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.     

Study on GDC-LSGM composite electrolytes for intermediate-temperature solid oxide fuel cells

The electrolyte materials Ce_0.9Gd_0.1O_1.9 (GDC) and La_0.9Sr_0.1Ga_0.8Mg_0.2O_2.85 (LSGM) were synthesized by means of glycine-nitrate processes, respectively, then GDC-LSGM composite electrolytes were prepared by mixing GDC and LSGM. The GDC and LSGM powders were mixed in the weight ratio of 95:5, 90:10 and 85:15 and named as GL9505, GL9010 and GL8515. Their structures and ionic conductivities were investigated by means of X-ray diffraction (XRD), scanning electron microscopy (SEM), Raman and AC impedance spectroscopy. The grain sizes of GDC-LSGM composites could be increased distinctly and the grain boundary resistance could be significantly decreased by small addition of LSGM. The experimental results show that the GDC-LSGM composites exhibit excellent ionic conductivity and could significantly enhance the fuel cell performances. The open circuit voltages are higher in the cell with composite electrolytes than in the cell with single GDC as electrolyte at the working temperature. Among these electrolytes, GL9505 has the highest ionic conductivity and the maximum power density.     

Numerical simulation of intermediate-temperature direct-internal-reforming planar solid oxide fuel cell

A numerical model for an anode-supported intermediate-temperature direct-internal-reforming planar solid oxide fuel cell (SOFC) was developed. In this model, the volume-averaging method is applied to the flow passages in the SOFC by assuming that a porous material is inserted in the passages as a current collector. This treatment reduces the computational time and cost by avoiding a full three-dimensional simulation while maintaining the ability to solve the flow and pressure fields in the streamwise and spanwise directions. In this model, quasi-three-dimensional multicomponent gas flow fields, the temperature field, and the electric potential/current fields were simultaneously solved. The steam-reforming reaction using methane, the water-gas shift reaction, and the electrochemical reactions of hydrogen and carbon monoxide were taken into account. It was found that the endothermic steam-reforming reaction led to a reduction in the local temperature near the inlet and limited the electrochemical reaction rates therein. Computational results indicated that the local temperature and current density distributions can be controlled by tuning the pre-reforming rate. It was also found that a small amount of heat loss from the sidewall can cause significant nonuniformity in the flow and thermal fields in the spanwise direction.     

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.     

Anode supported solid oxide fuel cells (SOFC) by electrophoretic deposition

Solid oxide fuel cells (SOFC), with its ability to use hydrocarbon fuels and capability to offer highest efficiency, have attracted great attention in India in recent years as an alternative energy generation system for future. But a great deal of problems associated with SOFC is needed to be solved before it can find commercial application. The relatively high operating temperature of 800-1000 °C of SOFC imposes a stringent requirement on materials that significantly increases the cost of SOFC technology. Reducing the operating temperature of an SOFC to below 800 °C can reduce degradation of cell components, improve flexibility in cell design, and lower the material and manufacturing cost by the use of cheap and readily available materials such as ferritic stainless steel. The operating temperature can be reduced by two possible approaches: (i) developing alternative electrolyte materials with high ionic conductivity at lower temperature, and (ii) developing much thinner and denser electrolyte layer such that the ohmic losses are minimised.In this work we report the use of inexpensive Electrophoretic deposition (EPD) technique in making about 10 micron thin and dense YSZ electrolyte on NiO-YSZ substrate. The effect of different operating parameters such as applied voltage, deposition time etc have been optimised during deposition from YSZ suspension in acetylacetone. The YSZ/NiO-YSZ bi-layers were then co-sintered at 1450 °C for 5 h. The single SOFC cells were then fabricated by brush painting LSM:YSZ (50:50) paste on the electrolyte layer followed by sintering at 1200 °C for 2 h. The single SOFC cell when tested using H₂ as fuel and ambient air as oxidant exhibited an open circuit voltage (OCV) of 1.03 V and the peak power density of about 624 mW/cm² at 800 °C.     

Mathematical modeling of ammonia-fed solid oxide fuel cells with different electrolytes

An electrochemical model was developed to study the ammonia (NH₃)-fed solid oxide fuel cells with proton-conducting electrolyte (SOFC-H) and oxygen ion-conducting electrolyte (SOFC-O). Different from previous thermodynamic analysis, the present study reveals that the actual performance of the NH₃-fed SOFC-H is considerably lower than the SOFC-O, mainly due to higher ohmic overpotential of the SOFC-H electrolyte. More analyses have been performed to study the separate overpotentials of the NH₃-fed SOFC-H and SOFC-O. Compared with the NH₃-fed SOFC-H, the SOFC-O has higher anode concentration overpotential and lower cathode concentration overpotential. The effects of temperature and electrode porosity on concentration overpotentials have also been studied in order to identify possible methods for improvement of SOFC performance. This study reveals that the use of different electrolytes not only causes different ion conduction characteristics at the electrolyte, but also significantly influences the concentration overpotentials at the electrodes. The model developed in this article can be extended to 2D and 3D models for further design optimization.     

Durability of direct internal reforming of methanol as fuel for solid oxide fuel cell with double-sided cathodes

Direct internal reforming of methanol is applied as fuel for a Ni-YSZ anode-supported solid oxide fuel cell with a flat tube based on double-sided cathodes. It achieves a power density (PD) of 0.25 W/cm² at 0.8 V, reaching about 90% of that is fueled by H₂. And the cell has been operated for more than 120 h by the direct internal reforming of methanol. The durability and apparent advantage for using humidified methanol may lead to widespread applications by direct internal reforming method for this new designed SOFC in the future.     

Effects of coal syngas major compositions on Ni/YSZ anode-supported solid oxide fuel cells

This paper presents a systematical evaluation of the effects of CO₂, H₂O, CO, N₂ and CH₄ in the coal syngas on the properties of typical Ni/YSZ anode-supported solid oxide fuel cells (SOFCs). The results show that CO₂, H₂O, CO, N₂ and CH₄ have complicated effects on the cell performance and the electrochemical impedance spectra (EIS) analysis reveals the addition of these gases influences electrode processes such as the oxygen ion exchange from YSZ to anode TPBs, the charge transfer at the anode TPBs, gas diffusion and conversion at the anode. Two kinds of mixture gases with different compositions are thus constituted and used as fuel for aging test on two cells at 750 °C. No degradation or carbon deposition is observed for the cell fueled with 40% H₂-20% CO-20% H₂O-20% CO₂ for 360 h while the cell fueled with 50% H₂-30% CO-10% H₂O-10% CO₂ exhibits an abrupt degradation after 50 h due to the severe carbon deposition.     

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.     

Ni-Sm2O3 cermet anodes for intermediate-temperature solid oxide fuel cells with stabilized zirconia electrolytes

Ni-LnO_x cermets (Ln = La, Ce, Pr, Nd, Sm, Eu, Gd), in which LnO_x is not an oxygen ion conductor, have shown high performance as the anodes for low-temperature solid oxide fuel cells (SOFCs) with doped ceria electrolytes. In this work, Ni-Sm₂O₃ cermets are primarily investigated as the anodes for intermediate-temperature SOFCs with scandia stabilized zirconia (ScSZ) electrolytes. The electrochemical performances of the Ni-Sm₂O₃ anodes are characterized using single cells with ScSZ electrolytes and LSM-YSB composite cathodes. The Ni-Sm₂O₃ anodes exhibit relatively lower performance, compared with that reported Ni-SDC (samaria doped ceria) and Ni-YSZ (yttria stabilized zirconia) anodes, the state-of-the-art electrodes for SOFCs based on zirconia electrolytes. The relatively low performance is possibly due to the solid-state reaction between Sm₂O₃ and ScSZ in fuel cell fabrication processes. By depositing a thin interlayer between the Ni-Sm₂O₃ anode and the ScSZ electrolyte, the performance is substantially improved. Single cells with a Ni-SDC interlayer show stable open circuit voltage, generate peak power density of 410 mW cm⁻² at 700 °C, and the interfacial polarization is about 0.7 Ω cm².     

Modelling of solid oxide fuel cells with internal glycerol steam reforming

The direct application of glycerol in solid oxide fuel cell (SOFC) for power generation has been demonstrated experimentally but the detailed mechanisms are not well understood due to the lack of comprehensive modeling study. In this paper, a numerical model is developed to study the glycerol-fueled SOFC. After model validation, the simulated SOFC demonstrates a performance of 7827 A m^?2 at 0.6 V, with a glycerol conversion rate of 49% at 1073 K. Then, parametric analyses are conducted to understand the effects of operation conditions on cell performance. It is found that the SOFC performance increases with decreasing operating voltage or increasing inlet temperature. However, increasing either the fuel flow rate or steam to glycerol ratio could decrease the cell performance. It is also interesting to find out that the contribution of H₂ and CO to the total current density is significantly different under various operating conditions, even sometimes CO dominates while H₂ plays a negative role. This is different from our conventional understanding that usually H₂ contributes more significantly to current generation. In addition, cooling measures are needed to ensure the long-term stability of the cell when operating at a high current density.     

Ni-samaria-doped ceria (Ni-SDC) anode-supported solid oxide fuel cell (SOFC) operating with CO

The performance of nickel-samaria-doped ceria (Ni-SDC) anode-supported cell with CO-CO₂ feed was evaluated. The aim of this work is to examine carbon formation on the Ni-SDC anode when feeding with CO under conditions when carbon deposition is thermodynamically favoured. Electrochemical tests were conducted at intermediate temperatures (550–700 °C) using 20 and 40% CO concentrations. Cell operating with 40% CO at 600–700 °C provided maximum power densities of 239–270 mW cm^?2, 1.5 times smaller than that achieved with humidified H₂. Much lower maximum power densities were attained with 20% CO (50–88 mW cm^?2). Some degradation was observed during the 6 h galvanostatic operation at 0.1 A cm^?2 with 40% CO fuel at 550 °C which is believed due to the accumulation of carbon at the anode. The degradation in cell potential occurred at a rate of 4.5 mV h^?1, but it did not lead to cell collapse. EDX mapping at the cross-section of the anode revealed that carbon formed in the Ni-SDC cell was primarily deposited in the anode section close to the fuel entry point. Carbon was not detected at the electrolyte-anode interface and the middle of the anode, allowing the cell to continue operation with CO fuel without a catastrophic failure.     

Electrochemical properties and thermal neutral state of solid oxide fuel cells with direct internal reforming of methane

Solid oxide fuel cells (SOFCs) with direct internal reforming (DIR) provide a promising method to realize clean and efficient utilization of hydrocarbon fuels. Thse endothermic reforming reactions occur simultaneously with exothermic electrochemical reactions at the anode, making thermal neutral state achievable inside a fuel cell, providing reference to the thermal management. In this study, a calculation model combining experimental data and thermodynamic results was established, validating the possibility of achieving thermal neutral state in DIR-SOFCs. In the process of modeling, the electrochemical and thermodynamic characteristics in direct internal steam and dry reforming were elaborately compared, contributing to a more scientific understanding of anode reaction mechanism. Detailed experimental investigation was carried out to determine the influence of H₂O/CO₂ on the electrochemical properties of DIR-SOFCs, based on which the optimum steam-carbon ratio (S/C) and CO₂ to CH₄ ratios were obtained. Besides, analysis of distribution of relaxation times (DRT) combined with elementary reactions in CH₄H₂O and CH₄CO₂ atmospheres were proposed to distinguish different physical and chemical processes within anodes. The results of this study can be conducive to a more precise understanding of reaction mechanism on SOFC anodes and meaningful for practical application of DIR-SOFCs.     

Thermodynamic investigation on hydrogen production via self-sufficient chemical looping reforming of glycerol (CLRG) using metal oxide oxygen carriers

The self-sufficient chemical looping reforming of glycerol (CLRG) utilizes the same basic principles as chemical looping combustion (CLC), the main difference being that the desired product in CLRG is not heat but H₂. Therefore, in the CLR process the O/C ratio is kept low to prevent the complete oxidation of glycerol to H₂O. A systematic thermodynamic study of CLRG using metal oxide oxygen carriers (NiO, CuO, CoO, Co₃O₄, Mn₃O₄, Mn₂O₃ and Fe₂O₃) is performed to analyze the product yield, carbon deposition and energy requirements at different temperatures and pressures. The calculation results show higher temperatures promote, but higher pressures inhibit H₂ production. Favorable conditions (800 °C and 1 atm) are obtained for H₂ manufacture from CLRG process. CuO is the best performing oxygen carrier followed by Mn-based oxygen carriers, while Fe₂O₃ is the least preferred oxygen carrier for CLRG. These results obtained in this theoretical study can offer helpful information for CLRG experimental tests.     

Optimizing strontium titanate anode in solid oxide fuel cells by ytterbium doping

One of advantages of solid oxide fuel cells (SOFCs) is able to utilize various hydrocarbon fuels. Whereas, the classical Ni anode suffers severe carbon deposition especially operated under CH₄. Strontium titanate (SrTiO₃) perovskite anodes with strong carbon deposition resistance and good structural stability have been extensively investigated. In this work, Sr_0.88Y_0.08-xYb_xTiO₃ and Sr_0.88Y_0.08Ti_1-xYb_xO₃ are synthesized by Yb³⁺ doping in A-site and B-site of Sr_0.88Y_0.08TiO₃ perovskite, respectively. XRD results confirm that the SrTiO₃ cubic perovskite phase is formed in all the samples. Among the Yb³⁺ doping samples, Sr_0.88Y_0.06Yb_0.02TiO₃ exhibits the lowest thermal expansion coefficient (11.48 × 10⁻⁶/K), indicating the best compatibility with the electrolyte. The ionic conductivity of Sr_0.88Y_0.08TiO₃ can be improved by proper Yb³⁺ doping both in A-site and B-site, and the Sr_0.88Y_0.06Yb_0.02TiO₃ sample has the highest ionic conductivity among all the samples. The maximum power density of SOFC with Sr_0.88Y_0.06Yb_0.02TiO₃ anode is 87 mW/cm² under CH₄ at 800 °C, which is much higher than that with Sr_0.88Y_0.08TiO₃ and Ni anode. This can be related to its high electrocatalytic activity to CH₄ oxidation. In addition, SOFC with the Sr_0.88Y_0.06Yb_0.02TiO₃ anode shows a superior stability operated under CH₄ due to the strong carbon deposition resistances.     

Thermodynamic analysis of ammonia fed solid oxide fuel cells: Comparison between proton-conducting electrolyte and oxygen ion-conducting electrolyte

A thermodynamic analysis has been performed to compare the theoretical performance of ammonia fed solid oxide fuel cells (SOFCs) based on proton-conducting electrolyte (SOFC-H) and oxygen ion-conducting electrolyte (SOFC-O). It is found that the ammonia fed SOFC-H is superior to SOFC-O in terms of theoretical maximum efficiency. For example, at a fuel utilization of 80% and an oxygen utilization of 20%, the efficiency of ammonia fed SOFC-H is 11% higher than that of SOFC-O. The difference between SOFC-H and SOFC-O becomes more significant at higher fuel utilizations and higher temperatures. This is because an SOFC-H has a higher hydrogen partial pressure and a lower steam partial pressure than an SOFC-O. In addition, an increase in oxygen utilization is found to increase the efficiency of ammonia fed SOFCs due to an increase in oxygen molar fraction and a reduction in steam molar fraction. With further development of new ceramics with high proton conductivity and effective fabrication of thin film electrolyte, the SOFC based on proton-conducting electrolyte is expected to be a promising approach to convert ammonia fuel into electricity.     

Advanced perovskite anodes for solid oxide fuel cells: A review

Solid oxide fuel cells (SOFCs) are at the frontline of clean energy generation technologies to convert chemical energy to electricity with high efficiency. In recent years, because of their fuel flexibility, multiple fuels are fed in anode, e.g., hydrogen, ammonia, hydrocarbons, solid carbon, etc.; in addition, these fuels are always mixed with a certain amount of H₂S. Perovskite is one of the most important classes of anode materials being investigated in laboratories, these materials to some extent are immune to coke formation and sulfur poisoning when using hydrocarbon fuels, and retain inherent stability upon reduction and oxidation cycling. In this review, recent developments in perovskite anode materials are summarized and future prospects are discussed.     

Nanoscale bismuth oxide impregnated (La,Sr)MnO3 cathodes for intermediate-temperature solid oxide fuel cells

Bismuth oxide based oxygen ion conductors are incorporated into (La,Sr)MnO₃ (LSM), the classical cathode material for solid oxide fuel cells (SOFC), to improve the cathode performance. Yttria-stabilized bismuth oxide (YSB) is taken as an example and is impregnated into a preformed porous LSM frame, forming a highly active cathode for intermediate-temperature SOFCs (IT-SOFCs) with doped ceria electrolytes. X-ray diffraction indicates that YSB is chemically compatible with LSM at intermediate temperatures below 800 °C. The impregnated YSB particles are nanosized and are deposited on the surface of the framework. Significant performance improvement is achieved by introducing nanosized YSB into the LSM electrodes. At 600 °C, the interfacial polarization resistance under open-circuit conditions for electrodes impregnated with 50% YSB is only 1.3% of the original value for a pure LSM electrode. The resistance is further reduced dramatically when current is passed through. In addition, the YSB impregnated LSM electrodes has the highest electrochemical performance among those based on LSM. Single cell with 25% of YSB impregnated LSM cathode generates maximum power density of 300 mW cm⁻² at 600 °C, indicating the promise of using LSM-based electrodes for IT-SOFC.     

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 modeling of direct internal reforming solid oxide fuel cells operating with syngas

In this paper a direct internal reforming solid oxide fuel cell (DIR-SOFC) is modeled thermodynamically from the energy point of view. Syngas produced from a gasification process is selected as a fuel for the SOFC. The modeling consists of several steps. First, equilibrium gas composition at the fuel channel exit is derived in terms mass flow rate of fuel inlet, fuel utilization ratio, recirculation ratio and extents of steam reforming and water–gas shift reaction. Second, air utilization ratio is determined according to the cooling necessity of the cell. Finally, terminal voltage, power output and electrical efficiency of the cell are calculated. Then, the model is validated with experimental data taken from the literature. The methodology proposed is applied to an intermediate temperature, anode-supported planar SOFC operating with a typical gas produced from a pyrolysis process. For parametric analysis, the effects of recirculation ratio and fuel utilization ratio are investigated. The results show that recirculation ratio does not have a significant effect for low current density conditions. At higher current densities, increasing the recirculation ratio decreases the power output and electrical efficiency of the cell. The results also show that the selection of the fuel utilization ratio is very critical. High fuel utilization ratio conditions result in low power output and air utilization ratio but higher electrical efficiency of the cell.