ SOFC button cell test apparatus integrated with a Sagnac interferometric optical method and an infrared sensor for in situ surface deformation and temperature measurements, respectively. The button cell is fed with hydrogen or simulated coal syngas under SOFC operating conditions. The surface deformation is measured over time to estimate the anode structural degradation. The cell surface transient temperature is also monitored with different applied current densities under hydrogen and simulated coal syngas. The experimental results are useful to validate and develop SOFC structural durability and electrochemical models.     

Development and Fabrication of a New Concept Planar‐tubular Solid Oxide Fuel Cell (PT‐SOFC)

The paper reports a new concept of planar‐tubular solid oxide fuel cell (PT‐SOFC). Emphasis is on the fabrication of the required complex configuration of Ni‐yttria‐stabilised zirconia (YSZ) porous anode support by tert‐butyl alcohol (TBA) based gelcasting, particularly the effects of solid loading, amounts of monomers and dispersant on the rheological behaviour of suspension, the shrinkage of a wet gelcast green body upon drying, and the properties of final sample after sintering at 1350 °C and reduction from NiO‐YSZ to Ni‐YSZ. The results show that the gelcasting is a powerful method for preparation of the required complex configuration anode support. The anode support resulted from an optimised suspension with the solid loading of 25 vol% has uniform microstructure with 37% porosity, bending strength of 44 MPa and conductivity of 300 S cm^—1 at 700 °C, meeting the requirements for an anode support of SOFC. Based on the as‐prepared anode support, PT‐SOFC single cell of Ni‐YSZ/YSZ/LSCF has been fabricated by slurry coating and co‐sintering technique. The cell peak power density reaches 63, 106 and 141 mW cm^—2 at 700, 750 and 800 °C, respectively, using hydrogen as fuel and ambient air as oxidant.     

In Situ Measurements on Solid Oxide Fuel Cell Cathodes – Simultaneous X‐Ray Absorption and AC Impedance Spectroscopy on Symmetrical Cells

A solid oxide fuel cell in operando is a complex multiphasic entity under electrical polarization and operating at high temperatures. In this work, we reproduce these conditions while studying transition metal redox chemistry in situ at the cathode. This was achieved by building a furnace that allowed for X‐ray absorption near‐edge structure and AC impedance spectroscopy data to be obtained simultaneously on symmetrical cells while at operating temperatures. The cell electrodes consisted of phases from the Ruddlesden–Popper family; La₂NiO_4+δ, La₄Ni₃O_10–δ, and composites thereof. The redox chemistry of nickel in these cathodes was probed in situ through investigation of changes in the position of the X‐ray absorption K‐edge. An oxidation state reduction (Ni³⁺ to Ni²⁺) was observed on heating the cells; this was correlated to changing concentrations of ionic charge carriers in the electrode. Polarizing the cells resulted in dramatic changes to their electrical performance but not to the bulk redox chemistry of the electrode. The implications of this with respect to explaining the polarization behavior are discussed.     

High Temperature Micro‐Fan for Solid Oxide Fuel Cell Applications

The possibility of using a μ‐fan in tubular solid oxide fuel cells module (SOFC‐M) is shown. The μ‐fan is placed instead of the ejector and fulfills its role. The main advantages of this solution are: lower power demanded by the fuel compressor (blower), more stable working characteristics, and the possibility of more accurate control of the recycled part of the anode gas during part load operation. A comparison of two SOFC‐Ms, with and without the ejector, is also shown and commented.     

Curvature Reversal and Residual Stress in Solid Oxide Fuel Cell Induced by Chemical Shrinkage and Expansion

Structural stability of layered functional ceramic composites is challenged by curvature effects and residual stresses caused by the thermal mismatch and chemical strains. In this study, a phenomenon of curvature reversal is found in the half‐cell structure of solid oxide fuel cell (SOFC) during the reduction of the half‐cell from NiO‐YSZ to Ni‐YSZ. An analytical model is derived to study the curvature and residual stress caused by the chemical shrinkage and expansion of anode. With reducing to Ni‐YSZ, the curvature of the half‐cell changes from the initial direction to an opposite direction, then back to the initial direction. This curvature reversal is inevitable during reduction while the thickness ratio of electrolyte to anode is between 0 and 0.102. The residual stress in electrolyte, calculated by the analytical model, is well agreement with the experiment result using X‐ray stress analysis. The YSZ layer is always subjected to compressive stress in despite of curvature reversal existing in half‐cell. It is impossible to get the residual stress by measuring the curvature unless the half‐cell was reduced completely.     

Local Evolution of Triple Phase Boundary in Solid Oxide Fuel Cell Stack After Long‐term Operation

In this research a 100 W solid oxide fuel cells (SOFCs) stack was tested. After 3,700 hours of continuous operation a subsequent post‐test analysis of the anodes' microstructure was conducted using a combination of focused ion beam and scanning electron microscopy. The obtained data was reconstructed into three‐dimensional images, based on which the microstructure parameters were obtained. The microstructure parameters were quantified at nine different locations in the stack. The discussion focuses on tripe phase boundaries as the most important microstructure parameter strongly affecting the anode performance and degradation. The obtained results indicate strong non‐homogeneous microstructure morphology changes after long‐term operation.     

Microscale Modeling of an Anode‐Supported Planar Solid Oxide Fuel Cell

A microscale model of a solid oxide fuel cell (SOFC) involving the mass transfer together with the electrochemical reaction, the transportation of electrons and ions through the respective spherical shaped electron conducting and ion conducting particles inside the electrodes was mathematically developed. Couples of useful parameters were introduced in order to represent the characteristics of the cell. The predicted cell performance was showed according to various operating and design conditions. The effects of microscale electrode geometry on the cell performance were also taken into account. Parametric study according to the volumetric fraction of ionic and electronic conducting particles was conducted in order to examine the effects of operating conditions on the cell overpotentials. The study results substantiate the fact that SOFC overpotential could be effectively decreased by increasing the operating temperature as well as operating pressure. This present study reveals the working mechanisms of SOFC at the microscale level, while demonstrating the use of microscale relations to enhance the SOFC performance. The accuracy of the presented model was validated by comparing with already existing experimental results from the available literatures.     

Redox Tolerance of Thin and Thick Ni/YSZ Anodes of Electrolyte‐Supported Single‐Chamber Solid Oxide Fuel Cells under Methane Oxidation Conditions

Redox tolerance of 50 and 500 μm thick Ni/YSZ (yttria‐stabilized zirconia) anodes supported on YSZ electrolytes were studied under single‐chamber solid oxide fuel cell conditions. Open circuit voltage, electrochemical impedance spectra, and discharge curves of the cells were measured under different methane/oxygen ratios at 700 °C. For the cell with the thin anode, a significant degradation accompanying oscillatory behaviors was observed, whereas the cell based on the thick anode was much more stable under the same conditions. In situ local anode resistance (R_s) results indicated that the Ni/NiO redox cycling was responsible for the oscillatory behaviors, and the cell degradation was primarily caused by the Ni reoxidation. Reoxidation of the thick anode took place at a low methane/oxygen ratio, but the anode can be recovered to its original state by switching to a methane‐rich environment. On the contrary, the thin anode was unable to be regenerated after the oxidation. Microstructure damage of the anode was attributed to its irreversible degradation.     

Three‐Dimensional Simulation of Pressure Fluctuation in a Granular Solid Propellant Chamber within an Ignition Stage

The effects of the conditions of the ignition system in the propellant chamber of a gun system using a granular solid propellant are numerically investigated with respect to ignition performance criteria such as the differential pressure generation between the breech and the projectile base. Simulations, in which the length of the primer and the igniter mass are varied, are performed using a solid/gas two‐phase fluid dynamics code for three‐dimensional calculation of gas flow and discrete solid propellant particles. This code simulates the igniter combustion in the primer, the movement of burning solid propellant grains, and the formation of pressure gradients inside the chamber in the ignition process. The differential pressures between the breech and the projectile base measured in experiments are well predicted by the simulations for various igniter conditions. In the process of igniting the solid propellant, the propellant grains are accelerated toward the projectile base by the igniter gas flows from the primer vents. Fixed‐particle simulation is also carried out in order to examine the effects of the movement of the solid propellant grains on the chamber pressure profile. The simulated results reveal that the movement of solid propellant grains causes differential pressure fluctuations, which depend on the discharge from the primer vents and the locations of these vents.     

固体氧化物燃料电池的研究进展

固体氧化物燃料电池(SOFC)是先进陶瓷材料的一种重要应用,可以通过电化学反应将燃料的化学能直接转换为电能。SOFC具有效率高、性能稳定、便携、低污染等优点,可以实现能源的有效清洁利用。本文结合国内外SOFC的研究情况,分析讨论了SOFC的技术优势、地方产业优势及产业难题,并结合国家政策方面对我国SOFC产业的未来发展做了展望。     

Biogas Catalytic Reforming Studies on Nickel‐Based Solid Oxide Fuel Cell Anodes

Heterogeneous catalysis studies were conducted on two crushed solid oxide fuel cell (SOFC) anodes in fixed‐bed reactors. The baseline anode was Ni/ScYSZ (Ni/scandia and yttria stabilized zirconia), the other was Ni/ScYSZ modified with Pd/doped ceria (Ni/ScYSZ/Pd‐CGO). Three main types of experiments were performed to study catalytic activity and effect of sulfur poisoning: (i) CH₄ and CO₂ dissociation; (ii) biogas (60% CH₄ and 40% CO₂) temperature‐programmed reactions (TPRxn); and (iii) steady‐state biogas reforming reactions followed by postmortem catalyst characterization by temperature‐programmed oxidation and time‐of‐flight secondary ion mass spectrometry. Results showed that Ni/ScYSZ/Pd‐CGO was more active for catalytic dissociation of CH₄ at 750 °C and subsequent reactivity of deposited carbonaceous species. Sulfur deactivated most catalytic reactions except CO₂ dissociation at 750 °C. The presence of Pd‐CGO helped to mitigate sulfur deactivation effect; e.g. lowering the onset temperature (up to 190 °C) for CH₄ conversion during temperature‐programmed reactions. Both Ni/ScYSZ and Ni/ScYSZ/Pd‐CGO anode catalysts were more active for dry reforming of biogas than they were for steam reforming. Deactivation of reforming activity by sulfur was much more severe under steam reforming conditions than dry reforming; a result of greater sulfur retention on the catalyst surface during steam reforming.     

平板式固体氧化物燃料电池的热机械行为

基于COMSOL Multiphysics仿真平台建立了多物理场耦合作用下的平板式固体氧化物燃料单电池模型,考虑多种温度相关的材料物理化学性质,研究了残余应力以及阳极材料中镍体积分数对电池内部热应力的影响.结果表明:残余应力的存在增大了电池关键构件电解质和阴极电极工作状态下的最大拉伸和压缩应力,减小了阳极电极的最大拉伸...     

Phenomenological Theory of Solid Oxide Fuel Cell Anode

We develop a phenomenological theory of oxygen‐ion‐conducting porous cermet anode for solid oxide fuel cells utilizing hydrogen, based on a simple picture of macro‐ and microkinetics of charge and gas transport in the cermet. Its basic equations account for the transport of hydrogen molecules and oxygen anions to the reaction spots, the hydrogen oxidation reaction (whose various mechanisms, including different adsorption stages, are considered) and the water‐product removal. Simple analytical results are obtained for a linear current‐voltage regime, which demonstrate the interplay of these three processes. The nonlinear behavior is analyzed and classified. Various mechanisms of reaction kinetics are considered, subject to three possible mechanisms of water adsorption, in order to specify the law of conversion of ionic current into electronic one. Revealed is the nature of the intermediate quasi‐Tafel regime, in which the anode is usually employed, and of two possible large current regimes: the saturation regime and the blocking regime (due to oxidation of the anode). The study rationalizes principles of anode functioning and builds a basis for a systematic analysis of the effects due to composite structure, that enter through the basic parameters of the theory.     

固体氧化物燃料电池材料的研究进展

本文对燃料电池的研究发展进行了概述,详细地介绍了固体氧化物燃料电池的电解质材料、阴极材料、阳极材料及互连材料,并对固体氧化物燃料电池以后的发展提出了一些建议。