Anode-supported micro tubular SOFCs for advanced ceramic reactor system

In this study, micro tubular SOFCs under 1 mm diameter have been fabricated and investigated at 450–550 °C operating temperature with H₂ fuel. The performance of the 0.8 mm diameter tubular SOFC was 110–350 mW cm⁻² at 450–550 °C operating temperatures. To maximize the performance of the cell as well as to optimize the geometry of tubular cells, a current collecting method used in the experiment was examined. A model was proposed to estimate the loss of performance for single cell due to the current collecting method as functions of anode tube length and thickness. The results showed that the losses of performance were calculated to be 0.8, 2.0, and 4.6% at 450, 500, and 550 °C operating temperatures, respectively, for the 0.8 mm diameter tubular SOFC with the length of 1.2 cm.     

Cube-type micro SOFC stacks using sub-millimeter tubular SOFCs

Fabrication and characterization of tubular SOFCs under sub-millimeter (0.8 mm), bundles and stacks for low temperature operation were shown. The materials used in this study were Gd doped CeO₂ (GDC) for electrolyte, NiO–GDC for anode and (La, Sr)(Co, Fe)O₃ (LSCF)–GDC for cathode, respectively, and LSCF for supports of the tubular cells for bundle fabrication. After applying a sealing layer and current collector for each bundle of five micro tubular SOFCs, each bundle was stacked vertically, to build a four-storey cube-type stack with volume of about 0.8 cm³. The performance of the stack was shown to be 3.6 V OCV and 2 W maximum output power under 500 °C operating temperature. Preliminary quick start-up test was also conducted at the condition of 3 min start-up time from 150 to 400 °C for 5 times, and the results showed no degradation of the performance during the test.     

Fabrication and characterization of components for cube shaped micro tubular SOFC bundle

Solid oxide fuel cells (SOFCs) have the highest energy efficiency among various power generators. However, SOFCs generally have problems regarding to heat stress due to the heating cycle during cell operation, especially quick start-up/shut-down and the size of SOFC systems, which limit their application use. Micro tubular SOFCs are expected to be a solution to these problems because they are considered to be robust for repeated cycling under rapid changes in cell operating temperatures. If highly dense micro tubular SOFC stacks become available, it will accelerate development of SOFC systems, as well as increase a variety of applications. Our study aims to fabricate compact and high power SOFC bundles, which are composed of tubular SOFCs with the diameter of sub-millimeters. In this study, as the first stage of the development, processing technologies of tubular SOFCs and cube shaped cathode matrices were examined. Micro tubular SOFCs were fabricated using extrusion and co-firing techniques. The tubular SOFCs were then, arranged in the cathode matrices, which were piled up to be a cube shaped bundle. Each component of the cube shaped micro tubular SOFC bundle (cube) will be discussed in detail.     

Modeling and control of tubular solid-oxide fuel cell systems. I: Physical models and linear model reduction

This paper describes the development of a transient model of an anode-supported, tubular solid-oxide fuel cell (SOFC). Physically based conservation equations predict the coupled effects of fuel channel flow, porous-media transport, heat transfer, thermal chemistry, and electrochemistry on cell performance. The model outputs include spatial and temporal profiles of chemical composition, temperature, velocity, and current density. Mathematically the model forms a system of differential-algebraic equations (DAEs), which is solved computationally. The model is designed with process-control applications in mind, although it can certainly be applied more widely. Although the physical model is computationally efficient, it is still too costly for incorporation directly into real-time process control. Therefore, system-identification techniques are used to develop reduced-order, locally linear models that can be incorporated directly into advanced control methodologies, such as model predictive control (MPC). The paper illustrates the physical model and the reduced-order linear state-space model with examples.     

Performance comparison of planar,tubular and Delta8 solid oxide fuel cells using a generalized finite volume model

A generalized, finite volume-based SOFC model is presented which includes charge, mass and heat transport as well as a Langmuir–Hinshelwood type applied kinetic model for steam reforming reactions. The model development aimed at fast applicability to various cell geometries, short calculation times to allow for system analysis calculations and high fuel flexibility. In the first part of the paper, the model approach and assumptions are presented in detail. In the second part, the generalized model is applied to a planar, the standard tubular and the triangular tube cell geometry. The validation against experimental and benchmark test data is stressed to assure comparability of the model results for the three investigated cell designs. In the last part, the three cell designs are compared, highlighting the differences with respect to internal heat- and mass transfer and the impact on the electrochemical performance. It is shown that the performance of the triangular tube cell is almost double that of the standard tubular cell designs. The planar cell is outperformed by the triangular tube cell as well.     

A simple analysis of current collection in tubular solid oxide fuel cells

A transmission line analysis is presented for the axial current collection in tubular solid oxide fuel cells (SOFC). Closed form analytical solutions are obtained for two modes of current collection: (1) Current collection at one end. (2) Current collection across opposite ends. The analysis shows that cell resistance is lower for current collection at one end compared to that at the opposite ends, with the best case scenario being current collection at both ends. In addition, the analysis shows that for the case of tubular cells, performance may not indefinitely increase with increasing temperature. Experimental data are presented on planar and tubular cells that demonstrate significant differences in temperature dependence. It is projected that under certain conditions, performance of tubular cells may actually decrease with increasing temperature. A design of tubular cells with spines which can substantially lower current collection losses is described.     

Mass transfer in hydrogen-fed anode-supported SOFCs

A comprehensive numerical study of the mass-transfer mechanisms inside the anode of a hydrogen-fed Solid-Oxide Fuel-Cell (SOFC) is presented. The study is based on a detailed mathematical model of the channel and anode, using for the latter the equations of the Dusty Gas Model (DGM) to describe mass transfer in the porous medium.     

Development of cube-type SOFC stacks using anode-supported tubular cells

Tubular SOFCs have shown many desirable characteristics such as high thermal stability during rapid heat cycling and large electrode area per unit volume, which can accelerate to realize SOFC systems applicable to portable devices and auxiliary power units for automobile. So far, we have developed anode-supported tubular SOFCs with 0.8–2 mm diameter using Gd-doped CeO₂ (GDC) electrolyte, NiO-GDC anode and (La, Sr)(Co, Fe)O₃ (LSCF)-GDC cathode. In this study, a newly developed cube-type SOFC stack which consists of three SOFC bundles was designed and examined. The bundle consists of three 2 mm diameter tubular SOFCs and a rectangular shaped cathode support where these tubular cells are arranged in parallel. The performance of the stack whose volume is less than 1 cm³ was shown to be 2.8 V OCV and over 1 W at 1.6 V under 500 °C. Cathode loss factor due to current collection from cathode matrix was also estimated using a proposed model.     

Modeling and control of tubular solid-oxide fuel cell systems: II. Nonlinear model reduction and model predictive control

This paper describes a systematic method for developing model-based controllers for solid-oxide fuel cell (SOFC) systems. To enhance the system efficiency and to avoid possible damages, the system must be controlled within specific operating conditions, while satisfying a load requirement. Model predictive control (MPC) is a natural choice for control implementation. However, to implement MPC, a low-order model is needed that captures the dominant dynamic behavior over the operating range. A linear parameter varying (LPV) model structure is developed and applied to obtain a control-oriented dynamic model of the SOFC stack. This approach effectively reduces a detailed physical model to a form that is compatible with MPC. The LPV structure includes nonlinear scheduling functions that blend the dynamics of locally linear models to represent nonlinear dynamic behavior over large operating ranges. Alternative scheduling variables are evaluated, with cell current being shown to be an appropriate choice. Using the reduced-order model, an MPC controller is designed that can respond to the load requirement over a wide range of operation changes while maintaining input-output variables within specified constraints. To validate the approach, the LPV-based MPC controller is applied to the high-order physical model.     

Numerical analysis of start-up operation of a tubular solid oxide fuel cell

The purpose of the current study is to numerically predict the start up behavior of a tubular solid oxide fuel cell (SOFC) using a 2-D transient model. The developed model provides the transient response of the start-up mode as well as the steady state operation of the SOFC. A code based on finite volume method is utilized to solve the transient nonlinear transport equations of the cell (momentum, species and energy equations). To account for the Ohmic losses and Joule heating of the current that passes through the cell body, a discretized network circuit is adopted. The local electrochemical parameters are calculated based on the local pressure, temperature, and concentrations of the species. At each time step an iterative procedure is used to solve the electrochemical, electrical and transport equations simultaneously. The model predicts the cell output voltage, the local EMF and the state variables (pressure, temperature and species concentration) during the start up. It also predicts the cell heat-up rate for hot input gases as well as the start up time of the SOFC. The results show that the gases mass flow rate and temperature affect the heat-up rate. Also during the start-up, the cell electrical response is about 2.5 times quicker than the cell temperature response. The start-up time for the cell output voltage is about 50 min.     

Radiative and convective heat transport within tubular solid-oxide fuel-cell stacks

This paper develops a relatively simple model that is intended to rapidly evaluate design configuration and operating conditions for tubular anode-supported solid-oxide fuel-cell (SOFC) stacks. Heat is removed from the SOFC tubes by a combination of convection and radiation. Heat is convected to air that circulates outside the SOFC tubes and radiated to a surrounding cylindrical wall. The tubes are assumed to be arranged in hexagonal arrays in which the distance between tubes centers form equilateral triangles. The paper presents new configuration-factor formulas that are needed to represent arrays of staggered cylinders. The configuration factors are derived for long cylinders using the crossed-string method. These configuration factors have general utility beyond the application to fuel-cell systems. The model is applied to a particular cell and stack system and used to evaluate the effects of a range of design and operating conditions.     

Stability and robustness of metal-supported SOFCs

Tubular metal-supported SOFCs with YSZ electrolyte and electrodes comprising porous YSZ backbone and infiltrated Ni and LSM catalysts are operated at 700 °C. Tolerance to five complete anode redox cycles and five very rapid thermal cycles is demonstrated. The power output of a cell with as-infiltrated Ni anode degrades rapidly over 15 h operation. This degradation can be attributed primarily to coarsening of the fine infiltrated Ni particles. A cell in which the infiltrated Ni anode is precoarsened at 800 °C before operation at 700 °C shows dramatically improved stability. Stable operation over 350 h is demonstrated.     

Performance comparison between partial oxidation and methane steam reforming processes for solid oxide fuel cell (SOFC) micro combined heat and power (CHP) system

The aim of this research work is to describe in qualitative and quantitative form the performance of a micro Combined Heat and Power system for residential application based on Solid Oxide Fuel Cell fueled by natural gas with two different types of pre-reforming systems, namely Steam Reforming and Partial Oxidation and recirculation of anode and cathode gas.The comparative analysis among the different configurations will lead us to conclude that maximum efficiency is achieved when cathode and anode gas recirculation are used along with steam methane reforming. Further Steam Methane Reforming process produces a higher electrical system efficiency compared to Partial oxidation reforming process.Efficiency is affected when running the system in part load mode mainly due to heat loss, additional natural gas supplied to the burner to satisfy the required heat demand inside the system, and ejector efficiency drop in the recirculation system. Due to high temperature of operation heat loss strongly affects the system efficiency especially at part load operation.     

A novel design and performance of cone-shaped tubular anode-supported segmented-in-series solid oxide fuel cell stack

A novel design of cone-shaped tubular segmented-in-series solid oxide fuel cell (SOFC) stack is presented in this paper. The cone-shaped tubular anode substrates are fabricated by slip casting technique and the yttria-stabilized zirconia (YSZ) electrolyte films are deposited onto the anode tubes by dip coating method. After sintering at 1400 °C for 4 h, a dense and crack-free YSZ film with a thickness of about 7 μm is successfully obtained. The single cell, NiO-YSZ/YSZ (7 μm)/LSM-YSZ, provides a maximum power density of 1.78 W cm⁻² at 800 °C, using moist hydrogen (75 ml min⁻¹) as fuel and ambient air as oxidant.A two-cell-stack based on the above-mentioned cone-shaped tubular anode-supported SOFC is fabricated. Its typical operating characteristics are investigated, particularly with respect to the thermal cycling test. The results show that the two-cell-stack has good thermo-mechanical properties and that the developed segmented-in-series SOFC stack is highly promising for portable applications.     

Characterization of a novel, highly integrated tubular solid oxide fuel cell system using high-fidelity simulation tools

A novel, highly integrated tubular SOFC system intended for small-scale power is characterized through a series of sensitivity analyses and parametric studies using a previously developed high-fidelity simulation tool. The high-fidelity tubular SOFC system modeling tool is utilized to simulate system-wide performance and capture the thermofluidic coupling between system components. Stack performance prediction is based on 66 anode-supported tubular cells individually evaluated with a 1-D electrochemical cell model coupled to a 3-D computational fluid dynamics model of the cell surroundings. Radiation is the dominate stack cooling mechanism accounting for 66-92% of total heat loss at the outer surface of all cells at baseline conditions. An average temperature difference of nearly 125 °C provides a large driving force for radiation heat transfer from the stack to the cylindrical enclosure surrounding the tube bundle. Consequently, cell power and voltage disparities within the stack are largely a function of the radiation view factor from an individual tube to the surrounding stack can wall. The cells which are connected in electrical series, vary in power from 7.6 to 10.8 W (with a standard deviation, σ = 1.2 W) and cell voltage varies from 0.52 to 0.73 V (with σ = 81 mV) at the simulation baseline conditions. It is observed that high cell voltage and power outputs directly correspond to tubular cells with the smallest radiation view factor to the enclosure wall, and vice versa for tubes exhibiting low performance. Results also reveal effective control variables and operating strategies along with an improved understanding of the effect that design modifications have on system performance. By decreasing the air flowrate into the system by 10%, the stack can wall temperature increases by about 6% which increases the minimum cell voltage to 0.62 V and reduces deviations in cell power and voltage by 31%. A low baseline fuel utilization is increased by decreasing the fuel flowrate and by increasing the stack current demand. Simulation results reveal fuel flow as a poor control variable because excessive tail-gas combustor temperatures limit fuel flow to below 110% of the baseline flowrate. Additionally, system efficiency becomes inversely proportional to fuel utilization over the practical fuel flow range. Stack current is found to be an effective control variable in this type of system because system efficiency becomes directly proportional to fuel utilization. Further, the integrated system acts to dampen temperature spikes when fuel utilization is altered by varying current demand. Radiation remains the dominate heat transfer mechanism within the stack even if stack surfaces are polished lowering emissivities to 0.2. Furthermore, the sensitivity studies point to an optimal system insulation thickness that balances the overall system volume and total conductive heat loss.     

Techno-economic comparison of anode-supported,cathode-supported,and electrolyte-supported SOFCs

Different types of self-supported SOFCs (i.e., anode-supported, cathode-supported and electrolyte-supported SOFCs) have been compared in literature mostly from technical point of view. In this study, the mentioned types of SOFCs are compared from technical and economic points of view simultaneously. In this regard, “maximum power density” and “material cost of PEN layer” are taken as objective functions. These functions are evaluated through numerical modeling and based on available cost data, respectively. The results illustrate that the cathode-supported SOFC is the optimal choice when power density is regarded alone. On the other hand, the electrolyte-supported SOFC is observed to be the optimal option when the material cost of PEN is considered as the only objective function. However, the anode-supported SOFC makes the best trade-off between the two objective functions when they are simultaneously taken into consideration. The results also indicate that the electrolyte-supported SOFC leads to a symmetrical and most uniform current density distribution as compared to the electrode-supported ones in which peak local current densities tend toward non-supporting side. The paper discusses in detail the reasoning for the mentioned observations.     

Comparative study on the performance of tubular and button cells with YSZ membrane fabricated by a refined particle suspension coating technique

Both tubular and button solid oxide fuel cells (SOFCs) with configuration NiO–YSZ/YSZ/PNSM–YSZ were assembled and compared in their performance. A refined particle suspension coating technique was used for preparing thin dense YSZ electrolyte layer on the two types of anode supports, and the thickness of YSZ membrane was controlled by the time of tubular anode dipped into YSZ suspension and the suspension volume dropped onto the button anode, respectively. Current–voltage tests and AC impedance measurements were carried out to characterize the performance and ohmic resistances in the two cells. Compared with tubular cell, higher peak power density values of 933 mW cm⁻² at 850 °C was achieved, which is 2.2 times higher than the value of tubular cell. AC impedance indicated that lower performance of tubular cell was restricted by the ohmic loss at the operating temperatures.     

Experimental study of dry reforming of biogas in a tubular anode-supported solid oxide fuel cell

The performance of a tubular Ni/YSZ anode supported SOFC directly fed by an anaerobic digestion simulated biogas, with an extra addition of carbon dioxide to operate in conservative operating conditions to avoid coking on the anode support, was investigated. The fuel cell has been tested at a fixed oven temperature of 800 °C and under biogas/CO₂ mixtures with different volumetric ratios, fuel utilization (FU) and current densities. Polarization curves and performance maps were obtained to better understand the influence of the investigated operational parameters on the cell behavior. Furthermore, since the tubular geometry enables an easy separation of the anode and cathode exhaust gases, the anode off-gas has been collected and monitored through a gas-chromatograph under open circuit voltage to investigate on the catalytic behavior of a Ni-based state-of-the-art anode. For corresponding operative conditions, performances of the cell for biogas/CO₂ 1/1.5 (i.e. CH₄/CO₂ 30/70) and 1/2 (i.e. CH₄/CO₂ 24/76) were at least 2% and 4% lower than the case 1/1 (i.e. CH₄/CO₂ 20/80), respectively. The highest efficiency of 43.4% was reached at 17.5 A and FU = 70%.     

A 2D transient numerical model combining heat/mass transport effects in a tubular solid oxide fuel cell

The purpose of this study is to present a 2D transient numerical model to predict the dynamic behavior of a tubular SOFC. In this model, the transient conservation equations (momentum, species and energy equations) are solved numerically and electrical and electrochemical outputs are calculated with an equivalent electrical circuit for the cell. The developed model determines the cell electrical and thermal responses to the variation of load current. Also it predicts the local EMF, state variables (pressure, temperature and species concentration) and cell performance for different cell load currents. Using this comprehensive model the dynamic behavior of Tubular SOFC is studied. First an initial steady state operating condition is set for the SOFC model and then the time response of the fuel cell to changes of some interested input parameters (like electrical load) is analyzed. The simulation starts when the cell is at the steady state in a specific output load. When the load step change takes place, the solution continues to reach to the new steady state condition. Then the cell transient behavior is analyzed. The results show that when the load current is stepped up, the output voltage decreases to a new steady state voltage in about 67 min.     

Comparison of heat and mass transfer between planar and MOLB-type SOFCs

A numerical simulation tool for calculating the planar and mono-block layer built (MOLB) type solid oxide fuel cells (SOFC) is described. The tool combines the commercial computational fluid dynamics simulation code with an electrochemical calculation subroutine. Its function is to simulate the heat and mass transfer and to predict the temperature distribution and mass fraction of gaseous species in the SOFC system. The three-dimensional geometry model of SOFC was designed to simulate a co-flow case and counter-flow case. The finite volume method was employed to calculate the conservation equations of mass, momentum and energy. Moreover, the influences of working conditions on the performances of planar and MOLB-type SOFCs were also discussed and compared, such as the delivery rate of gas and the components of fuel gas. Simulation results show that the MOLB-type SOFC has higher fuel utilization than the planar SOFC. For the co-flow case, average temperatures of PEN (positive electrode–electrolyte–negative electrode) in both types of SOFCs rise with the increase in delivery rate and mass fraction of hydrogen. In particular, the temperature of planar SOFC is more sensitive to the working conditions. In order to decrease the average temperatures in SOFC, it is effective to increase the delivery rate of air.