Performance and Stability of Large Planar Solid Oxide Fuel Cells Using Phosphine Contaminated Hydrogen Fuel

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

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

Numerical investigation of the effect of operating parameters on a planar solid oxide fuel cell

It is always an important research direction to improve the performance of solid oxide fuel cells (SOFCs) through structural optimization. For anode-supported SOFC, the thin cathode thickness results in an uneven distribution of oxygen concentration in the porous electrode, which limits the output performance. In this paper, a three-dimensional model of the anode-supported planar SOFC was established, and the thickness of the cathode diffusion layer in the area covered by the connector was increased to improve the uniformity of oxygen distribution in the cathode. The results show that increasing the thickness of the cathode diffusion layer under the connector can significantly improve the overall output performance of SOFC. The uniformity of oxygen concentration distribution in the cathode is improved, the local current density under the connector is increased, and the maximum output power density of the cell is increased by 29.14%. The results show that the output performance of the SOFC and the uniformity of gas distribution in the porous electrode can be improved by increasing the thickness of the cathode diffusion layer under the connector in the structure design and practical application of the SOFC. The research of this paper provides a reference for the optimization design of SOFC.

It is well known that the main overpotentials during the operation of a fuel cell are activation, ohmic and concentration overpotentials. In order to operate more efficiently these devices that convert the chemical energy of the fuel into electrical energy, it is necessary to reduce as much as possible the overpotentials aforementioned. Some of the components of a fuel cell are the so called current collectors. These components affect the fuel cell performance mainly by means of two overpotentials, the ohmic and concentration overpotentials. The second one, is however, affected indirectly by the current collector design, since it may only help to distribute more uniformly the gases over the electrodes. The activation overpotential is basically not affected because it is mainly related with the electrode properties such as the exchange current density. In this work, the effect of the current collectors design on the performance of planar Solid Oxide Fuel Cells (SOFCs) is assessed by means of fully three-dimensional numerical simulations by comparing the V-I and power density curves of a planar cell. The goal of this study is not to find the optimal design of the current collectors but a way in which the overpotentials relate with their design in order to propose some helpful recommendations during the design process of these fuel cell components. These recommendations may lead to design an improved or optimal flow distributor.

In order to develop solid oxide fuel cells (SOFCs) running on hydrocarbon fuels, we have focused on a new method of improving electrode performance and reducing carbon deposition by coating thin films of samaria-doped ceria (SDC) within the pores of electrode by a sol-gel coating technique. The SDC coating on the pores of anode made it possible to have a good stability for long-term operation due to low carbon deposition and nickel sintering. In this study, we demonstrated a new method of improving electrode performance and reducing carbon deposition by coating thin films of samaria-doped ceria and applied the modification technique to two different types of fuel cell structures, anode-supported SOFC and comb-shaped SOFC. From our results, the maximum power density of an anode-supported cell (electrolyte; 8 mol% YSZ and thickness of 30μm, and cathode; La0.85Sr0.15MnO3) with the modified anode was ∼300mW∕cm2 at 700°C in the mixture of methane (25%) and air (75%) as the fuel, and air as the oxidant. The cell was operated for 500hr without significant degradation of cell performance. For the comb-shaped SOFCs operated in the mixed-fuels fuel cell conditions, the cell performance was 40mW∕cm2 at 700°C in the CH4∕O2 ratio of 1.

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.

Integrated gasification fuel cell (IGFC) systems combining coal gasification and solid oxide fuel cells (SOFC) are promising for highly efficient and environmentally friendly utilization of coal for power production. Most IGFC system analyses performed to-date have used nondimensional thermodynamic SOFC models that do not resolve the intrinsic constraints of SOFC operation. In this work a quasi-two-dimensional (2D) finite volume model for planar SOFC is developed and verified using literature data. Special attention is paid to making the model capable of supporting recent SOFC technology improvements, including the use of anode-supported configurations, metallic interconnects, and reduced polarization losses. Activation polarization parameters previously used for high temperature electrolyte-supported SOFC result in cell performance that is much poorer than that observed for modern intermediate temperature anode-supported configurations; thus, a sensitivity analysis was conducted to identify appropriate parameters for modern SOFC modeling. Model results are shown for SOFC operation on humidified H2 and CH4 containing syngas, under coflow and counterflow configurations; detailed internal profiles of species mole fractions, temperature, current density, and electrochemical performance are obtained. The effects of performance, fuel composition, and flow configuration of SOFC performance and thermal profiles are evaluated, and the implications of these results for system design and analysis are discussed. The model can be implemented not only as a stand-alone SOFC analysis tool, but also a subroutine that can communicate and cooperate with chemical flow sheet software seamlessly for convenient IGFC system analysis.

This report summarizes the results of Phase II of this program, 'Low-Cost Manufacturing Of Multilayer Ceramic Fuel Cells'. The objective of the program is to develop advanced ceramic manufacturing technologies for making planar solid oxide fuel cell (SOFC) components that are more economical and reliable for a variety of applications. Phase II development work focused on three distinct manufacturing approaches (or tracks) for planar solid oxide fuel cell elements. Two development tracks, led by NexTech Materials and Oak Ridge National Laboratory, involved co-sintering of planar SOFC elements of cathode-supported and anode-supported variations. A third development track, led by the University of Missouri-Rolla, focused on a revolutionary approach for reducing operating temperature of SOFCs by using spin-coating to deposit ultra-thin, nano-crystalline YSZ electrolyte films. The work in Phase II was supported by characterization work at Ohio State University. The primary technical accomplishments within each of the three development tracks are summarized. Track 1--NexTech's targeted manufacturing process for planar SOFC elements involves tape casting of porous electrode substrates, colloidal-spray deposition of YSZ electrolyte films, co-sintering of bi-layer elements, and screen printing of opposite electrode coatings. The bulk of NexTech's work focused on making cathode-supported elements, although the processes developed at NexTech also were applied to the fabrication of anode-supported cells. Primary accomplishments within this track are summarized below: (1) Scale up of lanthanum strontium manganite (LSM) cathode powder production process; (2) Development and scale-up of tape casting methods for cathode and anode substrates; (3) Development of automated ultrasonic-spray process for depositing YSZ films; (4) Successful co-sintering of flat bi-layer elements (both cathode and anode supported); (5) Development of anode and cathode screen-printing processes; and (6) Demonstration of novel processes for composite cathode and cermet anode materials. Track 2--ORNL's development work focused solely on making anode-supported planar cells by tape casting of a porous anode substrate, screen printing of a YSZ electrolyte film, co-sintering of the bi-layer element, and screen-printing of an opposite cathode coating. Primary accomplishments within this track are summarized below: (1) Development and scale-up of anode tape casting and lamination processes; (2) Development of proprietary ink vehicle for screen-printing processes; (3) Development of screen-printing process for depositing YSZ films; (4) Successful co-sintering of flat bi-layer anode-supported elements; and (5) Development of cathode screen-printing process. Track 3--UMR's process development work involved fabrication of a micro-porous cathode substrate, deposition of a nano-porous interlayer film, deposition of nano-crystalline YSZ electrolyte films from polymeric precursor solutions, and deposition of an anode coating. Primary accomplishments within this track are summarized below: (1) Development and scale up of tape casting and sintering methods for cathode substrates; (2) Deposition of nano-porous ceria interlayer films on cathode substrates; (3) Successful deposition of dense YSZ films on porous cathode substrates; and (4) Identification of several anode material options.

Solid oxide fuel cell (SOFC) is a promising power source with its strong advantage being the use of solid oxide electrolyte. This allows long time operation of the cell without electrolyte depletion. Due to the solid nature of SOFCs, sealing of the cell to the peripheral attachments becomes an issue, especially in planar SOFC type. This defect in gas sealing causes gas-leakage to the outside, as well as, gas-crossover through the peripheral areas of the cell. These leakages lead to a reduction in the open-circuit voltage (OCV) and the overall cell performance. Most previous reports made on gas crossover were only based on H2 crossover through the thin electrolyte membrane. In this work, the performance of a gas-leaked cell was compared with one with a gas-tight sealing. Both cells were 100 cm2 planar SOFCs operated at 750 and supplied with H2 and air gases at the anode and cathode respectively. The cells were supplied by a commercial SOFC producer in South Korea. Electrochemical Impedance Spectroscopy (EIS) and steady-state polarization (SSP) techniques were used in comparing the performance of the cells. An inert gas step addition (ISA) method [1] was also employed in determining quantitatively the partial pressure of water formed at the anode and its resulting internal short current. The ISA was first used to investigate the flow and partial pressure effect on the performance of a molten carbonate fuel cell (MCFC). The method adds nitrogen gas to the anode gas flow and the addition simultaneously increases the reactant gas flow until the added nitrogen arrives at the cell. The nitrogen addition port is placed ca. 5 m ahead of the anode electrode and is supplied through a 1/4-inch stainless tube, thus several seconds are required by the N2 gas to reach the cell. The SSP behavior showed that the OCV and the polarization voltages recorded were higher in the gas-tight cell than in the gas-leaked cell. The impedance spectra, on the other hand, showed a remarkable decrease in the gas-leaked cell and was attributed to the decrease in the water-induced mass transfer resistance of the cell. Through the ISA method, the partial pressure of water formed at the anode as a result of the gas leak was quantitatively determined and was observed to be significantly higher in the case of the gas-leaked cell. Similarly, the computed internal short current was greater in the case of the gas-leaked cell.[1] C.-G. Lee, B.-S. Kang, H.-K. Seo, H.-C. Lim, J. Electroanal. Chem., 540, 169–188 (2003).

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 planar anode-supported electrolyte was fabricated using a tape casting method that involved a single step cofiring process. A standard NiO∕8YSZ cermet anode, 8mol% YSZ electrolyte, and a lanthanum strontium manganite cathode were used for the solid oxide fuel cell unit cell. A pressurized cofiring technique allows the creation of a thin layer of dense electrolyte about 10μm without warpage. The open circuit voltage of the unit cell indicated negligible fuel leakage through the electrolyte film due to the dense and crack-free electrolyte layer. An electrochemical test of the unit cell showed a maximum power density up to 0.173W∕cm2 at 900°C. Approximated electrochemical properties, e.g., activation energy, Ohmic resistance, and exchange current density, indicated that the cell performance was significantly influenced by the electrode properties of the unit cell.

Ceramic high-temperature fuel cells and electrolysers are efficient energy conversion systems for electrical power generation and hydrogen production. Their core components are constituted by a stack of electroactive Solid Oxide Cells (SOCs) in which the electrochemical reactions take place. Thanks to their flexibility, the same stack can be alternatively operated in both fuel cell and electrolysis modes. However, the insufficient durability of SOCs still constitutes a major limitation for the technology. The present study addresses this issue and aims to bring some new insights on the effect of the Solid Oxide Fuel Cell (SOFC) versus Solid Oxide Electrolysis Cell (SOEC) operating modes on degradation of a typical Ni-YSZ//YSZ//CGO//LSCF-CGO cell. The electrochemical degradations are generally attributed to several underlying phenomena such as electrode microstructural evolution, material chemical decomposition or electroactive sites poisoning by contaminants. Among them, it is generally considered that Ni agglomeration in the Ni-YSZ cermet and Lanthanum Strontium Cobalt Ferrite (LSCF) material destabilization are two prevalent mechanisms involved in the cell performance deterioration. Therefore, these two mechanisms have been specifically investigated by a coupled approach of long-term testing in both SOFC and SOEC modes (1000 ≤ t (h) ≤9000) and post-test characterizations. The experimental results have then been analyzed in the frame of an in-house multi-scale model with the purpose to interpret them and to quantify the effect of material ageing on cell performances. The extent of Ni agglomeration has been characterized by three-dimensional electrode reconstructions obtained by X-ray nano-holotomography at European Synchrotron Radiation Facility (ESRF) (on the new Nano-Imaging beamline ID16A-NI). The new set-up and protocol enable the reconstructions of valuable 3D volumes (Fig. 1) with a large field of view (~50 µm) along with a high spatial resolution (~50 nm). The electrode morphological properties, which have been measured on the 3D volumes, have revealed a substantial Ni coarsening over time at 850°C and 750°C, whereas no Ni depletion was detected at the electrolyte interface. The increase of the Ni particle size is found to induce a decrease in both (i) the density of Triple Phase Boundary (TPBs) lines and (ii) the interfacial surface area between Ni and gas. Moreover, it was found that the Ni/YSZ interfacial surface area does not evolve during the experiments. This statement indicates that the ceramic backbone in the cermet prevents a massive Ni agglomeration at the SOFC/SOEC operating temperature. The compilation of all experimental data have allowed fitting the parameters of a physically-based law for Ni coarsening that was introduced in the modelling framework. The simulations have revealed that Ni agglomeration explains around 20-25% of the electrochemical degradation at 850°C after 1000 hrs of operation. However, the electrode microstructural evolution is found not to be affected by the cell polarizations. Therefore, the mechanism cannot explain the higher degradation rates recorded in electrolysis mode compared to the fuel cell ones. To explain the impact of the operating modes (SOFC or SOEC) on the degradation rates, several post-test analyses (i.e. Scanning Electron Microscopy, Transmission Electron Microscopy, X-ray µfluorescence and µdiffraction techniques) have been employed to investigate the phase reactivity in the region of the CGO barrier layer. The characterizations have revealed that Sr diffusion across the barrier layer and formation of SrZrO3 secondary phase occur mainly during electrolysis operation, whereas the process is very limited in fuel cell mode (Fig. 2). As a consequence, LSCF destabilization is found not to be involved in the degradation of cell performances during fuel cell operation while it could explain the highest degradation rates recorded in electrolysis mode. The post-test analyses have also revealed a diffusion and an accumulation of Co in the region of the barrier layer which is concomitant with the formation of SrZrO3. The formation of these Co-rich segregates in contact with SrZrO3 grains have been identified as cobalt-ferrite type compound. The in-house multi-scale model has been used to interpret the role of the cell operating mode on the LSCF destabilization mechanism. The cell polarization curves and the local quantities within the O2 electrode have been computed in both fuel cell and electrolysis modes. The simulations have shown that the electrolysis operation leads to a strong depletion of oxygen vacancies in the LSCF material. It has been proposed that the depletion in oxygen vacancies under electrolysis polarization could drive the Sr release from the structure, and in turn, could explain the experimental results. Based on this proposition, a possible mechanism for the LSCF destabilization and SrZrO3 formation has been detailed. Figure 1

A solid oxide fuel cell (SOFC) electrochemically converts chemical energy of a fuel into electricity at temperatures from about 650 to 1000oC. SOFCs offer certain advantages over lower temperature fuel cells, notably ability to use CO as a fuel rather than being poisoned by it, and high grade exhaust heat for combined heat and power, or combined cycle gas turbine applications. This paper reviews the operating principle, materials for different cell and stack components, cell designs, and applications of SOFCs. Among different designs of solid oxide fuel cells (SOFCs), the electrical resistance of tubular SOFCs is high, and areal power density (W/cm2) and volumetric power density (W/cm3) low. Planar SOFCs, in contrast, are capable of achieving very high power densities.

Integrated gasification fuel cell (IGFC) systems combining coal gasification and solid oxide fuel cells (SOFC) are promising for highly efficient and environmentally friendly utilization of coal for energy production. Most IGFC system analyses performed to date have used non-dimensional thermodynamic SOFC models that do not resolve the intrinsic constraints of SOFC operation. In this work, a one-dimensional finite volume model for planar SOFC is developed and verified using literature data. Special attention is paid to making the model capable of supporting recent SOFC technology improvements, including the use of anode-supported configurations, metallic interconnects, and reduced polarization losses. Results are presented for SOFC operation on humidified hydrogen and methane-containing syngas, under co-flow and counter-flow configurations; detailed internal profiles of species mole fractions, temperature, current density and electrochemical performance are obtained. The effects of performance, fuel composition and flow configuration on SOFC performance and thermal profiles are evaluated, and the implications of these results for system design and analysis are discussed.