Developing fuel map to predict the effect of fuel composition on the maximum voltage of solid oxide fuel cells

A thermodynamic model is developed to determine the fuels that would yield an identical maximum cell voltage (MCV) for solid oxide fuel cells (SOFCs) at a given operating condition. These fuels make a continuous curve in the ternary coordinate system. A fuel map is established by developing the continuous fuel curves for different MCVs at the same operating condition and representing them in the carbon-hydrogen-oxygen (C-H-O) ternary diagram. Using the fuel map, the effect of the composition of a fuel containing carbon, hydrogen, oxygen, and inert gas atoms on the MCV of SOFCs can be easily studied. In addition to the effect of the fuel composition, the graphical representation of fuel maps can be applied to study the effect of the fuel processors on the MCV of SOFCs. As a general result, among fuels that can be directly utilized in SOFCs, at the same temperature and pressure, the one located at the intersection of the H-C axis and the carbon deposition boundary (CDB) curve in the C-H-O ternary diagram, provides the highest MCV for SOFCs. The results also show that for the fuels that cannot be directly utilized in SOFC, the steam reforming fuel processor always yields a higher MCV than the autothermal reforming or the partial oxidation fuel processors at the same inlet fuel temperature.     

Novel materials for solid oxide fuel cell technologies: A literature review

This study aims to review novel materials for solid oxide fuel cell (SOFC) applications covered in literature. Thence, it was found that current SOFC operating conditions lead to issues, such as carbon surface deposition, sulfur poisoning and quick component degradation at high temperatures, which make it unsuitable for a few applications. Therefore, many researches are focused on cell performance enhancement through replacing the materials being used in order to improve properties and/or reduce operating temperatures. Most modifications in the anode aim to avoid some issues concerning conventionally used Ni-based materials, such as carbon deposition and sulfur poisoning, besides enhancing catalytic activity, once this component is directly exposed to the fuel. It was also found literature about the cathode with the aim of developing a material with enhanced properties in a wider temperature range, which has been compared to the currently used one: LSM perovskite (La_1-xSr_xMnO₃). Novel electrolyte materials can have ionic or protonic conductivity, thus performance degradation must be avoided at several operating conditions. In order to enhance its electrochemical performance, different materials for electrodes (cathode and anode) and electrolytes have been assessed herein.     

A direct-flame solid oxide fuel cell (DFFC) operated on methane,propane, and butane

This paper presents an experimental study of a direct-flame type solid oxide fuel cell (DFFC). The operation principle of this system is based on the combination of a combustion flame with a solid oxide fuel cell (SOFC) in a simple, no-chamber setup. The flame front serves as fuel reformer located a few millimeters from the anode surface while at the same time providing the heat required for SOFC operation. Experiments were performed using 13-mm-diameter planar SOFCs with Ni-based anode, samaria-doped ceria electrolyte and cobaltite cathode. At the anode, a 45-mm-diameter flat-flame burner provided radially homogeneous methane/air, propane/air, and butane/air rich premixed flames. The cell performance reaches power densities of up to 120 mW cm⁻², varying systematically with flame conditions. It shows a strong dependence on cell temperature. From thermodynamic calculations, both H₂ and CO were identified as species that are available as fuel for the SOFC. The results demonstrate the potential of this system for fuel-flexible power generation using a simple setup.     

The impact of steam and current density on carbon formation from biomass gasification tar on Ni/YSZ, and Ni/CGO solid oxide fuel cell anodes

The combination of solid oxide fuel cells (SOFCs) and biomass gasification has the potential to become an attractive technology for the production of clean renewable energy. However the impact of tars, formed during biomass gasification, on the performance and durability of SOFC anodes has not been well established experimentally. This paper reports an experimental study on the mitigation of carbon formation arising from the exposure of the commonly used Ni/YSZ (yttria stabilized zirconia) and Ni/CGO (gadolinium-doped ceria) SOFC anodes to biomass gasification tars. Carbon formation and cell degradation was reduced through means of steam reforming of the tar over the nickel anode, and partial oxidation of benzene model tar via the transport of oxygen ions to the anode while operating the fuel cell under load. Thermodynamic calculations suggest that a threshold current density of 365 mA cm⁻² was required to suppress carbon formation in dry conditions, which was consistent with the results of experiments conducted in this study. The importance of both anode microstructure and composition towards carbon deposition was seen in the comparison of Ni/YSZ and Ni/CGO anodes exposed to the biomass gasification tar. Under steam concentrations greater than the thermodynamic threshold for carbon deposition, Ni/YSZ anodes still exhibited cell degradation, as shown by increased polarization resistances, and carbon formation was seen using SEM imaging. Ni/CGO anodes were found to be more resilient to carbon formation than Ni/YSZ anodes, and displayed increased performance after each subsequent exposure to tar, likely due to continued reforming of condensed tar on the anode.     

Direct ammonia solid-oxide fuel cells: A review of progress and prospects

With the rapidly declining cost of renewable energy, efficient ways are needed for its transportation between different regions. Hydrogen is becoming a major energy vector, with the key challenges of its storage and transportation commonly overcome by using ammonia for chemical storage of hydrogen energy. Ammonia, which is more energy dense than hydrogen and easier to transport, is a carbon-free alternative fuel that can be used in a variety of ways to generate power. Owing to their robustness and efficiency, solid-oxide fuel cells (SOFC) stand out as one of the most promising technologies that convert ammonia to electricity. Unlike other fuel cells, such as polymer electrolyte membranes, SOFCs do not require the fuel to be cleaned by energy-intensive external cracking and extensive cleaning; their high operating temperature provides the flexibility to crack the ammonia inside the anode or to use it directly. Here, we discuss experimental and numerical studies of ammonia SOFCs and critically review the status and opportunities for ammonia-fuelled SOFC technology. In the first section, we briefly outline the potential cathode and electrolyte materials for SOFCs. Only the anode component poses additional challenges with ammonia over the well-established hydrogen-fuelled SOFC technology, and this topic has been addressed in detail. Anode catalysts for ammonia decomposition, parameters affecting ammonia decomposition and anode catalyst degradation are also discussed. In the second section, we review the modelling studies for ammonia SOFCs. Finally, we run through the major commercial initiatives and demonstrations in green ammonia production and ammonia SOFCs.     

Fabrication of micro-tubular solid oxide fuel cells with a single-grain-thick yttria stabilized zirconia electrolyte

This study discusses the fabrication and electrochemical performance of micro-tubular solid oxide fuel cells (SOFCs) with an electrolyte consisting a single-grain-thick yttria stabilized zirconia (YSZ) layer. It is found that a uniform coating of an electrolyte slurry and controlled shrinkage of the supported tube leads to a dense, crack-free, single-grain-thick (less than 1 μm) electrolyte on a porous anode tube. The SOFC has a power density of 0.39 W cm⁻² at an operating temperature as low as 600 °C, with YSZ and nickel/YSZ for the electrolyte and anode, respectively. An examination is made of the effect of hydrogen fuel flow rate and shown that a higher flow rate leads to better cell performance. Hence a YSZ cell can be used for low-temperature SOFC systems below 600 °C, simply by optimizing the cell structure and operating conditions.     

Reducing the operation temperature of a solid oxide fuel cell using a conventional nickel-based cermet anode on dimethyl ether fuel through internal partial oxidation

Dimethyl ether (DME)-oxygen mixture as the fuel of an anode-supported SOFC with a conventional nickel-cermet anode for operating at reduced temperatures is systematically investigated. The results of the catalytic tests indicate that sintered Ni-YSZ has high activity for DME partial oxidation, and DME conversion exceeds 90% at temperatures higher than 700 °C. Maximum methane selectivity is reached at 700 °C. Cell performance is observed between 600 and 800 °C. Peak power densities of approximately 400 and 1400 mW cm⁻² at 600 and 800 °C, respectively, are reached for the cell operating on DME-O₂ mixture. These values are comparable to those obtained using hydrogen as a fuel, and cell performance is reasonably stable at 700 °C for a test period of 340 min. SEM results demonstrate that the cell maintains good geometric integrity without any delimitation of respective layer after the stability test, and EDX results show that carbon deposition occurrs only at the outer surface of the anode. O₂-TPO analysis shows that carbon deposition over the Ni-YSZ operating on DME is greatly suppressed in the presence of oxygen. Internal partial oxidation may be a practical way to achieve high cell performance at intermediate-temperatures for SOFCs operating on DME fuel.     

Thermodynamic analysis of solid oxide fuel cells operated with methanol and ethanol under direct utilization,steam reforming,dry reforming or partial oxidation conditions

There is increasing interest in developing solid oxide fuel cells (SOFC) for portable applications. For these devices it would be convenient to directly use a liquid fuel such as methanol and ethanol rather than hydrogen. The direct utilization of alcohol fuels in SOFC involves several processes, including the deposition of carbon, which can lead to irreversible deactivation of the fuel cell. Several publications have addressed the thermodynamic analysis of the reforming of methanol (MeOH) and ethanol (EtOH) in SOFC, but none have considered the direct utilization of these fuels. The equilibrium compositions, the carbon deposition boundaries, and the electromotive forces for the direct utilization and partial oxidation of methanol and ethanol in SOFC as a function of the fuel utilization are obtained in this study. In addition, the minimum amounts of H₂O, and CO₂ for direct and indirect reforming with MeOH and EtOH to avoid carbon formation are calculated.     

Performance of solid oxide fuel cell with chemical looping gasification products as fuel

Chemical looping gasification (CLG) can achieve the utilization of solid fuels for syngas production. The CLG system integrated with solid oxide fuel cell (SOFC) is a promising energy conversion way. In this work, an integration system of CLG and SOFC is evaluated via the implementation of a multi-field coupling modelling, where the products from the CLG are directly transported into the SOFC as the fuel and the coke deposition effect on the cell performance is evaluated. The results reveal that SOFC temperature using pure hydrogen as fuel has an increase of around 4 K compared to that with gas mixture as fuel owing to the inhibition of carbon deposition. It is found that the arrangement of anode and cathode in the countercurrent mode can promote the overall uniformity of current density compared to that in the cocurrent flow. Moreover, the impact of operating parameter of the CLG system on the SOFC performance is also examined. The results demonstrate that the increase of fuel reactor (FR) temperature and H₂O/C molar ratio in the CLG system is beneficial to the inhibition of carbon deposition and the enhancement of the SOFC performance.     

Operation of solid oxide fuel cells with alternative hydrogen carriers

Future electricity production will use fossil-free sources with zero CO₂ emission or closed carbon cycle technologies based on renewable sources. While hydrogen is considered a key energy source, its production at present time relies heavily on fossil fuels. Furthermore, distribution and storage are not well established and require substantial investments. This is a strong motivation to identify alternative, safe, high power density hydrogen carriers, where existing logistics and infrastructure can be utilized. In this contribution, ammonia and biogas are considered for high-efficient electricity production in solid oxide fuel cells (SOFCs). It is demonstrated that the properties and operating conditions of SOFC allow for direct use of these fuels, with fuel pretreatment inside the SOFC anode. The high efficient electricity production using pure ammonia or real biogas was successfully proven on state-of-the-art SOFCs. Even without optimization of operating parameters, electrical efficiencies of 40–50% and high and stable power output were demonstrated.     

Developing fuel map to predict the effect of fuel composition on the maximum efficiency of solid oxide fuel cells

At any given cell operating condition, a fuel map can be developed to predict the effect of a fuel containing carbon, hydrogen, oxygen and inert gas atoms on the maximum cell efficiency (MCE) of solid oxide fuel cells (SOFCs). To create a fuel map, a thermodynamic model is developed to obtain the fuels that would yield identical MCE for SOFCs. These fuels make a continuous curve in the ternary coordinate system. A fuel map is established by developing continuous fuel curves for different MCEs at the same operating condition of a cell and representing them in the carbon-hydrogen-oxygen (C-H-O) ternary diagram. The graphical representation of fuel maps can be applied to predict the effect of the fuel composition and fuel processor on the MCE of SOFCs. As a general result, among the fuels that can be directly utilized in SOFCs, at the same temperature and pressure, the one located at the intersection of the H-C axis and the carbon deposition boundary (CDB) curve in the C-H-O ternary diagram provides the highest MCE. For any fuel that can be indirectly utilized in SOFCs, the steam reforming fuel processor always yields a higher MCE than auto-thermal reforming or partial oxidation fuel processors at the same anode inlet fuel temperature.     

The interaction of biomass gasification syngas components with tar in a solid oxide fuel cell and operational conditions to mitigate carbon deposition on nickel-gadolinium doped ceria anodes

The combination of biomass gasification with solid oxide fuel cells (SOFCs) is gaining increasing interest as an efficient and environmentally benign method of producing electricity and heat. However, tars in the gas stream arising from the gasification of biomass material can deposit carbon on the SOFC anode, having detrimental effects to the life cycle and operational characteristics of the fuel cell. This work examines the impact of biomass gasification syngas components combined with benzene as a model tar, on carbon formation on Ni/CGO (gadolinium-doped ceria) SOFC anodes. Thermodynamic calculations suggest that SOFCs operating at temperatures > 750 °C are not susceptible to carbon deposition from a typical biomass gasification syngas containing 15 g m⁻³ benzene.However, intermediate temperature SOFCs operating at temperatures < 650 °C require threshold current densities well above what is technologically achievable to inhibit the effects of carbon deposition. SOFC anodes have been shown to withstand tar levels of 2-15 g m⁻³ benzene at 765 °C for 3 h at a current density of 300 mA cm⁻², with negligible impact on the electrochemical performance of the anode. Furthermore, no carbon could be detected on the anode at this current density when benzene levels were <5 g m⁻³.     

Thermodynamic study on glycerol-fuelled intermediate-temperature solid oxide fuel cells (IT-SOFCs) with different electrolytes

In this paper, a thermodynamic analysis was carried out to provide useful information about the operation of intermediate-temperature Solid Oxide Fuel Cells (IT-SOFCs) with direct internal reforming (DIR) fuelled by glycerol. A methodology, based on the principle of minimizing the Gibbs energy of a given system, using spreadsheets and the Microsoft Excel’s Solver function, was described for DIR operation of the SOFC with oxygen ion conducting electrolyte (SOFC-O²⁻) and proton conducting electrolyte (SOFC-H⁺). The effect of temperature, fuel utilization and type of electrolyte on the equilibrium composition of the anode gas mixture as well as on the boundary of carbon formation has been investigated in the temperature range of 773–1073 K. Based on the results of this thermodynamic study, glycerol can be considered an alternative fuel with suitable characteristics for electricity generation in IT-SOFCs. Operating at carbon-free conditions, between 773 and 1073 K, with a fuel utilization of 99.99% in the anode channel outlet, glycerol-fuelled IT-SOFCs systems attain high theoretical efficiencies in the range of 80.7–89.9% (SOFC-O²⁻ case) and 90.3–96.7% (SOFC-H⁺ case). Regarding the maximum values of the average electromotive force (EMF) and efficiency, it was verified that glycerol exhibits very similar potential for power generation with ethanol. Although glycerol fed SOFC-H⁺ is superior to SOFC-O²⁻ in terms of maximum theoretical efficiency, it should be taken into account that the SOFC-H⁺ shows a greater tendency for carbon deposition than does the SOFC-O²⁻ during the operation. Besides, it was found that decreasing temperature increases the efficiency but also favors carbon formation, for both SOFC-O²⁻ and SOFC-H⁺. When the system runs at 70% of its maximum power and the partial pressure of residual hydrogen in the anode outlet is kept equal to 0.1 atm, the highest efficiency (67%) is achieved by operating an SOFC-H⁺ at 823 K.     

Recent progress on solid oxide fuel cell: Lowering temperature and utilizing non-hydrogen fuels

A solid oxide fuel cell (SOFC) is a promising energy conversion device with high efficiency and low pollutant emission. The practical application of the conventional SOFCs is limited mainly because of their high operating temperature and the inconvenience brought by the H₂ fuel utilization. This work reviews the recent progress on intermediate temperature SOFCs especially with non-hydrogen fuels. Composite electrolyte consisting of a solid oxide ionic conducting phase and a molten carbonate phase exhibits sufficient ionic conductivity in the intermediate temperature range, i.e. 500–800 °C, and facilitates the simultaneous conduction of H⁺, O²⁻ and CO₃²⁻ ions. A single cell with the composite electrolyte shows a promising power density, 1700 mW cm⁻² at 650 °C with hydrogen as the fuel. The composite electrolyte has been also employed in a direct carbon fuel cell (DCFC), and the simultaneous conduction of O²⁻ and CO₃²⁻ in the electrolyte has been proposed. Recently, perovskite structured materials are found to have good resistance to coke formation as the anode of the direct hydrocarbon solid oxide fuel cell, and several carbon resistant perovskite anodes are employed in all-perovskite structured SOFCs, which exhibit excellent performance with CH₄ and methanol as the fuel.     

Ammonia‐fed solid oxide fuel cells for power generation—A review

Ammonia has been identified as a promising sustainable fuel and hydrogen source for solid oxide fuel cells (SOFC). This paper aims to provide a literature review on ammonia‐fed SOFCs. Both experimental studies and mathematical modeling investigations on NH₃‐fed SOFC are included and discussed. It is found that NH₃ is a technically feasible fuel for direct use in SOFCs and the performance of NH₃‐fed SOFC is comparable with that of the H₂ fed SOFC. Experimental study in literature also demonstrates that both oxygen ion‐conducting electrolyte (SOFC‐O) and proton‐conducting electrolyte (SOFC‐H) can be used in NH₃‐fed SOFC, as the amount of NO_x generated in a SOFC‐O is negligible. Fabricating thin film electrolyte and developing more reactive electrode materials are important to improve the performance of NH₃‐fed SOFCs. Mathematical models are useful design tools for understanding the coupled transport and reaction phenomena and for optimizing the SOFC performance. Thermodynamic and pioneering 1D electrochemical models have been developed, validated and demonstrated to be reliable by the present author. Copyright © 2009 John Wiley & Sons, Ltd.     

Electrochemical performance assessment of low-temperature solid oxide fuel cell with YSZ-based and SDC-based electrolytes

In this work, solid oxide fuel cells (SOFCs) based on different electrolytes, i.e., the yttria-stabilized zirconia (YSZ) and the samaria-doped ceria (SDC), were investigated to study their performances at low-temperature operation. The predicted performance of both SOFCs was validated with the experimental results. The verified models were implemented to study the impact of operating conditions, i.e., cell temperature, pressure, thicknesses of cathode, anode, and electrolyte, on their performances. The decrease in the operating temperature from intermediate range (800–900 °C) to low range (550–650 °C) has a considerable effect on the performance of the YSZ-based SOFC as conventional type, which dropped from 0.67–1.40 W/cm² to 0.027–0.13 W/cm². Under the low operating temperature range, the performance of SDC-based SOFC was superior to that of the YSZ-based SOFC, due to the lower ohmic loss. Nevertheless, the SDC-based SOFC has higher concentration overpotentials than the YSZ-based SOFC. The concentration overpotentials of the SDC-based SOFC can be reduced by the thinner anode and cathode thicknesses. In addition, the SDC-based SOFC at low operating temperature with the pressurized operation could significantly improve its power density, about 20% at 2 bar, which was close to that of YSZ-based SOFC at intermediate temperature of 800 °C.     

Characterization of electrolyte–electrode interlayers in thin film solid oxide fuel cells

In order to reduce the operating temperature of solid oxide fuel cells (SOFCs), anode-supported cells incorporating thin film (∼10 μm) electrolytes in conjunction with anode/electrolyte and cathode/electrolyte interlayers were studied. SOFC button cells were prepared through deposition of colloidal slurries onto anode supported substrates and were analyzed as a function of temperature and polarization via voltammetry and electrochemical impedance spectroscopy (EIS). It was found that the electro-catalytic activity or electrode/electrolyte interfacial areas were enhanced through the addition of these interlayers. This performance improvement was attributed to the introduction of a diffuse mixed conduction region associated with these interlayers. The cathode is thought to benefit disproportionately from this enhancement. Single SOFC button cells with electrode interlayers were then characterized as a function of temperature and polarization to assess the involvement of these interfacial layers. EIS was applied and the data were used to deconvolute component impedances. Finally electrochemical models were developed to provide a more complete understanding of these assemblies under operation.     

Experimental characterization and mechanistic modeling of carbon monoxide fueled solid oxide fuel cell

The paper presents an elementary reaction based solid oxide fuel cell (SOFC) model coupled with anodic elementary heterogeneous reactions and electrochemical charge transfer reactions for CO/CO₂ fuel based on an anode supported button cell. The model is calibrated and validated using experimental data obtained for various CO/CO₂ fuel compositions at 750, 800 and 850 °C. The comparison shows that the modeling results agree well with the experimental data. The effects of operating conditions on the cell performance and the detailed species concentration distribution are predicted. Then, the carbon deposition on the SOFC anode with CO/CO₂ fuel is experimentally measured and simulated using the elementary reaction model. The results indicate that lower temperature and lower operation voltage are helpful to reduce the possibilities of carbon deposition on Ni particle surfaces.     

Anode recirculation behavior of a solid oxide fuel cell system: A safety analysis and a performance optimization

Anode recirculation, which is generally driven by an ejector, is commonly used in solid oxide fuel cell (SOFC) systems that operate with natural gas. Alternative fuels such as gasification syngas from biomass have been proposed for potential use in the SOFC systems because of the fuel flexibility of SOFCs and the sustainability of biomass resources. Because the ejector was initially designed to use natural gas, its recirculation behavior when using alternative fuels is not well understood. The aim of this research work is to study anode recirculation behavior and analyze its effect on safety issues regarding carbon deposition and nickel oxidation and the performance of an SOFC system fed with gasification syngas under steady state operation. We developed a detailed model including a recirculation model and an SOFC stack model for this study, which was well validated by experimental data. The results show that the entrainment ratio with the gasification syngas is much smaller than that with the natural gas, and the gasification syngas does not have the tendency toward carbon deposition or nickel oxidation under the operating conditions studied. In addition, the recirculation affects the performance of the SOFC, especially the net electrical efficiency, which could be promoted by 160%.     

Fundamentals of electro- and thermochemistry in the anode of solid-oxide fuel cells with hydrocarbon and syngas fuels

High fuel flexibility of solid-oxide fuel cells (SOFCs) affords the possibility to use relatively cheap, safe, and readily available hydrocarbon (e.g., CH₄) or coal syngas (i.e., CO-H₂ mixtures) fuels. Utilization of such fuels would greatly lower fuel cost and increase the feasibility of SOFC commercialization, especially for near-term adoption in anticipation of the long-awaited so-called “hydrogen economy”. Current SOFC technology has shown good performance with a wide range of hydrocarbon and syngas fuels, but there are still significant challenges for practical application. In this paper, the basic operating principles, state-of-the-art performance benchmarks, and SOFC-relevant materials are summarized. More in-depth reviews on those topics can be found in Kee and co-workers [Combust Sci and Tech 2008; 180:1207–44 and Proc Combust Inst 2005; 30:2379–404] and McIntosh and Gorte [Chem Rev 2004; 104:4845–65]. The focus of this review is on the fundamentals and development of detailed electro- and thermal (or simply, electrothermal) chemistry within the SOFC anode, including electrochemical oxidation mechanisms for H₂, CO, CH₄, and carbon, as well as the effects of carbon deposition and sulfur poisoning. The interdependence of heterogeneous chemistry, charge-transfer processes, and transport are discussed in the context of SOFC membrane-electrode assembly modeling.