Development of methanol‐fueled low‐temperature solid oxide fuel cells

Low‐temperature solid oxide fuel cell (SOFC, 300–600°C) technology fueled by methanol possessing significant importance and application in polygenerations has been developed. Thermodynamic analysis of methanol gas‐phase compositions and carbon formation indicates that direct operation on methanol between 450 and 600°C may result in significant carbon deposition. A water steam/methanol ratio of 1/1 can completely suppress carbon formation in the same time enrich H₂ production composition. Fuel cells were fabricated using ceria–carbonate composite electrolytes and examined at 450–600°C. The maximum power density of 603 and 431 mW cm^?2 was achieved at 600 and 500°C, respectively, using water steam/methanol with the ratio of 1/1 and ambient air as fuel and oxidant. These results provide great potential for development of the direct methanol low–temperature SOFC for polygenerations. Copyright © 2010 John Wiley & Sons, Ltd.     

A review of numerical modeling of solid oxide fuel cells

The solid oxide fuel cell (SOFC) is one of the most promising fuel cells for direct conversion of chemical energy to electrical energy with the possibility of its use in co-generation systems because of the high temperature waste heat. Various mathematical models have been developed for three geometric configurations (tubular, planar, and monolithic) to solve transport equations coupled with electrochemical processes to describe the reaction kinetics including internal reforming chemistry in SOFCs. In recent years, considerable progress has been made in modeling to improve the design and performance of this type of fuel cells. The numbers of the contributions on this important type of fuels have been increasing rapidly. The objective of this paper is to summarize the present status of the SOFC modeling efforts so that unresolved problems can be identified by the researchers.     

High performance metal-supported solid oxide fuel cells fabricated by thermal spray

Metal-supported solid oxide fuel cells (SOFCs) have been fabricated and characterized in this work. The cells consist of porous NiO-SDC as anode, thin SDC as electrolyte, and SSCo as cathode on porous stainless steel substrate. The anode and electrolyte layers were consecutively deposited onto porous metal substrate by thermal spray, using standard industrial thermal spray equipment, operated in an open-air atmosphere. The cathode materials were applied to the as-sprayed half-cells by screen-printing and heat-treated at 800 °C for 2 h. The cell components and performance were examined by scanning electron microscopy (SEM), X-ray diffraction, leakage test, ac impedance and electrochemical polarization at temperatures between 500 and 700 °C. The half-inch button cells exhibit a maximum power density in excess of 0.50 W cm⁻² at 600 °C and 0.92 W cm⁻² at 700 °C operated with humidified hydrogen fuel, respectively. The half-inch button cell was run at 0.5 A cm⁻² at 603 °C for 100 h. The cell voltage decreased from 0.701 to 0.698 V, giving a cell degradation rate of 4.3% kh⁻¹. Impedance analysis indicated that the cell degradation included 4.5% contribution from ohmic loss and 1.4% contribution from electrode polarization. The 5 cm × 5 cm cells were also fabricated under the same conditions and showed a maximum power density of 0.26 W cm⁻² at 600 °C and 0.56 W cm⁻² at 700 °C with dry hydrogen as fuel, respectively. The impedance analysis showed that the ohmic resistance of the cells was the major polarization loss for all the cells, while both ohmic and electrode polarizations were significantly increased when the operating temperature decreased from 700 to 500 °C. This work demonstrated the feasibility for the fabrication of metal-supported SOFCs with relatively high performance using industrially available deposition techniques. Further optimization of the metal support, electrode materials and microstructure, and deposition process is ongoing.     

Scientometric review of proton-conducting solid oxide fuel cells

Proton-conducting solid oxide fuel cells (P–SOFCs) are promising energy conversion devices that convert chemical energy directly to electrical energy. P–SOFCs have attracted significant attention in the past few years because of their superiority over the oxygen-ion-conducting solid oxide fuel cells (O–SOFCs) in terms of better feasibility of efficient operation at lower temperatures, non-dilution of fuel at the anode, and higher theoretical efficiency. This review focuses on the scientometric analysis of 1008 quality articles retrieved from the Scopus database. The historical trends and progress in P–SOFCs are presented starting from the inception of the demonstration of the concept of proton conductivity in solid oxide fuel cells from 1986 to 2021. Furthermore, the notable achievements in the material development of various components of P–SOFC are expounded. The scientometric analysis reveals that only 28% of the countries in the world are involved in P–SOFC research and the National Natural Science Foundation of China is the top featured funding sponsor for many research studies related to P–SOFC development. This article can serve as an easy guide for P–SOFC research enthusiasts to navigate through the overview of this research area and identify potential collaborators, funding sponsors, most impactful researchers, countries, and articles.     

YSZ films fabricated by a spin smoothing technique and its application in solid oxide fuel cell

A dense single-layer YSZ film has been successfully fabricated by a spin smoothing method. Followed by a simplified slurry coating, an additional spin smoothing process was conducted to obtain a thinner and smoother film. By employment of high-viscosity slurry including high YSZ content, the film has a suitable thickness by a single coating cycle. With Sm_0.2Ce_0.8O_1.9 (SDC)-impregnated La_0.7Sr_0.3MnO₃ (LSM) cathode and porous NiO–YSZ anode, single solid oxide fuel cell (SOFC) based on an 8-μm-thick YSZ film was obtained. Open-circuit voltage (OCV) of the cell was 1.04 V at 800 °C, and maximum power densities were 676, 965 and 1420 mW cm⁻² at 700, 750 and 800 °C, respectively, using H₂ at a flow rate of 40 mL min⁻¹ as fuel and ambient air as oxidant. The power density could be increased to 1648 mW cm⁻² at 800 °C when the flow rate of H₂ was enhanced to 200 mL min⁻¹.     

Study on GDC-KZnAl composite electrolytes for low-temperature solid oxide fuel cells

Development of low-temperature solid oxide fuel cells (LTSOFC) is now becoming a mainstream research direction worldwide. The advancement in the effective electrolyte materials has been one of the major challenges for LTSOFC development. To further improve the performance of electrolyte, composite approaches are considered as common strategies. The enhancement on ionic conductivity or sintering behavior ceria-based electrolyte can either be done by adding a carbonate phase to facilitate the utilization of the ionic-conducting interfaces, or by addition of alumina as insulator to reduce the electronic conduction of ceria. Thus the present report aims to design a composite electrolyte materials by combining the above two composite approaches, in order to enhance the ionic conductivity and to improve the long-term stability simultaneously. Here we report the preparation and investigation of GDC-KAlZn materials with composition of Gd doped ceria, K₂CO₃, ZnO and Al₂O₃. The structure and morphology of the samples were characterized by XRD, SEM, etc. The ionic conductivity of GDC-KAlZn sample was determined by impedance spectroscopy. The composite samples with various weight ratio of GDC and KAlZn were used as electrolyte material to fabricate and evaluate fuel cells as well as investigate the composition dependent properties. The good ionic conductivity and notable fuel cell performance of 480 mW cm⁻² at 550 °C has demonstrated that GDC-KAlZn composite electrolyte can be regarded as a potential electrolyte material for LTSOFCs.     

Latest development of double perovskite electrode materials for solid oxide fuel cells: a review

Recently, the development and fabrication of electrode component of the solid oxide fuel cell (SOFC) have gained a significant importance, especially after the advent of electrode supported SOFCs. The function of the electrode involves the facilitation of fuel gas diffusion, oxidation of the fuel, transport of electrons, and transport of the byproduct of the electrochemical reaction. Impressive progress has been made in the development of alternative electrode materials with mixed conducting properties and a few of the other composite cermets. During the operation of a SOFC, it is necessary to avoid carburization and sulfidation problems. The present review focuses on the various aspects pertaining to a potential electrode material, the double perovskite, as an anode and cathode in the SOFC. More than 150 SOFCs electrode compositions which had been investigated in the literature have been analyzed. An evaluation has been performed in terms of phase, structure, diffraction pattern, electrical conductivity, and power density. Various methods adopted to determine the quality of electrode component have been provided in detail. This review comprises the literature values to suggest possible direction for future research.     

Performance comparison of cocurrent and countercurrent flow solid oxide fuel cells

Solid oxide fuel cell (SOFC) is a complicated system with heat and mass transfer as well as electrochemical reactions. The flowing configuration of fuel and oxidants in the fuel cell will greatly affect the performance of the fuel cell stack. Based on the developed mathematical model of direct internal reforming SOFC, this paper established a distributed parameters simulation model for cocurrent and countercurrent types of SOFC based on the volume-resistance characteristic modeling method. The steady-state distribution characteristics and dynamic performances were compared and were analyzed for cocurrent and countercurrent types of SOFCs. The results indicate that the cocurrent configuration of SOFC is more suitable with regard to performance and safety.     

Self-rising synthesis of Ni-SDC cermets as anodes for solid oxide fuel cells

Ni-SDC cermets have been obtained using a self-rising approach by two different ways, one-step direct synthesis (OS) and ball milling the separately prepared NiO and SDC powders (BM). The results showed that self-rising approach was an efficient way for the synthesis of porous materials composed of evenly distributed uniform size nanocrystals. The as-synthesized powders have been applied as anodes for solid oxide fuel cells, whose electrochemical properties have been systematically studied. Cells with anodes from the BM method showed better performance compared with those of the OS method, achieving a maximum power density of 400 mW cm⁻² at 600 °C.     

Silver (Ag) as anode and cathode current collectors in high temperature planar solid oxide fuel cells

Planar electrolyte supported solid oxide fuel cells were operated at 900 °C with humidified H₂ for 200 h using silver mesh and paste for cathode current collection. Continuous potentiostatic tests at 0.7 V appeared to induce migration of Ag towards electrode-electrolyte interphase, while continuous OCV tests caused no mass transport. Similar SOFCs fueled by coal syngas at 850 °C using Ag for both anode and cathode current collection indicated little, if any, Ag migration; providing the possibility of employing Ag for 100 h laboratory scale tests using coal-derived syngas. Use of high temperature steam, carbon dioxide and carbon monoxide did not result in the formation of silver carbonates.     

A review on macro‐level modeling of planar solid oxide fuel cells

In this review paper, a comprehensive literature survey on macro‐level modeling of solid oxide fuel cells (SOFCs) is presented. First, the current status of the SOFC modeling is assessed. Second, modeling techniques are discussed in detail. These include the thermodynamics, electrochemistry and heat transfer aspects of the modeling. Thermodynamic relations for pure hydrogen as the fuel and then gas mixture as the fuel are given. Additionally, exergy destructed due to polarizations is shown. Then, modeling equations for ohmic, activation, and concentration polarizations are given. Handling the carbon deposition problem in the modeling is discussed. The inclusion of the convection and radiation heat transfer processes to the modeling is explained. Finally, the models in literature are compared in terms of the methodology used and suggestions for increasing the accuracy of the future models are given. Copyright © 2007 John Wiley & Sons, Ltd.     

Air plasma spray processing and electrochemical characterization of Cu-SDC coatings for use in solid oxide fuel cell anodes

Air plasma spraying has been used to produce porous composite anodes based on Ce_0.8Sm_0.2O_1.9 (SDC) and Cu for use in solid oxide fuel cells (SOFCs). Preliminarily, a range of plasma conditions has been examined for the production of composite coatings from pre-mixed SDC and CuO powders. Plasma gas compositions were varied to obtain a range of plasma temperatures. After reduction in H₂, coatings were characterized for composition and microstructure using EDX and SEM. As a result of these tests, symmetrical sintered electrolyte-supported anode-anode cells were fabricated by air plasma spraying of the anodes, followed by in situ reduction of the CuO to Cu. Full cells deposited on SS430 porous substrates were then produced in one integrated process. Fine CuO and SDC powders have been used to produce homogeneously mixed anode coatings with higher surface area microstructures, resulting in area-specific polarization resistances of 4.8 Ω cm² in impedance tests in hydrogen at 712 °C.     

Layered perovskite GdBaCoFeO5+x as cathode for intermediate-temperature solid oxide fuel cells

A layered perovskite oxide, GdBaCoFeO_5+x (GBCF), was investigated as a novel cathode for intermediate-temperature solid oxide fuel cells (IT-SOFCs). A laboratory-sized Sm_0.2Ce_0.8O_1.9 (SDC)-based tri-layer cell of NiO–SDC/SDC/GBCF was tested under intermediate-temperature conditions of 550–650 °C with humidified H₂ (∼3% H₂O) as a fuel and the static ambient air as oxidant. A maximal power density of 746 mW cm⁻² was achieved at 650 °C. The interfacial polarization resistance was as low as 0.42, 0.18 and 0.11 Ω cm² at 550, 600 and 650 °C, respectively. The experimental results indicate that the layered perovskite GBCF is a promising cathode candidate for IT-SOFCs.     

Alkaline metal doped strontium cobalt ferrite perovskites as cathodes for intermediate-temperature solid oxide fuel cells

Perovskite oxides Sr_0.9K_0.1Fe_xCo_1-xO_3-δ (SKFCx, x = 0.1, 0.3, 0.5, 0.7, 0.9 and 1.0) are investigated as potential cathode materials for intermediate-temperature solid oxide fuel cells (IT-SOFCs) on Sm_0.2Ce_0.8O_1.9 (SDC) electrolyte. The cubic phase of the SKFCx oxides is demonstrated by x-ray diffraction. The SKFCx cathode shows good compatibility with the SDC electrolyte up to 900 °C. Among the investigated compositions, SKFC0.1 displays the highest electrical conductivity of 443–146 S·cm^?1 from 350 °C to 800 °C in flow air. The area specific resistances (ASRs) of the SKFCx (x = 0.1, 0.3, 0.5, 0.7, 0.9 and 1.0) cathodes are 0.047, 0.058, 0.066, 0.101, 0.155 and 0.175 Ω cm² at 650 °C in air on an SDC electrolyte. Among the five tested cathodes, SKFC0.1 exhibits the lowest area specific resistances between 550 °C and 750 °C, when tested on its symmetric cell configuration of cathode|SDC|cathode. The thermally stabilized cubic perovskite structure of the SKFC0.1 powder is demonstrated by high-temperature XRD. The average linear thermal expansion coefficient α_L of SKFC0.1 is 18.9$\times$10^?6 K^?1. A peak power density of 1643 mW·cm^?2 is achieved on SKFC0.1|SDC|Ni-SDC anode supported fuel cell at 650 °C. These features, and excellent electrocatalytic activity and good stability, indicate the potential of alkaline metal doped strontium cobalt ferrite perovskites are promising cathode materials for IT-SOFCs.     

Ceria coated Ni as anodes for direct utilization of methane in low-temperature solid oxide fuel cells

A new type of anode, a Ni framework coated with Sm-doped ceria (SDC), was developed for direct utilization of methane fuel in low-temperature solid oxide fuel cells (SOFCs) with thin-film SDC electrolytes. The coated SDC was prepared with an ion impregnating method and the electrolyte films were fabricated with a co-pressing and co-firing technique. The impregnating process produced an ideal anode microstructure where nickel particles were effectively connected and uniformly covered with nanosized SDC. This anode microstructure was believed to enlarge the triple-phase boundaries and therefore enhance the anode performance. The cell performance was much higher than that of a conventional fuel cell with a Ni-SDC composite anode. In addition, the performance increased with impregnated SDC loading up to a maximum at 20 mg cm⁻², indicating that the coated SDC is the contributing factor for the enhanced fuel cell performance. Power density as high as 571 and 353 mW cm⁻² were obtained at 600 °C when humidified hydrogen and methane were used as fuels, respectively. The stability of the cell also increased with the SDC loading. No significant degradation was observed for anodes coated with 20 and 25 mg cm⁻² SDC. This verifies that the coated SDC electrodes are very effective in suppressing catalytic carbon formation by blocking methane from approaching the Ni, which is catalytically active towards methane pyrolysis. The high performance of this anode shows high promise in the developing field of direct hydrocarbon SOFCs.     

Performance analysis of a solid oxide fuel cell with reformed natural gas fuel

In the present study a two‐dimensional model of a tubular solid oxide fuel cell operating in a stack is presented. The model analyzes electrochemistry, momentum, heat and mass transfers inside the cell. Internal steam reforming of the reformed natural gas is considered for hydrogen production and Gibbs energy minimization method is used to calculate the fuel equilibrium species concentrations. The conservation equations for energy, mass, momentum and voltage are solved simultaneously using appropriate numerical techniques. The heat radiation between the preheater and cathode surface is incorporated into the model and local heat transfer coefficients are determined throughout the anode and cathode channels. The developed model has been compared with the experimental and numerical data available in literature. The model is used to study the effect of various operating parameters such as excess air, operating pressure and air inlet temperature and the results are discussed in detail. The results show that a more uniform temperature distribution can be achieved along the cell at higher air‐flow rates and operating pressures and the cell output voltage is enhanced. It is expected that the proposed model can be used as a design tool for SOFC stack in practical applications. Copyright © 2009 John Wiley & Sons, Ltd.     

Ceria-based nanocomposite with simultaneous proton and oxygen ion conductivity for low-temperature solid oxide fuel cells

The samarium doped ceria-carbonate (SDC/Na₂CO₃) nanocomposite systems have shown to be excellent electrolyte materials for low-temperature SOFCs, yet, the conduction mechanism is not well understood. In this study, a four-probe d.c. technique has been successfully employed to study the conduction behavior of proton and oxygen ion in SDC/Na₂CO₃ nanocomposite electrolyte. The results demonstrated that the SDC/Na₂CO₃ nanocomposite electrolyte possesses unique simultaneous proton and oxygen ion conduction property, with the proton conductivity 1-2 orders of magnitude higher than the oxygen ion conductivity in the temperature range of 200-600 °C, indicating the proton conduction in the nanocomposite mainly accounts for the enhanced total ionic conductivity. It is suggested that the interface in composite electrolyte supplies high conductive path for proton, while oxygen ions are probably transported by the SDC grain interiors. An empirical “Swing Model” has been proposed as a possible mechanism of superior proton conduction.     

Temperature and performance variations along single chamber solid oxide fuel cells

The catalytic activity of single chamber solid oxide fuel cells (SC-SOFCs) with respect to hydrocarbon fuels induces a major overheating of the fuel cell, temperature variations along its length, and changes in the original fuel/air composition mainly over the anode component. This paper assesses the temperature gradients and the variations in performance along electrolyte-supported Ni-YSZ/YSZ/LSM cells fed with methane gas. The investigations are performed in a useful range of CH₄/O₂ ratios between 1.0 and 2.0, in which the furnace temperature and flow rate of methane–air mixtures are held constant at 700 °C and 450 sccm, respectively. Electrochemical impedance spectroscopy (EIS) is used to sense the temperature at the location where smaller size cathodes are positioned on the opposite side of a full-size anode. Due to temperature increases, cells always perform better when the small cathodes are located at the inlet as well as at a CH₄/O₂ ratio of 1.0. With an increase in ratio, the results show the presence of artefacts due to the use of an active LSM material for the combustion of methane, and open-type gas distribution plates for the single chamber reactor.