The effects of fuel variability on the electrical performance and durability of a solid oxide fuel cell operating on biohythane

Biohythane is typically composed of 60/30/10 vol% CH₄/CO₂/H₂ and can be produced via two-stage anaerobic digestion of renewable and low carbon biomass with much greater efficiency compared with CH₄/CO₂ biogas. This work investigates the effects of fuel variability on the electrical performance and fuel processing of a commercially available anode supported solid oxide fuel cell (SOFC) operating on biohythane mixtures at 750 °C. Cell electrical performance was characterised using current-voltage curves and electrochemical impedance spectroscopy. Fuel processing was characterised using quadrupole mass spectroscopy. It is shown that when H₂/CO₂ is blended with CH₄ to make biohythane, the SOFC efficiency is significantly increased, high SOFC durability is achieved, and there are considerable savings in CH₄ consumption. Enhanced electrical performance was due to the additional presence of H₂ and promotion of CH₄ dry reforming, the reverse Boudouard and reverse water-gas shift reactions. These processes alleviated carbon deposition and promoted electrochemical oxidation of H₂ as the primary power production pathway. Substituting 50 vol% CH₄ with 25/75 vol% H₂/CO₂ was shown to increase cell power output by 81.6% at 0.8 V compared with pure CH₄. This corresponded to a 3.4-fold increase in the overall energy conversion efficiency and a 72% decrease in CH₄ consumption. A 260 h durability test demonstrated very high cell durability when operating on a typical 60/30/10 vol% CH₄/CO₂/H₂ biohythane mixture under high fuel utilisation due to inhibition of carbon deposition. Overall, this work suggests that decarbonising gas grids by substituting natural gas with renewably produced H₂/CO₂ mixtures (rather than pure H₂ derived from fossil fuels), and utilising in SOFC technology, gives considerable gains in energy conversion efficiency and carbon emissions savings.     

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.     

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.     

Thermodynamic evaluation of sorption-enhanced chemical looping gasification with coal as fuel

Chemical looping gasification (CLG) is regarded as an efficient way for the utilization of solid fuel and hydrogen-enriched syngas production. In this work, a thermodynamic analysis is carried out to evaluate the CLG performance of coal on the basis of Gibbs free energy minimization. In order to enhance the gasification process, CO₂ sorption is employed and sorbents are circulated in the whole system. The influence of operating parameters on the CLG performance as well as heat requirement of the system is further examined. The results reveal that the addition of sorbent can promote the hydrogen production and provide the heat for the reaction in the fuel reactor (FR), whereas additional energy input is still required for the whole system. A proper increase of oxygen carrier circulation rate can achieve the auto-thermal condition of the system.     

Perovskite materials for highly efficient catalytic CH4 fuel reforming in solid oxide fuel cell

SOFC (solid oxide fuel cell, SOFC) is recognized to be efficient green energy technology in the 21st century. However, when hydrocarbons are directly used as fuel, carbon deposition is easy to occur in Ni-based anode, thus losing electrochemical catalytic activity. Fuel pre-reforming is also called on-cell reforming of hydrocarbons, which has been a promising solution for alleviating the carbon deposition problem in cermet anodes to varying degrees. And the key factor is to find an efficient and stable fuel reforming catalyst. Perovskite oxides have stable structure, highly catalytic activity and adjustable thermal expansion coefficient for using on the cells, showing great potentials of application for fuel reforming. In this paper, we summarize the application of perovskite catalyst in CH₄ fuel reforming based on the research of our group and other scholars, and puts forward the corresponding views and perspective, especially in perovskite catalyst with Ni exsolution.     

Lignite as a fuel for direct carbon fuel cell system

Lignite, also known as brown coal, and char derived from lignite by pyrolysis were investigated as fuels for direct carbon solid oxide fuel cells (DC-SOFC). Experiments were carried out with 16 cm² active area, electrolyte supported solid oxide fuel cell (SOFC), using pulverized solid fuel directly fed to DC-SOFC anode compartment in a batch mode, fixed bed configuration. The maximum power density of 143 mW/cm² was observed with a char derived from lignite, much higher than 93 mW/cm² when operating on a lignite fuel. The cell was operating under electric load until fuel supply was almost completely exhausted. Reloading fixed lignite bed during a thermal cycle resulted in a similar initial cell performance, pointing to feasibility of fuel cell operation in a continuous fuel supply mode. The additional series of experiments were carried out in SOFC cell, in the absence of solid fuels, with (a) simulated CO/CO₂ gas mixtures in a wide range of compositions and (b) humidified hydrogen as a reference fuel composition for all cases considered. The solid oxide fuel cell, operated with 92%CO + 8%CO₂ gas mixture, generated the maximum power density of 342 mW/cm². The fuel cell performance has increased in the following order: lignite (DC-SOFC) < char derived from lignite (DC-SOFC) < CO + CO₂ gas mixture (SOFC) < humidified hydrogen (SOFC).     

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.     

Effects of fuel processing methods on industrial scale biogas-fuelled solid oxide fuel cell system for operating in wastewater treatment plants

The performance of three solid oxide fuel cell (SOFC) systems, fuelled by biogas produced through anaerobic digestion (AD) process, for heat and electricity generation in wastewater treatment plants (WWTPs) is studied. Each system has a different fuel processing method to prevent carbon deposition over the anode catalyst under biogas fuelling. Anode gas recirculation (AGR), steam reforming (SR), and partial oxidation (POX) are the methods employed in systems I-III, respectively. A planar SOFC stack used in these systems is based on the anode-supported cells with Ni-YSZ anode, YSZ electrolyte and YSZ-LSM cathode, operated at 800 °C. A computer code has been developed for the simulation of the planar SOFC in cell, stack and system levels and applied for the performance prediction of the SOFC systems. The key operational parameters affecting the performance of the SOFC systems are identified. The effect of these parameters on the electrical and CHP efficiencies, the generated electricity and heat, the total exergy destruction, and the number of cells in SOFC stack of the systems are studied. The results show that among the SOFC systems investigated in this study, the AGR and SR fuel processor-based systems with electrical efficiency of 45.1% and 43%, respectively, are suitable to be applied in WWTPs. If the entire biogas produced in a WWTP is used in the AGR or SR fuel processor-based SOFC system, the electricity and heat required to operate the WWTP can be completely self-supplied and the extra electricity generated can be sold to the electrical grid.     

Performance evaluation of combined solid oxide fuel cells with different electrolytes

The performance of a hybrid system of solid oxide fuel cells with different electrolytes, i.e., an oxygen-ion conducting electrolyte (SOFC-O²⁻) and a proton-conducting electrolyte (SOFC-H⁺) is evaluated in this study. Due to an internal reforming operation, SOFC-O²⁻ can produce electrical power as well as high-temperature exhaust gas containing remaining fuel, i.e., H₂ and CO that can be used for SOFC-H⁺ operation. The remaining CO can further react with H₂O via water gas-shift reaction to produce more H₂ within SOFC-H⁺ and thus, the possibility of carbon formation in SOFC-H⁺ can be eliminated and overall system efficiency can be improved. The simulation results show that the performance of the SOFC-O²⁻–SOFC-H⁺ system provides a higher efficiency (54.11%) compared with the use of a single SOFC. Further, the SOFC hybrid system performance is investigated with respect to important operating conditions, such as temperature, pressure, degree of pre-reforming, inlet fuel velocity, and cell voltage.     

Thermodynamic analysis and experimental study of electrode reactions and open circuit voltages for methane-fuelled SOFC

Natural gas is one of the most important fuels for solid oxide fuel cell (SOFC). The relationships among the reactions of methane over the nickel-based anode, fuel compositions, carbon deposition, electromotive force (EMF) and open circuit voltage (OCV) of SOFC are investigated in this work. With the increase of temperature, EMF and OCV of SOFC decrease gradually when the cell uses humidified hydrogen as fuel. Reactivity of methane increases gradually with the increase of temperature, which can affect the EMF and OCV of SOFC. When the humidified mixture of nitrogen and methane is used as the fuel, the EMF and OCV of SOFC increase gradually with the increase of temperature. EMF and OCV of SOFC with humidified mixture of hydrogen and methane (M_CH4: M_H2: M_H2O = 12.2: 85.3: 2.5) as fuel decrease gradually with the increase of temperature when the temperature is lower than 873 K, which is similar to that with humidified hydrogen as fuel. While when the temperature is higher than 923 K, the EMF and OCV of SOFC with humidified mixture of hydrogen and methane as fuel increase gradually with the increase of temperature, which is similar to that with humidified mixture of nitrogen and methane as fuel. OCV of SOFC is mainly affected by thermodynamic equilibriums for methane-fuelled SOFC when the anode activity is high enough, which is close to the EMF calculated according to the thermodynamic equilibriums. While with the increase of carbon deposition, the anode activity decreases apparently and the OCV of SOFC also decreases apparently, which shows that the OCV is affected by the anode activity for methane-fuelled SOFC when the anode activity is low.     

Design of highly efficient coal-based integrated gasification fuel cell power plants

Integrated gasification fuel cell (IGFC) technology combining coal gasification and solid oxide fuel cell (SOFC) is believed to be the only viable solution to achieving U.S. Department of Energy (DOE)’s performance goal for next generation coal-based power plants, producing electricity at 60% efficiency (coal HHV-AC) while capturing more than 90% of the evolved CO₂. Achieving this goal is challenging even with high performance SOFCs; design concepts published to date have not demonstrated this performance goal. In this work an IGFC system concept consisting of catalytic hydro-gasification, proven low-temperature gas cleaning and hybrid fuel cell-gas turbine power block (with SOFC operating at about 10 bar) is introduced. The system is demonstrating an electricity efficiency greater than 60% (coal HHV basis), with more than 90% of the carbon present in the syngas separated as CO₂ amenable to sequestration. A unique characteristic of the system is recycling de-carbonized, humidified anode exhaust back to the catalytic hydro-gasifier for improved energy integration. Alternative designs where: (1) anode exhaust is recycled directly back to SOFC stacks, (2) SOFC stack operating pressure is reduced to near atmospheric and (3) methanation reactor in the reactor/expander topping cycle is removed, have also been investigated and the system design and performance differences are discussed.     

Operation of solid oxide fuel cells on glycerol fuel: A thermodynamic analysis using the Gibbs free energy minimization approach

Solid oxide fuel cells (SOFCs) are very flexible, unlike other fuel cells. In principle, SOFCs can operate on almost any fuel. Currently much effort is invested in the development of SOFCs for portable applications operating directly on liquid fuels such as methanol and ethanol rather than hydrogen. However, there are very few publications dealing with the direct use of glycerol in SOFCs for portable systems. A recently published study shows that the performance achieved for an SOFC fueled by pure glycerol is quite interesting even when there is a thick electrolyte membrane, indicating that glycerol is a promising fuel for portable applications. For this reason a thermodynamic analysis for SOFCs operating directly on glycerol fuel is performed in the present study. The Gibbs energy minimization method computes the equilibrium compositions of the anode gas mixture, carbon deposition boundaries and electromotive forces (EMFs) as a function of fuel utilization and temperature. Moreover, the minimum amounts of H₂O, CO₂ (direct internal reforming case) and air (partial oxidation case) to be added to glycerol in the feedstock to avoid carbon deposition at the open circuit voltage (OCV) are calculated. Finally, a thermodynamic analysis is performed, taking into account the experimental conditions employed in a previous study. Experimental observations concerning carbon deposition in an SOFC operating on glycerol can be explained by the theoretical analysis developed in the present study. Additionally, the effect of mixed electronic-ionic conduction of the electrolyte on carbon deposition at the anode is discussed based on the thermodynamic analysis of the C-O system.     

Effects of methane processing strategy on fuel composition,electrical and thermal efficiency of solid oxide fuel cell

Natural gas is a cheap and abundant fuel for solid oxide fuel cell (SOFC), generally integrating the SOFC system with methane pre-treating system for improving the stability of SOFC. In this paper, the accurate effects of methane processing strategy on fuel composition, electrical efficiency and thermal efficiency of SOFC are investigated based on the thermodynamic equilibrium. Steam reforming of methane is an endothermic process and can produce 3 mol of H₂ and 1 mol of CO from 1 mol of methane, and thus the electrical efficiency of SOFC is high at the same O/C ratio and equivalent fuel utilization, whereas the thermal efficiency is low. On the contrary, partial oxidation of methane is an exothermal process and only produces 2 mol of H₂ and 1 mol of CO from 1 mol of methane, and thus the electrical efficiency of SOFC is low at the same O/C ratio and equivalent fuel utilization, whereas the thermal efficiency is high. When the O/C ratio is 1.5, the electrical efficiency of SOFC is 55.3% for steam reforming of methane, while 32.7% for partial oxidation of methane. High electrical efficiency of SOFC can be achieved and carbon deposition can be depressed by selecting suitable O/C ratio from methane pretreatment according to the accurate calculation and analysis of effects of different methane processing strategies on the electrical efficiency and thermal efficiency of SOFC.     

Tolerance tests of H2S-laden biogas fuel on solid oxide fuel cells

Biogas is a variable mixture of methane, carbon dioxide and other gases. It is a renewable resource which comes from numerous sources of plant and animal matter. Ni-YSZ anode-supported solid oxide fuel cell (SOFC) can directly use clean synthesized biogas as fuel. However, trace impurities, such as H₂S, Cl₂ and F₂ in real biogas can cause degradation in cell performance. In this research, both uncoated and coated Ni-YSZ anode-supported cells were exposed to three different compositions of synthesized biogases (syn-biogas) with 20 ppm H₂S under a constant current load at 750-850 °C and their performance was evaluated periodically using standard electrochemical methods. Postmortem analysis of the SOFC anode was performed using X-ray diffraction (XRD), scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS). The results show that H₂S causes severe electrochemical degradation of the cell when operating on biogas, leading to both complete electrochemical and mechanical failure. The Ni-CeO₂ coated cell showed excellent stability during CH₄ reforming and some tolerance to H₂S contamination.     

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%.     

Operation of solid oxide fuel cell on biomass product gas with tar levels >10 g Nm−3

This work assesses experimentally the feasibility of feeding a high tar load product gas from biomass gasification to a planar solid oxide fuel cell (SOFC) for renewable electricity generation. The SOFC had a nickel gadolinium-doped ceria anode (Ni-GDC) and the gasifier was a pilot scale circulating fluidized bed, employing hot gas-cleaning to remove particulates, HCl and H₂S. The SOFC operated for several hours on either pre-reformed gas (reduced tar levels < 0.5 g Nm^?3) as well as on high tar-laden wood gas (tar levels > 10 g Nm^?3) i.e. with no pre-reforming of tars. The tests were carried out at low fuel utilization U_f of around 20% at a current density j = 130 mA cm^?2. In all cases stable continuous SOFC performance was established. Post experimental examination of the SOFC showed that the anode was not affected by carbon deposition or other impurity accumulation.     

Performance analysis of hybrid solid oxide fuel cell and gas turbine cycle (part I): Effects of fuel composition on output power

In this paper, the model of hybrid solid oxide fuel cell (SOFC) and gas turbine (GT) cycle is applied to investigate the effects of the inlet fuel type and composition on the performance of the hybrid SOFC–GT cycle. The sensitivity analyses of the impacts of the concentration of the different components, namely, methane, hydrogen, carbon dioxide, carbon monoxide, and nitrogen, in the inlet fuel on the performance of the hybrid SOFC–GT cycle are performed. The simulation results are presented with respect to a reference case, when the system is fueled by pure methane. Then, the performance of the hybrid SOFC–GT system when methane is partially replaced by each component within a corresponding range of concentration with an increment of 5% at each step is investigated. The results point out that the output powers of the SOFC, GT, and cycle as a whole decrease sharply when methane is replaced with other species in majority of the cases.     

On the intrinsic transient capability and limitations of solid oxide fuel cell systems

The intrinsic transient performance capability and limitation of integrated solid oxide fuel cell (SOFC) systems is evaluated based on the system balance-of-plant response and fuel cell operating requirements (i.e., allowable deviation from nominal operation). Specifically, non-dimensional relations are derived from conservation principles that quantify the maximum instantaneous current increase that a solid oxide fuel cell system can safely manage based on (1) the desired fuel cell operating point, (2) the maximum allowable fuel utilization, (3) the maximum average fuel cell temperature deviation, (4) the response delay and (5) the operating requirements of the system balance-of-plant components. New non-dimensional numbers representing the ratio of species or thermal convection to volumetric capacitance in the fuel cell during balance-of-plant delay have been developed.     

Combined methane reforming by carbon dioxide and steam in proton conducting solid oxide fuel cells for syngas/power co-generation

Methane and carbon dioxide mixture can be used as the fuel in a proton conducting solid oxide fuel cell (SOFC) for power/syngas co-generation and greenhouse gas reduction. However, carbon deposition and low conversion ratio are potential problems for this technology. Apart from using functional catalytic layer in the SOFC to enhance CH₄ dry reforming, adding H₂O into the fuel stream could facilitate the CH₄ conversion and enhance the co-generation performance of the SOFC. In this work, the effects of adding H₂O to the CO₂CH₄ fuel on the performance of a tubular proton conducting SOFC are studied numerically. Results show that the CH₄ conversion is improved from 0.830 to 0.898 after adding 20% H₂O to the anode. Meanwhile, the current density is increased from 2832 A m⁻² to 3064 A m⁻² at 0.7 V. Sensitivity studies indicate that the H₂:CO ratio can be effectively controlled by the amount of H₂O addition and the H₂ starvation can be alleviated, especially at high current density conditions.     

Simulation analysis of a system combining solid oxide and polymer electrolyte fuel cells

We evaluated the performance of system combining a solid oxide fuel cell (SOFC) stack and a polymer electrolyte fuel cell (PEFC) stack by a numerical simulation. We assume that tubular-type SOFCs are used in the SOFC stack. The electrical efficiency of the SOFC–PEFC system increases with increasing oxygen utilization rate in the SOFC stack. This is because the amount of exhaust heat of the SOFC stack used to raise the temperature of air supplied to it decreases as its oxygen utilization rate increases and because that used effectively as the reaction heat of the steam reforming reaction of methane in the stack reformer increases. The electrical efficiency of the SOFC–PEFC system at 190 kW ac is 59% (LHV), which is equal to that of the SOFC-gas turbine combined system at 1014 kW ac.