Direct Ethanol Anode-Supported Solid Oxide Fuel Cell

Long term durability was demonstrated on high-performance direct ethanol solid oxide fuel cell operating in gradual internal reforming. Anode supported single cells, fabricated at Forschungszentrum Jülich, composed of (La,Sr)MnO3 cathode, 8 mol% yttria-stabilized zirconia (YSZ) electrolyte, and YSZ-Ni anode were used for long term testing on anhydrous (direct) ethanol. Gadolinia-doped ceria (CGO), with 0.1 wt.% of Ir, catalyst was produced by the impregnation of Ir salt in commercial CGO (Praxair) and mixed with organic additives. The CGO-Ir suspension was deposited onto the surface of the YSZ-Ni anode support with an air brush. Such a catalytic layer acts both as a physical barrier to avoid direct contact of the fuel with Ni-based anode and to promote the gradual internal reforming of ethanol. The CGO-Ir catalyst was designed for the reforming of the main compounds resulting from the thermal decomposition of ethanol at high temperature and to inhibit the formation of ethylene, which is a known source of carbon deposits. After deposition the sample was heated at 850ºC in inert atmosphere to ensure good adhesion between the catalytic layer and the anode. Gold grid and paint were used as current collectors in both cathode and anode sides. The single fuel cells were mounted in the test apparatus, sealed with gold rings and alumina cement and heated to the measuring temperature (850°C) under inert atmosphere. After gas tightness was checked by flowing air on the cathode side and argon on the anode side, the anode was reduced under hydrogen. The fuel cell was kept at 0.6 V while monitoring the current drained from the cell at 850 °C. Samples were initially operated in hydrogen for a few hours and fuel was switched to dry ethanol, carried by nitrogen. It is important to mention that no oxidizing agent was added to the fuel and that water produced by the electrochemical reaction of hydrogen at the anode promoted the reforming of the ethanol in the CGO-based layer, in the so-called gradual internal reforming. In such conditions the current output was recorded and observed to not be significantly different form that under hydrogen. Moreover, the direct ethanol fuel cell was continuously operated for 650 hours without major losses due to carbon formation. The experimental results demonstrate that the water released by the electrochemical oxidation of reformate hydrogen at the electrolyte/anode active interfaces is sufficient for the reforming of the primary fuel in the catalytic layer, provided that a minimum fuel utilization is respected. After the durability tests, energy dispersive X-ray spectroscopy and scanning electron microscopy analyses of the samples revealed no carbon deposit formation in the anode. The experimental results provided compelling evidence for the viability of gradual internal reforming of ethanol in high performance solid oxide fuel cells.

Development and testing of anode-supported solid oxide fuel cells with slurry-coated electrolyte and cathode

Microtubular anode-supported solid oxide fuel cells (μt-SOFC) were created with a metallic coil embedded in the anode to act as current collector. The electrochemical performance was experimentally examined by comparing the power density (PD) of μt-SOFC with embedded coils of different turns per unit length and composition (nickel and palladium). It is shown that an increase in the turns per unit length results in a proportional current density increase and in a quadratic increment of PD. Additional performance improvement is found for the cell with palladium current collector due to the higher catalytic activity for hydrogen oxidation.

Anode-supported solid oxide fuel cells (SOFCs) offer the advantage of thinner electrolyte membranes which greatly reduce the ohmic loss and enables lower operating temperature and higher performance. However, a significant contribution to the polarization resistance is attributed to the anode, as the thickest component in the cell, which can influence the distribution of hydrogen partial pressure, p(H2) and water vapor pressure, p(H2O) especially when combined with current density to achieve high fuel utilization. To understand the degradation mechanism in long-term operation of a commonly used anode material, Ni/YSZ, commercial anode-supported cells were evaluated under varied current density (up to 1 A/cm2) and humidity (1-60%) using electrochemical impedance spectroscopy. The impedance spectra were analyzed using distribution of relaxation times (DRT) method to separate the resistance contribution from each component of the cell. The Ni/YSZ anode resistance was observed to increase with higher current density and humidity, suggesting that the degradation may be correlated to microstructural factors such as Ni agglomeration leading to reduced Ni interparticle contact, causing the increase in anode resistance. In addition, analysis using the 1-D transmission line model to determine the effective reaction length (ERL) of Ni/YSZ anode, revealed that the ERL moves further from the TPB with increasing degradation. Details of the post-test microstructural characterization of the cells will be discussed during the presentation.

In this chapter, the construction, principle of operation, types and production technologies of SOFCs are presented and characterized. Three main types of SOFC are described according to the type of support layer responsible for the mechanical strength of the cell: electrolyte-supported solid oxide fuel cells (ES-SOFC), anode-supported solid oxide fuel cells (AS-SOFC), and metal-supported solid oxide fuel cells (MS-SOFC). Base and raw materials for particular functional layers of solid oxide fuel cells are characterized, i.e., anode, electrolyte, and cathode layers. Thick- and thin-film technologies for the production of particular elements of SOFC fuel cells are presented. Using the example of technology developed in the Institute of Power Engineering Ceramic Department CEREL, the production technology of anode-supported solid oxide fuel cells and the method of characterizing the microstructure and electrochemical properties of the produced cells are presented.

A systematic study was initiated of anode-supported solid oxide fuel cells (SOFCs) with Nd2NiO4 cathodes. This type of cathode, a mixed conducting K2NiF4-type material, can be considered as a candidate for SOFC applications. In this study, the influence of (1) the presence of a Ce0.8Gd0.2O1.9 (CGO) interlayer between the electrolyte and the cathode, (2) sintering conditions, and (3) the grain size of the powder on the performance of SOFCs with Nd2NiO4 cathodes was investigated in more detail. Results from current density-voltage characteristics and permeation and gas diffusion measurements showed that the electrochemical performance was promising for SOFCs including a CGO interlayer and a Nd2NiO4 cathode (prepared with a powder with a d50 of 0.5A∕cm2 or 0.8μm) sintered at 1100°C or higher; current density at 800°C and 700mV between 1.2 and 1.3A∕cm2. The microstructure of the cathode was such that no gas diffusion problems occurred.

Solid oxide fuel cells (SOFCs), as highly efficient energy conversion devices, are anticipated to play a significant role in the realization of a low-carbon society. ENE-FARM type S (EF), equipped with SOFC stack, has been commercialized since 2012 by Osaka Gas. To further expand the market of EF, higher electrical efficiency, higher durability, lower cost of SOFC stack, and downsizing of EF are needed. For realizing these issues, two model changes were conducted in 2016 and 2020. The SOFC stack installed in the current EF, which is composed of Anode-supported SOFC (ASC), has established durability of over 12 years. For further widespread adoption in the EF market, we have focused on Metal-supported SOFCs (MSC), which have the potential to reduce costs by using fewer expensive ceramics.However, the use of a metal substrate in MSCs introduces unknown degradation phenomena that differ from those in ASCs. These phenomena include the degradation of the metal substrate and the interfacial reaction between the metal substrate and anode due to interdiffusion from the metal substrate and anode. Understanding and addressing the degradation phenomena originating from a metal substrate are significant challenges for the commercialization of MSCs. In this study, we investigated the degradation phenomena of MSCs, especially at the metal substrate/anode interface.The degradation phenomena are influenced by evaluation conditions such as durability time, temperature, and gas composition. The concentration of water vapor at the fuel gas outlet is much higher than at the fuel gas inlet throughout electrochemical reactions. To confirm the differences in the degradation phenomena due to gas composition, two MSC pieces were prepared. MSCs were fabricated at a lower temperature compared to ASCs, utilizing ceramic electrodes and electrolytes on a 16 cm2 ferritic stainless-steel substrate. Single cell tests were conducted using air at the cathode and fuel at the anode. The operating conditions for the evaluation were as follows: current density was varied from 0 to 0.42 A/cm², with H₂/H₂O used as the anode gas at two different dew points (DP). Test 1 was conducted at a DP of 30°C, and Test 2 was conducted at a DP of 88°C, while air served as the cathode gas. Both the anode gas and air flow rates were fixed during the evaluation. The operation was conducted with a fuel utilization factor (Uf) of approximately 10% and an air utilization factor (Ua) of approximately 20% at 0.42 A/cm².Figure 1 shows the results of the durability tests of 16 cm2-MSC cells conducted at 800°C. The change in voltage from the initial value is denoted as ΔV. The reduction in voltage on the fuel outlet side was approximately 25 mV greater than that on the fuel inlet side after 1000 hours. During these durability tests, the IR and electrode overvoltage (η) were measured by the current interruption method. The open circuit voltage remained stable without significant changes throughout the 1000 hours durability tests for both the fuel inlet and outlet sides. Figure 2 shows the results of IR and η during the durability tests conducted at 800°C. The observed reduction in voltage was attributed to increases in both IR and η, with similar increments noted for both the fuel inlet and outlet sides in relation to IR. It was found that no abnormally high resistance layer formation or significant increase in oxidation layer occurred on the outlet side after 1000 hours at 800°C.The more pronounced voltage drop observed at the outlet side is primarily due to a more significant increase in η. Considering that the evaluation was conducted under uniform conditions, except for the water vapor concentration on the anode gas side, it is plausible that the factors contributing to the increase in η are associated with the sintering or poisoning of the anode. These findings suggest that the reduction in reaction area and decreased gas diffusivity are significant contributors to the observed effects. In the presentation, we will discuss the insights derived from the electrochemical measurement results along with detailed cross-sectional analyses conducted after the durability tests. Figure 1

Direct internal reforming (DIR) operation provides many benefits for solid oxide fuel cells (SOFCs) by eliminating the need for an extra reformer. Anode-supported SOFCs (AS-SOFCs) are commonly used for DIR operations. However, the strong endothermic reforming reactions at the cell entrance may result in large thermal stresses and lead to premature failure. In this study, a two-dimensional model was developed to analyze the differences between the AS-SOFC and the new generation metal-supported SOFC (MS-SOFC) in DIR operations. The model considered the coupling effects of the chemical/electrochemical reactions, the mass/charge/heat transport processes and the thermal mechanical stress. The distributions of temperature, species composition, current density and thermal stress were determined and compared for both structures. The failure probability of the cell was estimated by stress distributions. The results showed that the MS-SOFC led to a gentler temperature distribution and a smaller failure probability with slight performance increase compared to the AS-SOFC.

Internal temperature prediction and control strategy design of anode-supported solid oxide fuel cell for hot start-up process

In recent years, anode-supported solid oxide fuel cell (SOFC) technology gains greater attention. Kinetic and thermodynamic parameters play a pivotal role in influencing the overall efficiency and functionality of SOFCs. In present study, 3D model of a single cell anode-supported SOFC is developed using ANSYS fluent. Kinetic and thermodynamic parameters are optimized by comparison with experimental data. Optimized parameters are subsequently used to investigate the impact of pressure and fuel utilization on the overpotential. Simulation results indicate that optimized parameters give rise to an increased fuel consumption and hence water formation. This can be explained by the fact that optimized parameters give rise to an increased rate of reaction. Optimized parameters lead to a reduction in cell overpotential thereby increasing current and power densities at elevated pressure. Increased fuel utilization correlates with a decrease in power and current densities.

Solid oxide fuel cells for stationary, mobile, and military applications

Precise porosity control is highly desirable for improving the electrochemical performance of solid oxide fuel cells (SOFCs). Freeze casting is an established method for enabling high bulk porosity in structures and controlling pore orientation. In this study, freeze casting was used to fabricate tubular, anode-supported SOFCs with aligned and varying amounts of porosity by controlling the solids/water ratio in different casting slurries. SOFCs were prepared with a Ni/yttria and scandia stabilized zirconia (ScYSZ) anode support (AS), an anode functional layer (AFL), a ScYSZ electrolyte, a lanthanum strontium manganite (LSM)/ScYSZ cathode interlayer (CIL), and an LSM cathode. The permeability of the anode support was found to increase from 1.4 × 10−2 to 1.8 × 10−2 m2 as porosity was increased from 57 to 64 vol%, while the total cell resistance decreased by 35% from 0.93 to 0.60 Ohm cm2. When evaluated with 30 vol% H2 as the fuel at 800 °C, the decrease of concentration polarization enabled an increase in electrochemical performance by 42% from 0.35 to 0.50 W/cm2 as the porosity in the anode support was increased. Mechanical strength characterization using a three-point method showed there is a practical upper limit of the amount of porosity that can be designed into the anode support. This work paves a way for controlling porosity by freeze casting and understanding the correlation between porosity and concentration polarization losses in SOFCs.

Three-dimensional computational fluid dynamics modeling of anode-supported planar SOFC

The anode-supported solid oxide fuel cells (SOFCs) with an yttria-stabilized zirconia (YSZ) electrolyte have been successfully prepared by the sequential steps of fabricating technique including tape casting, spin coating, and screen-printing. Two types of the SOFCs are manufactured and their cell performances are characterized via the detail analysis of the electrochemical impedance spectroscopy (EIS). The maximum power densities are 411 and for the high and low performance cells at , respectively. According to the EIS analysis, the electrochemical performance of the poor cell is dominated by the anodic non-charge-transfer resistance, which is mainly resulted by the gas diffusion polarization due to the low porosity of the anode. The high performance cell is controlled by the simultaneous contributions of the ohmic resistance , the anodic polarization , and the cathodic polarization at the operation temperature of . However, the will dominate the performance of the cell as the temperature is lowered down to .

A simple, rapid spray method for preparing anode-supported solid oxide fuel cells with GDC electrolyte thin films