Development of solid oxide fuel cells (SOFCs) by tape-casting and single-step co-firing of monolithic laminates

We developed a cost-effective method to manufacture high performance-monolithic solid oxide fuel cells using nano-composite electrodes, tape-casting and single-step co-firing.     

Geometrical modeling of the triple-phase-boundary in solid oxide fuel cells

A geometrical model was developed to predict the influences of solid grain size, pore size and porosity on the triple-phase-boundary (TPB) length in electronic composite electrodes of solid oxide fuel cells. It shows that the TPB length is inversely proportional to grain size and can be optimized by the pore size and porosity.     

Ni-Sm2O3 cermet anodes for intermediate-temperature solid oxide fuel cells with stabilized zirconia electrolytes

Ni-LnO_x cermets (Ln = La, Ce, Pr, Nd, Sm, Eu, Gd), in which LnO_x is not an oxygen ion conductor, have shown high performance as the anodes for low-temperature solid oxide fuel cells (SOFCs) with doped ceria electrolytes. In this work, Ni-Sm₂O₃ cermets are primarily investigated as the anodes for intermediate-temperature SOFCs with scandia stabilized zirconia (ScSZ) electrolytes. The electrochemical performances of the Ni-Sm₂O₃ anodes are characterized using single cells with ScSZ electrolytes and LSM-YSB composite cathodes. The Ni-Sm₂O₃ anodes exhibit relatively lower performance, compared with that reported Ni-SDC (samaria doped ceria) and Ni-YSZ (yttria stabilized zirconia) anodes, the state-of-the-art electrodes for SOFCs based on zirconia electrolytes. The relatively low performance is possibly due to the solid-state reaction between Sm₂O₃ and ScSZ in fuel cell fabrication processes. By depositing a thin interlayer between the Ni-Sm₂O₃ anode and the ScSZ electrolyte, the performance is substantially improved. Single cells with a Ni-SDC interlayer show stable open circuit voltage, generate peak power density of 410 mW cm⁻² at 700 °C, and the interfacial polarization is about 0.7 Ω cm².     

Recent anode advances in solid oxide fuel cells

Solid oxide fuel cells (SOFCs) are electrochemical reactors that can directly convert the chemical energy of a fuel gas into electrical energy with high efficiency and in an environment-friendly way. The recent trends in the research of solid oxide fuel cells concern the use of available hydrocarbon fuels, such as natural gas. The most commonly used anode material Ni/YSZ cermet exhibits some disadvantages when hydrocarbons were used as fuels. Thus it is necessary to develop alternative anode materials which display mixed conductivity under fuel conditions. This article reviews the recent developments of anode in SOFCs with principal emphasis on the material aspects. In addition, the mechanism and kinetics of fuel oxidation reactions are also addressed. Various processes used for the cost-effective fabrication of anode have also been summarized. Finally, this review will be concluded with personal perspectives on the future research directions of this area.     

Synthesis and characterization of aluminum-doped perovskites as cathode materials for intermediate temperature solid oxide fuel cells

(Ba_0.5Sr_0.5)(Fe_1-xAl_x)O_3-δ (BSFAx, x = 0–0.2) oxides have been synthesized as novel cobalt-free cathode materials for intermediate temperature solid oxide fuel cells (IT-SOFCs) using a sol-gel method. The BSFAx (x = 0–0.2) materials have been characterized by X-ray diffraction and scanning electron microscopy. The electrical conductivities and electrochemical properties of the prepared samples have also been measured. At 800 °C, the conductivity drops from 15 S cm⁻¹ to 5 S cm⁻¹ when the doping level of aluminum is increased to 20%. The aluminum-doping concentration has important impacts on the electrochemical properties of BSFAx materials. The BSFA0.09 cathode shows a significantly lower polarization resistance (0.26 Ω cm²) and cathodic overpotential value (55 mV at the current density of 0.1 A cm⁻²) at 800 °C. Furthermore, an anode-supported single cell with BSFA0.09 cathode has been fabricated and operated at a temperature range from 650 to 800 °C with humidified hydrogen (∼3vol% H₂O) as the fuel and the static air as the oxidant. A maximum power density of 676 mWcm⁻² has been achieved at 800 °C for the single cell. We believe that BSFA0.09 is a promising cathode material for future IT-SOFCs application.     

Fundamental mechanisms limiting solid oxide fuel cell durability

The fundamental issues associated with solid oxide fuel cell (SOFC) durability have been reviewed with an emphasis on general features in SOFCs and respective anode and cathode related phenomena. As general features, physicochemical properties and cell performance degradation/failure are correlated and bridged by the electrode reaction mechanisms. Particular emphasis is placed on the elemental behaviour of gaseous impurities and the possible role of liquids formed from gaseous substances. The lifetime of a state-of-the-art Ni cermet anodes is limited by a variety of microstructural changes, which mainly result from material transport-, deactivation- and thermomechanical mechanisms. Anode degradation can mainly be influenced by processing, conceptual and operating parameters. Designing a redox stable anode is currently one of the biggest challenges for small scale SOFC systems. Degradation mechanisms of different cathode materials are reviewed with a focus on the intrinsic degradation of doped lanthanum manganites (e.g. LSM) and doped lanthanum ferro-cobaltites (LSCF). Manganese-based perovskites can be regarded to be sufficiently stable, while for the better performing LSCF cathodes some intrinsic degradation was detected. New materials that are supposed to combine a better stability and high performance are also shortly mentioned.     

Out-of-cell measurements of H2-H2O effective binary diffusivity in the porous anode of solid oxide fuel cells (SOFCs)

The effective binary diffusivity of H₂ and H₂O in a Ni and yittria-stabilized zirconia (YSZ) anode of the solid oxide fuel cells (SOFCs) was measured between 650 and 800 °C using an electrochemical cell consisting of an oxygen pump, an oxygen sensor, and a porous SOFC anode pellet. The effective binary diffusivity was obtained from the relationship between the current density across the oxygen pump, and the H₂ partial pressure gradient across the anode sample measured using the oxygen sensor. The anode limiting current density and concentration polarization were estimated using the experimental results.     

A review of numerical modeling of solid oxide fuel cells

The solid oxide fuel cell (SOFC) is one of the most promising fuel cells for direct conversion of chemical energy to electrical energy with the possibility of its use in co-generation systems because of the high temperature waste heat. Various mathematical models have been developed for three geometric configurations (tubular, planar, and monolithic) to solve transport equations coupled with electrochemical processes to describe the reaction kinetics including internal reforming chemistry in SOFCs. In recent years, considerable progress has been made in modeling to improve the design and performance of this type of fuel cells. The numbers of the contributions on this important type of fuels have been increasing rapidly. The objective of this paper is to summarize the present status of the SOFC modeling efforts so that unresolved problems can be identified by the researchers.     

An efficient ceramic-based anode for solid oxide fuel cells

A new ceramic-based multi-component material, containing one electronic conductor (Y-substituted SrTiO₃, SYT), one ionic conductor (YSZ) and a small amount (∼5 vol.%) of Ni catalyst, was investigated as an alternative anode material for solid oxide fuel cells (SOFCs). The ceramic framework SYT/YSZ shows good dimensional stability upon redox cycling and has an electrical conductivity of ∼10 S cm⁻¹ under typical anode conditions. Owing to the substantial electrocatalytic activity of the fine and well-dispersed Ni particles on the surface of the ceramic framework, the electrode polarization resistance of 5 vol.% Ni-impregnated SYT/YSZ anode reached 0.21 Ω cm² at 800 °C in wet Ar/5%H₂. Based on these results, a redox-stable anode-supported planar SOFC is expected using this anode material, thus offering great advantages over the current generation of Ni/YSZ-based SOFCs.     

Alternative anode materials for solid oxide fuel cells

The electrolyte of a solid oxide fuel cell (SOFC) is an O²⁻-ion conductor. The anode must oxidize the fuel with O²⁻ ions received from the electrolyte and it must deliver electrons of the fuel chemisorption reaction to a current collector. Cells operating on H₂ and CO generally use a porous Ni/electrolyte cermet that supports a thin, dense electrolyte. Ni acts as both the electronic conductor and the catalyst for splitting the H₂ bond; the oxidation of H₂ to H₂O occurs at the Ni/electrolyte/H₂ triple-phase boundary (TPB). The CO is oxidized at the oxide component of the cermet, which may be the electrolyte, yttria-stabilized zirconia, or a mixed oxide-ion/electron conductor (MIEC). The MIEC is commonly a Gd-doped ceria. The design and fabrication of these anodes are evaluated. Use of natural gas as the fuel requires another strategy, and MIECs are being explored for this application. The several constraints on these MIECs are outlined, and preliminary results of this on-going investigation are reviewed.     

Polarization measurements of anode-supported solid oxide fuel cells studied by incorporation of a reference electrode

A three-electrode system configuration was applied to an anode-supported solid oxide fuel cell where the anode to cathode surface area ratio was ∼7.9, and Ni/YSZ was used as the anode, LSM as the cathode, Pt as the reference electrode, and thin YSZ film as the electrolyte. The cell was polarized potentiostatically at −0.2, −0.4, −0.6 and −0.8 V versus open circuit voltage (OCV) and the potential change versus a reference electrode were recorded to ascertain the relative electrode polarization contributions. The results of these studies suggested that, while the anode contributions to cell polarization were less significant than that observed for the cathode, they were not negligible. Furthermore, the disparity in the relative electrode polarization contribution was observed to decrease with increasing temperature and polarization. Electrode polarization studies suggested that cathodic overvoltage decreased remarkably with increasing temperature whereas anodic overvoltage increased slightly with increasing temperature. Electrode kinetic parameters were extracted from these polarization experiments and the implications of these parameters to cell performance were discussed. Lastly, electrochemical impedance spectroscopy (EIS) data was presented to further elucidate the relative contributions of the anode and cathode impedances on button cell performance.     

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.     

Sulfur poisoning of La(Ni0.6Fe0.4)O3 cathode material for solid oxide fuel cells

Sulfur poisoning of cathode materials is one of the important factors to cause cathode performance degradation resulting in shortening lifetime of SOFC. The sulfur attacks alkali earth components of the rare earth-transition metal perovskite oxides, such as Ba, Ca, Sr, which reacts with SO₂ to form sulfates. In this work, the La(Ni_0.6Fe_0.4)O₃ (LNF) cathode material without alkali earth elements was employed to investigate the sulfur poisoning behavior by flowing 30 ppm SO₂ at different temperatures of 500 °C–800 °C. It was found that SO₂ readily reacts with the La₂O₃ component in LNF to form La₂O₂SO₄ at 700 °C and 800 °C. The extent of the chemical reaction is temperature dependent. These results confirm that sulfur poisoning also occurs in cathode materials free of alkali earth components. The study prompts the exploration of new materials and new strategies for the developing new cathode materials with high sulfur tolerance.     

Thin films for micro solid oxide fuel cells

Thin film deposition as applied to micro solid oxide fuel cell (μSOFC) fabrication is an emerging and highly active field of research that is attracting greater attention. This paper reviews thin film (thickness ≤1 μm) deposition techniques and components relevant to SOFCs including current research on nanocrystalline thin film electrolyte and thin-film-based model electrodes. Calculations showing the geometric limits of μSOFCs and first results towards fabrication of μSOFCs are also discussed.     

Short review on cobalt-free cathodes for solid oxide fuel cells

Cobalt-containing cathodes are known for their ability to operate under high-temperature applications in solid oxide fuel cells (SOFCs). Reducing the operation temperature into intermediate temperature-to-low temperature (IT-LT) zones may lead to a mismatch in the thermal expansion coefficient between the cathodes and the developed IT-LTSOFC electrolyte materials. Hence, cathode materials are adjusted to resolve this issue. Studies on IT-LTSOFC propose cobalt-free cathodes as an alternative way to produce high electrochemical performance cells for operation within the IT-LT range. Novel cobalt-free cathode powders are developed using perovskite structured materials, such as strontium ferrite oxide, as the main components together with dopants. This paper reviews various studies on cobalt-free cathode development, including the most important parameter in determining cathode performance, namely, the polarization resistance of SOFC cathodes.     

Oxidation-induced degradation and performance fluctuation of solid oxide fuel cell Ni anodes under simulated high fuel utilization conditions

High fuel utilization (Uf) conditions in a small-scale electrolyte-supported solid oxide fuel cell (SOFC) with an Ni-ScSZ anode were approximated by adjusting the gas composition to correspond to that in the downstream region of an SOFC stack. At Uf = 80%, and with a cell voltage of 0.5 V, the ohmic resistance fluctuated slightly from the early stages of operation, and became much more significant after 80 h. High current density and large polarization were found to promote Ni agglomeration, leading to insufficient connectivity of the Ni nanoparticles. At Uf = 95%, and with a cell voltage of 0.6 V, fluctuations in the polarization were observed at a much earlier stage, which are attributed to the highly humidified fuel. In particular, significant degradation was observed when the compensated anode potential (which incorporates the anode ohmic losses) approached the Ni oxidation potential. Ohmic losses in the anode are considered to influence Ni oxidation by exposing Ni near the electrolyte to a more oxidizing atmosphere with the increase in oxygen ion transport. Stable operation is therefore possible under conditions in which the compensated anode potential does not approach the Ni oxidation potential, assuming a stable interconnected Ni network.     

Fabrication of solid oxide fuel cells (SOFCs) by solvent-controlled co-tape casting technique

A co-tape casting process has an advantage of cost-effectiveness for mass production. To fabricate solid oxide fuel cells (SOFCs) with high electrochemical performance by co-tape casting, high solid loading and binder content of tape cast slurry are required to improve particle network strength. However, high solid loading and binder content cause high viscosity of the slurry, which makes removal of air bubbles and handling difficult. In this study, a new method to fabricate uniform green tapes with high solid loading and binder content by controlling solvent ratio under vacuum condition is proposed. As a result, high solid loading and binder content with 39% improved storage shear modulus, 26% improved LVR length, tensile strength of 5.0 MPa, and packing density of 57.5% were achieved at solvent ratio of 22 wt%. To fabricate unit cells using the green tapes, thermal decomposition and shrinkage behavior are characterized, and heat treatment steps at 250 °C, 350 °C, and 500 °C and co-sintering temperature were determined at 1250 °C. A fabricated unit cell showed open circuit voltage (OCV) of 1.10 V and the maximum power density of 1.20 W cm^?2 at 800 °C. To fabricate crack-free Ф5.0 cm unit cells, the mechanical strength of the anode support tapes after thermal decomposition was measured to determine the tape compositions that can minimize cracks at the unit cell. As a result, a crack-free unit cell with a diameter of 5.0 cm was fabricated, achieving OCV of 1.05 V and power of 4.3 W at 800 °C.     

Advanced perovskite anodes for solid oxide fuel cells: A review

Solid oxide fuel cells (SOFCs) are at the frontline of clean energy generation technologies to convert chemical energy to electricity with high efficiency. In recent years, because of their fuel flexibility, multiple fuels are fed in anode, e.g., hydrogen, ammonia, hydrocarbons, solid carbon, etc.; in addition, these fuels are always mixed with a certain amount of H₂S. Perovskite is one of the most important classes of anode materials being investigated in laboratories, these materials to some extent are immune to coke formation and sulfur poisoning when using hydrocarbon fuels, and retain inherent stability upon reduction and oxidation cycling. In this review, recent developments in perovskite anode materials are summarized and future prospects are discussed.     

Anode supported solid oxide fuel cells (SOFC) by electrophoretic deposition

Solid oxide fuel cells (SOFC), with its ability to use hydrocarbon fuels and capability to offer highest efficiency, have attracted great attention in India in recent years as an alternative energy generation system for future. But a great deal of problems associated with SOFC is needed to be solved before it can find commercial application. The relatively high operating temperature of 800-1000 °C of SOFC imposes a stringent requirement on materials that significantly increases the cost of SOFC technology. Reducing the operating temperature of an SOFC to below 800 °C can reduce degradation of cell components, improve flexibility in cell design, and lower the material and manufacturing cost by the use of cheap and readily available materials such as ferritic stainless steel. The operating temperature can be reduced by two possible approaches: (i) developing alternative electrolyte materials with high ionic conductivity at lower temperature, and (ii) developing much thinner and denser electrolyte layer such that the ohmic losses are minimised.In this work we report the use of inexpensive Electrophoretic deposition (EPD) technique in making about 10 micron thin and dense YSZ electrolyte on NiO-YSZ substrate. The effect of different operating parameters such as applied voltage, deposition time etc have been optimised during deposition from YSZ suspension in acetylacetone. The YSZ/NiO-YSZ bi-layers were then co-sintered at 1450 °C for 5 h. The single SOFC cells were then fabricated by brush painting LSM:YSZ (50:50) paste on the electrolyte layer followed by sintering at 1200 °C for 2 h. The single SOFC cell when tested using H₂ as fuel and ambient air as oxidant exhibited an open circuit voltage (OCV) of 1.03 V and the peak power density of about 624 mW/cm² at 800 °C.