Start‐Up Characteristics of Segmented‐In‐Series Tubular SOFC Power Modules Improved by Catalytic Combustion at Cathodes

For large‐scale SOFC power generation systems, a shorter start‐up time of SOFC cell stacks with relatively large heat capacity is one of the most important technological issues to determine the flexibility in SOFC system operation. In this study, start‐up procedures have been examined to shorten the start‐up time period. The conventional heating procedure using pre‐heated hot air and self‐heating by SOFC operation at low temperatures had a difficulty to shorten the start‐up time period because of the limitation in power generation at lower temperatures. In this study, as an alternative start‐up procedure, catalytic combustion at the SOFC cathodes is, for the first time, demonstrated to be useful on the system level. The applicability of the catalytic combustion to shorten the start‐up time period has been verified numerically as well as experimentally by using a large‐scale cell stack cartridge. This unique start‐up procedure enables to operate SOFC‐based large‐scale power generation systems.     

SOFC Thermal Transients: Modeling by Application of Experimental System Identification Techniques

Solid oxide fuel cell (SOFC) is one of the most promising technologies for future power generation. In order to make this technology marketable, many issues as cost reduction, durability, and operational management have to be overcome. Therefore, the understanding of thermodynamic and electrochemical mechanisms, that govern the SOFC behavior in steady‐state and in transient operation, becomes fundamental. In this context, the modeling of fuel cell (FC) thermal transient is of great interest because it can predict the temperature time variation, useful to the dimensioning of auxiliary devices and to avoid unwanted operational states affecting cell durability. In the present study, a 0‐D model of SOFC thermal transients was developed by applying system identification techniques, starting from experimental tests carried out on a stack made up of four single cells. Moreover, it was successfully validated in reference to further experimental data. The model allows to evaluate, in term of dynamic response, the effect of the main operating parameters on FC temperature. As further result, some control/regulation considerations useful to limit thermal stresses were proposed.     

Analysis of a solid oxide fuel cell system for combined heat and power applications under non-nominal conditions

In this paper, a model for a solid oxide fuel cell (SOFC) system for decentralized electricity production is developed and studied. The proposed system, operated on natural gas, consists of a planar anode supported fuel cell section and a balance of plant (BoP) which includes gases supply, a fuel processor, a heat management system, an after-burner and a power conditioning system. A reference case is defined and evaluated taking into account the state of the art of the technology and the related technical constrains. Electrical and thermal efficiency of the system, for non-reference conditions are evaluated. In particular, the effect of the deviation from the reference conditions of fuel utilization, gas temperature spring in fuel cell stack, anode off-gas recirculation rate, air inlet temperature and external pre-reforming reaction extent is analyzed. The present study revealed to be a powerful tool for evaluating the SOFC system performance under a wide range of operation and paves the way for defining control strategies in order to maintain high system efficiency under part-load operations.     

Exergoeconomic Analysis of a Combined Ammonia Based Solid Oxide Fuel Cell System

An exergoeconomic study of an ammonia‐fed solid oxide fuel cell (SOFC) based combined system for transportation applications is presented in this paper. The relations between capital costs and thermodynamic losses for the system components are investigated. The exergoeconomic analysis includes the SOFC stack and system components, including the compressor, microturbine, pressure regulator, and heat exchangers. A parametric study is also conducted to investigate the system performance and costs of the components, depending on the operating temperature, exhaust temperature, and fuel utilization ratio. A parametric study is performed to show how the ratio of the thermodynamic loss rate to capital cost changes with operating parameters. For the devices and the overall system, some practical correlations are introduced to relate the capital cost and total exergy loss. The ratio of exergy consumption to capital cost is found to be strongly dependent on the current density and stack temperature, but less affected by the fuel utilization ratio.     

New Fabrication Technique for Series‐Connected Stack With Micro Tubular SOFCs

Solid oxide fuel cell (SOFC) is highly efficient and is a promising candidate for future power systems. Among the many types of SOFCs which have been reported, the micro tubular design offers improved thermal robustness, with the possibility of rapid start‐up/shut‐down. In this study, a new stack structure for anode‐supported micro tubular SOFCs was developed in which porous MgO matrices were used to position the micro tubular cell elements. This arrangement allowed for electrical interconnection of each cell in a series, using a silver paste and a connecting LSCF paste for the anode and the cathode, respectively, in the MgO support structure. With this technique, the bundle size could be easily increased towards the kW class module design.     

Power Generation from Biogas using SOFC – Results for a 1 kWe Demonstration Unit

A stand‐alone system for power generation from biogas‐based on a commercial SOFC module in the 1 kW_e range shall demonstrate its applicability to biogas, quantify the efficiency gain compared to conventional combined heat and power technology and justify further development toward SOFC modules in the hundreds of kilowatt range. The system includes biogas cleaning, combined dry and steam reforming, electrochemical oxidation of synthesis gas, offgas burning, and heat usage for steam generation and support of the endothermic reforming reaction. The system demonstrated a performance of 1 kW_e at 52% gross efficiency for a synthetic biogas containing 55 vol.% CH₄ during 500 h in the lab. In addition, the performance using real biogas derived from the wastewater treatment process of a sugar plant was demonstrated for different operating points. Based on the experimentally validated results, it is possible to predict the benefit of operating larger SOFC biogas systems. Investment costs of 2.5 times compared to the conventional technology of a 75 kW_e biogas unit get paid off due to higher electricity revenues over time.     

Stady‐state and Dynamical Simulation of an Autothermal Gasoline Reformer

Detailed numerical simulation is an important tool for the analysis, development and optimization of new reactor systems. In this contribution results of steady‐state and dynamic simulations of a hydrogen production system for mobile applications based on gasoline are presented. The system consists of an autothermal reformer, a high temperature shift reactor and a countercurrent heat exchanger for heat integration. The simulations are based on 1‐D, multiphase, dynamic models, which are solved with the simulation tool PDEX‐Pack. Firstly steady‐state and dynamic simulations of the autothermal reformer alone are presented. Concentration and temperature profiles in the reformer under different operation conditions are discussed and possibilities to improve the performance are assessed. Dynamic simulations of load change and cold start show the fast dynamic response of the reformer due to its low thermal mass. Simulations of the coupled system underline the impact of the heat exchanger design for the system performance, especially under dynamic conditions. Finally dynamic simulations of a possible cold start strategy for the system are discussed.     

Thermodynamics of Hydrogen Generation from Methane for Domestic Polymer Electrolyte Fuel Cell Systems

Low temperature fuel cells such as the Polymer Electrolyte Fuel Cell (PEFC) are preferably used for domestic applications because of their moderate operating conditions. Using the existing distribution system, natural gas is used as a source for a hydrogen rich gas to power this fuel cell type. The high requirements on the fuel gas quality as well as high conversion efficiencies for the small local gas processing units are critical aspects in the evaluation of decentralized fuel cell systems. In the present paper, three typical gas processing methods are evaluated for the supply of a hydrogen rich gas for PEFCs: steam reforming, partial oxidation, and autothermic conversion. All three processes are studied in detail by varying the relevant process parameters: temperature, pressure, steam to fuel ratio, and oxygen to fuel ratio. The results are graphically displayed in numerous nomograms. With the help of these graphs, regions of stable operation and the sensitivity to the operational parameters are discussed. For all three gas processing methods, the graphs generated display methane conversion, the hydrogen yield, and the yields of unwanted components, i.e., carbon monoxide and solid carbon. Although only steady‐state operating conditions were simulated, critical modes of operation, which might occur during start‐up or transient operation can easily be identified. For instance, operating conditions where soot is generated have to be avoided under all circumstances. All simulations were done with the Gibb's reactor model of a commercial simulation program. The Gibb's reactor model was found to be a suitable tool, since the simulated results compared well with reported literature data. According to the simulation results, the methane‐steam‐reforming process appears to be favorable for application to PEFCs. Methane conversion and hydrogen yields are highest for this process while the yield of CO is relatively low.     

Start‐Up of HT‐PEFC Systems Operating with Diesel and Kerosene for APU Applications

Fuel‐cell‐based auxiliary power units offer power generation with reduced fuel consumption and low emissions. A very promising system is the combination of an autothermal reformer with a high‐temperature polymer electrolyte fuel cell. A fast start‐up procedure is a crucial requirement for the use of this system as an auxiliary power unit. This paper reports on the development of a suitable start‐up strategy for a 10 kW_el auxiliary power unit with a start‐up burner. A commercially available diesel burner was tested as a start‐up device. A dynamic MATLAB/Simulink model was developed to analyze different start‐up strategies. With the currently available apparatus and start‐up burner it takes 2,260 s before power generation can begin according to simulation results. The fuel processor alone would be ready for operation after 1,000 s. An optimization of the fuel cell stack with regard to its thermal mass would lead to a start‐up time of 720 s. A reduction to 600 s is possible with a slight customization of the start‐up burner.     

Improved crack resistance and thermal conductivity of cubic zirconia containing graphene nanoplatelets

Composites of 8 mol.% yttria-stabilized zirconia (8YSZ) with graphene nanoplatelets (GNP) have been pointed as alternative interconnectors in SOFC due to their mixed ionic-electronic conduction. Here we show that GNP addition provides rising crack-resistance behavior, with long crack toughness up to 78% higher than that of 8YSZ, also improving its thermal conductivity (up to 6 times for the in-plane direction). Toughness versus crack length is measured for 7 and 11 vol.% of GNP using single edge V-notched beam technique and ultrashort pulsed laser notching; and thermal behavior is analyzed by the laser flash method. Materials also have highly anisotropic coefficient of thermal expansion. These properties contribute to enhance their performance under the harsh operating conditions of SOFC, as thermal residual stresses could be reduced while significantly improving the system mechanical stability. Moreover, the heat transfer may be enhanced especially along the interface direction which would increase the system efficiency.     

Temperature effects during practical operation of microfluidic chips

The temperature dependent fluorescence of Rhodamine B was used to investigate the temperature effect of several system parameters in a microfluidic chip. This was combined with computational fluid dynamics calculations. Limited air movement over the chip had no significant effect on the temperature of the fluid running through the chip. Also, fluid flow through the channels at had no effect on the chip temperature or heating and cooling dynamics. The temperature varied greatly over the length of the chip. During transient operation of the chip, the heat up and cool down rates varied over the chip, and were dependent on the distance to the heater. The thermal time constant for heat up was four to five times lower than for cool down. The results can be used as tools for operating a temperature controlled microfluidic chip.     

Direct Operation of IP‐Solid Oxide Fuel Cell with Hydrogen and Methane Fuel Mixtures under Current Load Cycle Operating Condition

The effects of methane concentration and current load cycle on the performance and durability of integrated planar solid oxide fuel cell (IP‐SOFC) obtained from Rolls Royce Fuel Cell Systems Ltd (RRFCS) has been investigated. The IP‐SOFC was operated with hydrogen–methane fuel mixture with up to 20% methane concentration at 900 °C for short term operation of the cells with high methane concentration increased the voltage of the IP‐SOFC due to increase in Gibbs free energy. However, it degraded the performance of the IP‐SOFC in long term operation due to carbon deposition on the anode surface. The current load cycle tests were carried out with 95% H₂–5% CH₄ and 80% H₂–20% CH₄ fuel mixtures at 900 °C with a constant current of 1 A. At low methane concentration, the decrease in the IP‐SOFC voltage was observed after operating nine current load cycles (384 h). At higher methane concentration, the voltage of IP‐SOFC decreased by almost 30% just after one current load cycle (48 h) due to faster carbon deposition. So future work is therefore required to identify viable alternative materials and optimum operating conditions.     

PBI‐Based Polymer Membranes for High Temperature Fuel Cells – Preparation,Characterization and Fuel Cell Demonstration

Proton exchange membrane fuel cell (PEMFC) technology based on perfluorosulfonic acid (PFSA) polymer membranes is briefly reviewed. The newest development in alternative polymer electrolytes for operation above 100 °C is summarized and discussed. As one of the successful approaches to high operational temperatures, the development and evaluation of acid doped polybenzimidazole (PBI) membranes are reviewed, covering polymer synthesis, membrane casting, acid doping, physicochemical characterization and fuel cell testing. A high temperature PEMFC system, operational at up to 200 °C based on phosphoric acid‐doped PBI membranes, is demonstrated. It requires little or no gas humidification and has a CO tolerance of up to several percent. The direct use of reformed hydrogen from a simple methanol reformer, without the need for any further CO removal, has been demonstrated. A lifetime of continuous operation, for over 5000 h at 150 °C, and shutdown‐restart thermal cycle testing for 47 cycles has been achieved. Other issues such as cooling, heat recovery, possible integration with fuel processing units, associated problems and further development are discussed.     

Thermodynamic Analysis of an Integrated SOFC,Solar ORC and Absorption Chiller for Tri‐generation Applications

Thermodynamic performance assessment of an integrated tri‐generation energy system for power, heating and cooling production is conducted through energy and exergy analyses. Sustainability assessment is performed and some parametric studies are undertaken to analyze the impact of system parameters and environmental conditions on the system performance. The tri–generation system consists of (a) an internal reforming tubular type solid oxide fuel cell (IR‐SOFC), which works at ambient pressure and fueled with syngas, (b) a combustor and a air heat exchanger, (c) a heat recovery and steam generation unit (HRSG), (d) a two‐ stage Organic Rankine cycle (ORC) driven by exhaust gases of SOFC, (e) parabolic trough solar collectors (PTSC), and (f) a lithium‐bromide absorption chiller (AC) cycle driven by exhaust gases from SOFC unit. The largest irreversibility occurs at the SOFC unit due to high temperature requirement for reactions. Fuel utilization factor, recirculation ratio, dead state conditions, and solar unit parameters have influential effects on the system efficiencies. Energy and exergy efficiencies of tri‐generation unit become 85.1% and 32.62%, respectively, for optimum SOFC stack and environmental conditions. The overall system energy and exergy efficiencies are 56.25% and 15.44% higher than that of conventional SOFC systems, respectively.     

Modelling and Performance Evaluation of Solid Oxide Fuel Cell for Building Integrated Co‐ and Polygeneration

Models of fuel cell based combined heat and power systems, used in building energy performance simulation codes, are often based on simple black or grey box models. To model a specific device, input data from experiments are often required for calibration. This paper presents an approach for the theoretical derivation of such data. A generic solid oxide fuel cell (SOFC) system model is described that is specifically developed for the evaluation of building integrated co‐ or polygeneration. First, a detailed computational cell model is developed for a planar SOFC and validated with available numerical and experimental data for intermediate and high temperature SOFCs with internal reforming (IT‐DIR and HT‐DIR). Results of sensitivity analyses on fuel utilisation and air excess ratio are given. Second, the cell model is extended to the stack model, considering stack pressure losses and the radiative heat transfer effect from the stack to the air flow. Third, two system designs based on the IT‐DIR and HT‐DIR SOFCs are modelled. Electric and CHP efficiencies are given for the two systems, as well as performance characteristics, to be used in simulations of building integrated co‐ and polygeneration systems.     

Experimental Investigations and Modeling of Direct Internal Reforming of Biogases in Tubular Solid Oxide Fuel Cells

Biogas‐fed Solid Oxide Fuel Cell (SOFC) systems can be considered as interesting integrated systems in the framework of distributed power generation. In particular, bio‐methane and bio‐hydrogen produced from anaerobic digestion of organic wastes represent renewable carbon‐neutral fuels for high efficiency electrochemical generators. With such non‐conventional mixtures fed to the anode of the SOFC, the interest lies in understanding the multi‐physics phenomena there occurring and optimizing the geometric and operation parameters of the SOFC, while avoiding operating and fuel conditions that can lead to or accelerate degradation processes. In this study, an anode‐supported (Ni‐YSZ) tubular SOFC was considered; the tubular geometry enables a relatively easy separation of the air and fuel reactants and it allows one to evaluate the temperature field of the fuel gas inside the tube, which is strictly related to the electrochemical and heterogeneous chemical reactions occurring within the anode volume. The experiments have been designed to analyze the behavior of the cell under different load and fuel utilization (FU) conditions, providing efficiency maps for both fuels. The experimental results were used to validate a multi‐physics model of the tubular cell. The model showed to be in good agreement with the experimental data, and was used to study the sensitive of some selected geometrical parameters modification over the cell performances.     

Effect of Creep of Ferritic Interconnect on Long‐Term Performance of Solid Oxide Fuel Cell Stacks

High‐temperature ferritic alloys are potential candidates as interconnect (IC) materials and spacers due to their low cost and coefficient of thermal expansion (CTE) compatibility with other components for most of the solid oxide fuel cells (SOFCs). However, creep deformation becomes relevant for a material when the operating temperature exceeds or even is less than half of its melting temperature (in degrees of Kelvin). The operating temperatures for most of the SOFCs under development are around 1,073 K. With around 1,800 K of the melting temperature for most stainless steel (SS), possible creep deformation of ferritic IC under the typical cell operating temperature should not be neglected. In this paper, the effects of IC creep behaviour on stack geometry change and the stress redistribution of different cell components are predicted and summarised. The goal of the study is to investigate the performance of the fuel cell stack by obtaining the changes in fuel‐ and air‐channel geometry due to creep of the ferritic SS IC, therefore indicating possible changes in SOFC performance under long‐term operations. The ferritic IC creep model was incorporated into software SOFC‐MP and Mentat‐FC, and finite element analyses (FEAs) were performed to quantify the deformed configuration of the SOFC stack under the long‐term steady‐state operating temperature. It was found that the creep behaviour of the ferritic SS IC contributes to narrowing of both the fuel‐ and the air‐flow channels. In addition, stress re‐distribution of the cell components suggests the need for a compliant sealing material that also relaxes at operating temperature.     

Steady-state multiplicity in a solid oxide fuel cell: Practical considerations

Steady-state multiplicity in a solid oxide fuel cell (SOFC) in three modes of operation, constant ohmic external load, potentiostatic and galvanostatic, is studied using a detailed first-principles lumped model. The SOFC model is derived by accounting for heat and mass transfer as well as electrochemical processes taking place inside the fuel cell. Conditions under which the fuel cell exhibits steady state multiplicity are determined. The effects of operating conditions such as convection heat transfer coefficient and inlet fuel and air temperatures and velocities on the steady state multiplicity regions are studied. Depending on the operating conditions, the cell exhibits one or three steady states. For example, it has three steady states: (a) at low external load resistance values in constant ohmic external load operation and (b) at low cell voltage in potentiostatic operation.     

Effect of methane slippage on an indirect internal reforming solid oxide fuel cell

Creation of an autothermal system by coupling an endothermic to an exothermic reaction demands matching the thermal requirements of the two reactions. The application studied here is the operation of a solid oxide fuel cell (SOFC) with both direct (DIR) and indirect (IIR) internal reforming of methane. Such internal reforming within a high-temperature fuel cell module can lead to an overall autothermal operation which simplifies the system design and increases efficiency. However, such coupling is not easy to achieve because of the mismatch between the thermal load associated with the rate of steam reforming at typical SOFC temperatures and the local amount of heat available from the fuel cell reactions. Previous results have shown that the use of typical metal-based (e.g. Ni) IIR catalysts leads to full methane consumption but undesirable local cooling at the reformer entrance and the use of less active IIR catalysts (e.g. non-metals or diffusion limited nickel) leads to methane being carried-over into the SOFC anode (methane slippage). In order to evaluate performance in the latter case, a combined DIR and IIR SOFC steady-state model has been developed. Simulation results have shown that, lowering the IIR catalyst activity to prevent local cooling effects at the reformer entrance is not adequate, as the fast kinetics of the direct reforming reaction then lead to full methane conversion and steep temperature gradients in the first 10% of the fuel channel length. It is shown that the simultaneous reduction of the anode DIR reaction rate improves performance considerably. The system behaviour towards changes in current density, operating pressure, and flow configuration (counter-flow vs. co-flow) has been studied. Reduction of both DIR and IIR catalyst activity combined with a counter-flow operation leads to the best performance. System performance with an IIR oxide-based catalyst is also evaluated.     

Investigation of Impactors on Cell Degradation Inside Planar SOFC Stacks

The impactors on cell degradation inside planar SOFC stacks were investigated using both coated and uncoated Fe–16Cr alloys as the interconnects under stable operating conditions at 750 °C and thermal cycling conditions from 750 to 200 °C. It was found that cell degradation inside the stack is primarily dependent on the interfacial contact between the cathode current‐collecting layer and the interconnect. Additionally, cell degradation is found to be independent of the high‐temperature oxidation and Cr vaporization of the interconnects during stack operation, as the stacks are well sealed. The coating on the interconnect can further improve the contact between the cell cathode and the interconnect when the latter is properly embedded into the current‐collecting layer.