Microtubular SOFC anode optimisation for direct use on methane

The main problems of small-scale solid oxide fuel cell (SOFC) devices are the rapid start-up, durability and operation on available fuels such as methane. This paper describes how microtubular anode-supported SOFCs can be started rapidly and run on methane. However, the key factor was the activity of the nickel anode, especially its surface area and conductivity, which were found to depend on the reduction method and the operating fuel. Controlled reduction experiments in hydrogen at temperatures between 650 and 850 °C were performed. Reduction temperature and gas composition were altered and the resultant electrical performance and exhaust gases recorded. The conclusion was that microtubular SOFC can be successfully run on methane to outperform pure hydrogen by up to 9%.     

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.     

Reactions of low and middle concentration dry methane over Ni/YSZ anode of solid oxide fuel cell

Directly using methane in solid oxide fuel cells (SOFC) requires the knowledge of the reaction of methane over the anode. The reactions of low and middle concentration dry methane were studied over the anode of solid oxide fuel cell with Ni/yttria-stabilized zirconia (YSZ) anode and YSZ electrolyte. The production rates of different types of gas at anode outlet were measured at different current density. Mass balance and relationships between production rates and reaction rates were used to analyze the chemical and electrochemical reactions that took place in parallel. When dry methane is in low concentration, methane decomposition and deposited carbon oxidation occurs at low current density with the overall reaction being partial oxidation of methane (POM). With increased current density, hydrogen oxidation and carbon monoxide oxidizing to carbon dioxide take place simultaneously, and the overall reaction becomes the direct oxidation of methane (DOM). When DOM occurs, a portion of methane participates the POM. However, the rate of POM decreases with increased current density. At medium methane concentration, only partial oxidation of methane takes place. Carbon deposition was found in all the tests across the concentration range investigated.     

Anti-carbon deposition mechanism of H2O on nickel-based anode of SOFC: A ReaxFF molecular modelling

Carbon deposition occurs when Dimethyl ether (DME) fuel is used for SOFC, leading to battery degradation. In order to study the effect of water addition on carbon deposition, this work used reactive force field molecular dynamics (Reaxff MD) to simulate the process of carbon deposition with or without water addition, and analyze its anti-carbon deposition mechanism on nickel-based anode.It is found that the number of carbon atoms on nickel can be effectively reduced by mixing water with fuel. As the H₂O/DME ratio increases, there are fewer carbon atoms on the nickel anode. And there are two main ways for water molecules to resist carbon deposition. First is that the OH group generated by decomposition of water molecules at high temperature reacts with CH component to form aldehyde group, which reduces the formation of carbon deposition precursor. The other is that the increase of water molecules introduces more oxygen atoms into the system, and the carbon atoms formed by DME molecules combine with oxygen atoms to form CO, thus reducing carbon deposition. This study is helpful to promote the industrialization of DME as SOFC fuel.     

Numerical modelling of methane-powered micro-tubular, single-chamber solid oxide fuel cell

An experimentally validated, two-dimensional, axisymmetric, numerical model of micro-tubular, single-chamber solid oxide fuel cell (MT-SC-SOFC) has been developed. The model incorporates methane full combustion, steam reforming, dry reforming and water-gas shift reaction followed by electrochemical oxidation of produced hydrogen within the anode. On the cathode side, parasitic combustion of methane along with the electrochemical oxygen reduction is implemented. The results show that the poor performance of single-chamber SOFC as compared to the conventional (dual-chamber) SOFC (in case of micro-tubes) is due to the mass transport limitation on the anode side. The gas velocity inside the micro-tube is far too low when compared to the gas-chamber inlet velocity. The electronic current density is also non-uniform over the cell length, mainly due to the short length of the anode current collector located at the cell outlet. Furthermore, the higher temperature near the cell edges is due to the methane combustion (very close to the cell inlet) and current collection point (at the cell outlet). Both of these locations could be sensitive to the silver current collecting wire as silver may rupture due to cell overheating.     

A new phenomenon of a fuel-free current during intermittent fuel flow over Ni-YSZ anode in direct methane SOFCs

A solid oxide fuel cell (SOFC) test unit was constructed with YSZ electrolyte as the support, and with Ni-YSZ anode (Ni:YSZ = 3:5 in weight) and Pt cathode. Direct methane SOFC operation at 800 °C with 10% CH₄ in argon was carried out. A new phenomenon of the generation of the electrical current without the fuel was observed and termed the fuel-free current. An operation of intermittent methane supply was designed to take advantage of three driving forces, i.e. methane in the gas phase, the deposited carbon at the anode surface, and a deficiency of the bulk lattice-oxygen concentration on the anode side, for the generation of the electrical current. A continuous generation of the electrical current is obtained with a methane pulse of only one-fifth of the total operation time. The operation of intermittent methane flow can reduce or even avoid SOFC deactivation by the carbon deposition; at the same time, the deposited carbon can be fully utilized for the power generation. It was also found that hydrogen from methane has been mostly evolved to the outlet gaseous product and the amount of CO formation is much higher than that of CO₂; the operation of intermittent methane flow can further increase the amount of CO over that of CO₂; these are beneficial for the co-generation of synthesis gas.     

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.     

High performance of direct methane-fuelled solid oxide fuel cell with samarium modified nickel-based anode

Natural gas is one of the most attractive fuels for solid oxide fuel cell (SOFC), while the anode activity for methane fuel has a great influence on the performance and stability of SOFC. Samarium is a good catalyst promoter for methane reforming. In this work, samarium is used to modify nickel catalyst, which results in small nickel oxide particles. The SmNi-YSZ (yttria-stabilized zirconia) anode has smaller particles and better interfacial contact between nickel and YSZ compared with conventional Ni-YSZ anode. The fine structure of SmNi-YSZ anode results in high activity for electrochemical oxidation of hydrogen and low polarization resistance of the cell. The performance of SmNi-YSZ anode cell with humidified methane as fuel is greatly improved, which is similar to that with hydrogen as fuel. The maximum power densities of SmNi-YSZ anode cell are 1.56 W cm⁻² for humidified hydrogen fuel and 1.54 W cm⁻² for humidified methane fuel at 800 °C. The maximum power density is increased by 221% when samarium is used to modify Ni-YSZ anode for humidified methane fuel at 650 °C. High cell performance results in good stability of SmNi-YSZ anode cell and the cell runs stably for more than 600 min for humidified methane fuel.     

Characterisation of electrical performance of anode supported micro-tubular solid oxide fuel cell with methane fuel

The reduction and operation of Ni–YSZ anode-supported tubular cells on methane fuel is described. Cells were reduced on pure methane from 650 °C to 850 °C, varying reduction time and methane flow rate. The effect on electrochemical performance with methane fuel was then investigated at 850 °C after which temperature-programmed oxidation (TPO) was employed to measure carbon deposition. Results showed that carbon deposition was minimized after certain reduction conditions. The conclusion was that 30 min reduction at 650 °C with 10 ml min⁻¹ methane reduction flow rate led to the highest current output over 1.2 A cm⁻² at 0.5 V when the cell operated at 850 °C between 10 ml min⁻¹ and 12.5 ml min⁻¹ methane running flow rate. From these results, it is evident that solid oxide fuel cell (SOFC) performance can be substantially improved by optimising preparation, reduction and operating conditions without the need for hydrogen.     

Simulation of SOFC performance using a modified exchange current density for pre-reformed methane-based fuels

Numerical simulations can be used to visualize and better understand various distributions such as gas concentration and temperature in solid oxide fuel cells (SOFCs) under realistic operating conditions. However, pre-existing models generally utilize an anode exchange current density equation which is valid for humidified hydrogen fuels – an unrealistic case for SOFCs, which are generally fueled by hydrocarbons. Here, we focus on developing a new, modified exchange current density equation, leading to an improved numerical analysis model for SOFC anode kinetics. As such, we experimentally determine the exchange current density of SOFC anodes fueled by fully pre-reformed methane. The results are used to derive a new phenomenological anode exchange current density equation. This modified equation is then combined with computational fluid dynamics (CFD) to simulate the performance parameters of a three-dimensional electrolyte-supported SOFC. The new modified exchange current density equation for methane-based fuels reproduces the I–V characteristics and temperature distribution significantly better than the previous models using humidified hydrogen fuel. Better simulations of SOFC performance under realistic operating conditions are crucial for the prediction and prevention of e.g. fuel starvation and thermal stresses.     

Performance analysis of hollow fibre-based micro-tubular solid oxide fuel cell utilising methane fuel

Solid oxide fuel cell (SOFC) has been studied as one of the most amazing development in energy production that could work directly with hydrocarbon fuel without reforming procedure. This study was conducted to analyse the micro-tubular solid oxide fuel cell (MT-SOFC) in terms of its performance by utilising methane as the fuel, subsequently compared with hydrogen. MT-SOFC that was investigated in this work consisted of thin cathode layer, coated onto co-extruded anode/electrolyte dual-layer hollow fibre (HF); in which its anode was made of nickel (Ni), coupled with cerium-gadolinium oxide (CGO) as an electrolyte, whereas the cathode was lanthanum strontium cobalt ferrite (LSCF) and CGO. The physical analyses carried out were three-point bending test and scanning electron microscopy (SEM). X-ray diffraction (XRD) analysis was further conducted to examine the carbon deposition in HFs. In evaluating the performance of HFs, current-voltage (IV) measurement, as well as impedance analysis of various temperatures range from 500 °C to 700 °C were performed. Based on the results, the OCV, maximum power density and ohmic ASR of MT-SOFC exposed to methane fuel, were at 0.79 V, 0.22 W cm⁻² and 0.31 Ω cm²; compared to the other that was exposed to hydrogen fuel, recorded at 0.89 V, 0.67 W cm⁻² and 0.19 Ω cm² respectively. This indicates that there was a significant reduction in cell performance when methane was used as the fuel, due to the carbon deposition as proven by SEM, three-point bending and XRD.     

Investigation of aluminosilicate as a solid oxide fuel cell refractory

Aluminosilicate represents a potential low cost alternative to alumina for solid oxide fuel cell (SOFC) refractory applications. The objectives of this investigation are to study: (1) changes of aluminosilicate chemistry and morphology under SOFC conditions, (2) deposition of aluminosilicate vapors on yttria stabilized zirconia (YSZ) and nickel, and (3) effects of aluminosilicate vapors on SOFC electrochemical performance. Thermal treatment of aluminosilicate under high temperature SOFC conditions is shown to result in increased mullite concentrations at the surface due to diffusion of silicon from the bulk. Water vapor accelerates the rate of surface diffusion resulting in a more uniform distribution of silicon. The high temperature condensation of volatile gases released from aluminosilicate preferentially deposit on YSZ rather than nickel. Silicon vapor deposited on YSZ consists primarily of aluminum rich clusters enclosed in an amorphous siliceous layer. Increased concentrations of silicon are observed in enlarged grain boundaries indicating separation of YSZ grains by insulating glassy phase. The presence of aluminosilicate powder in the hot zone of a fuel line supplying humidified hydrogen to an SOFC anode impeded peak performance and accelerated degradation. Energy dispersive X-ray spectroscopy detected concentrations of silicon at the interface between the electrolyte and anode interlayer above impurity levels.     

Mini CHP based on the electrochemical generator and impeded fluidized bed reactor for methane steam reforming

The paper presents a configuration of mini CHP with the methane reformer and planar solid oxide fuel cell (SOFC) stacks. This mini CHP may produce electricity and superheated steam as well as preheat air and methane for the reformer along with cathode air used in the SOFC stack as an oxidant. Moreover, the mathematical model for this power plant has been created. The thermochemical reactor with impeded fluidized bed for autothermal steam reforming of methane (reformer) considered as the basis for the synthesis gas (syngas) production to fuel SOFC stacks has been studied experimentally as well. A fraction of conversion products has been oxidized by the air fed to the upper region of the impeded fluidized bed in order to carry out the endothermic methane steam reforming in a 1:3 ratio as well as to preheat products of these reactions. Studies have shown that syngas containing 55% of hydrogen could be produced by this reactor. Basic dimensions of the reactor as well as flow rates of air, water and methane for the conversion of methane have been adjusted through mathematical modelling.The paper provides heat balances for the reformer, SOFC stack and waste heat boiler (WHB) intended for generating superheated water steam along with preheating air and methane for the reformer as well as the preheated cathode air. The balances have formed the basis for calculating the following values: the useful product fraction in the reformer; fraction of hydrogen oxidized at SOFC anode; gross electric efficiency; anode temperature; exothermic effect of syngas hydrogen oxidation by air oxygen; excess entropy along with the Gibbs free energy change at standard conditions; electromotive force (EMF) of the fuel cell; specific flow rate of the equivalent fuel for producing electric and heat energy. Calculations have shown that the temperature of hydrogen oxidation products at SOFC anode is 850 °C; gross electric efficiency is 61.0%; EMF of one fuel cell is 0.985 V; fraction of hydrogen oxidized at SOFC anode is 64.6%; specific flow rate of the equivalent fuel for producing electric energy is 0.16 kg of eq.f./(kW·h) while that for heat generation amounts to 44.7 kg of eq.f./(GJ). All specific parameters are in agreement with the results of other studies.     

Fine interface contact and high activity of nickel-based anode modified by gadolinium for hydrogen and methane fuel

In this work, gadolinium is used to modify nickel catalyst, which can improve the properties of nickel oxide particle and inhibit its sintering and grain growth. Interface contact between nickel catalyst and YSZ is significantly improved and fine anode microstructure can be obtained when gadolinium is used to modify Ni-YSZ anode. Fine interface contact of GdNi-YSZ anode can accelerate charge transfer process and steam formation process, which leads to high activity for electrochemical oxidation of hydrogen and low impedance resistance. The remarkable characteristic of GdNi-YSZ anode cell is that the cell performance for humidified methane fuel is greatly improved due to the high anode activity for methane reforming and electrochemical oxidation of hydrogen. The maximum power density of GdNi-YSZ anode cell with humidified methane as fuel can reach 1.59 W/cm² at 800 °C and 0.46 W/cm² at 650 °C. High performance of GdNi-YSZ anode cell with humidified methane as fuel leads to much H₂O produced during the electrochemical oxidation process, which can depress carbon deposition and improve the cell stability for humidified methane fuel.     

3D modeling of anode-supported planar SOFC with internal reforming of methane

Deposition of carbon on conventional anode catalysts and formation of large temperature gradients along the cell are the main barriers for implementing internal reforming in solid oxide fuel cell (SOFC) systems. Mathematical modeling is an essential tool to evaluate the effectiveness of the strategies to overcome these problems. In the present work, a three-dimensional model for a planar internal reforming SOFC is developed. A co-flow system with no pre-reforming, methane fuel utilization of 75%, voltage of 0.7 V and current density of 0.65 A cm⁻² was used as the base case. The distributions of both temperature and gas composition through the gas channels and PEN (positive electrode/electrolyte/negative electrode) structure were studied using the developed model. The results identified the most susceptible areas for carbon formation and thermal stress according to the methane to steam ratio and temperature gradients, respectively. The effects of changing the inlet gas composition through recycling were also investigated. Recycling of the anode exhaust gas, at an optimum level of 60% for the conditions studied, has the potential to significantly decrease the temperature gradients and reduce the carbon formation at the anode, while maintaining a high current density.     

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.     

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.     

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.     

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.     

Steam reforming on Ni-samaria-doped ceria cermet anode for practical size solid oxide fuel cell at intermediate temperatures

Direct internal and external reforming operations on Ni-samaria-doped ceria (SDC) anode with the practical size solid oxide fuel cell (SOFC) at intermediate temperatures from 600 to 750 °C are carried out to reveal the reforming activities and the electrochemical activities, being compared with the hydrogen-fueled power generation. The cell performance with direct internal and external steam reforming of methane and their limiting current densities were almost the same irrespective of the progress of reaction in the methane reformate at 700 and 750 °C. The durability test for 5.5 h at 750 °C with direct internal reforming operation confirmed that the cell performance did not deteriorate. The operation temperature of the cell controlled the reforming activities on the anode, and the large size electrode gave rise to high conversion due to the slow space velocity of the steam reforming. Direct internal steam reforming attained sufficient level of conversion for SOFC power generation with methane at 700 and 750 °C on the large Ni-SDC cermet anode.