Probing and Mapping Electrode Surfaces in Solid Oxide Fuel Cells

Solid oxide fuel cells (SOFCs) are potentially the most efficient and cost-effective solution to utilization of a wide variety of fuels beyond hydrogen ^1-7. The performance of SOFCs and the rates of many chemical and energy transformation processes in energy storage and conversion devices in general are limited primarily by charge and mass transfer along electrode surfaces and across interfaces. Unfortunately, the mechanistic understanding of these processes is still lacking, due largely to the difficulty of characterizing these processes under in situ conditions. This knowledge gap is a chief obstacle to SOFC commercialization. The development of tools for probing and mapping surface chemistries relevant to electrode reactions is vital to unraveling the mechanisms of surface processes and to achieving rational design of new electrode materials for more efficient energy storage and conversion². Among the relatively few in situ surface analysis methods, Raman spectroscopy can be performed even with high temperatures and harsh atmospheres, making it ideal for characterizing chemical processes relevant to SOFC anode performance and degradation^8-12. It can also be used alongside electrochemical measurements, potentially allowing direct correlation of electrochemistry to surface chemistry in an operating cell. Proper in situ Raman mapping measurements would be useful for pin-pointing important anode reaction mechanisms because of its sensitivity to the relevant species, including anode performance degradation through carbon deposition^{8, 10, 13, 14} ("coking") and sulfur poisoning^{11, 15} and the manner in which surface modifications stave off this degradation¹⁶. The current work demonstrates significant progress towards this capability. In addition, the family of scanning probe microscopy (SPM) techniques provides a special approach to interrogate the electrode surface with nanoscale resolution. Besides the surface topography that is routinely collected by AFM and STM, other properties such as local electronic states, ion diffusion coefficient and surface potential can also be investigated^17-22. In this work, electrochemical measurements, Raman spectroscopy, and SPM were used in conjunction with a novel test electrode platform that consists of a Ni mesh electrode embedded in an yttria-stabilized zirconia (YSZ) electrolyte. Cell performance testing and impedance spectroscopy under fuel containing H₂S was characterized, and Raman mapping was used to further elucidate the nature of sulfur poisoning. In situ Raman monitoring was used to investigate coking behavior. Finally, atomic force microscopy (AFM) and electrostatic force microscopy (EFM) were used to further visualize carbon deposition on the nanoscale. From this research, we desire to produce a more complete picture of the SOFC anode.     

Solid Oxide Fuel Cell Anode Materials for Direct Hydrocarbon Utilization

Solid oxide fuel cells (SOFC) are highly efficient energy conversion devices with the advantage of directly utilizing hydrocarbon fuels. Starting with a short introduction about the fuel challenges and early achievements in this field, this review paper focuses on advances in oxygen‐ion conducting electrolyte‐based SOFC during the last 15 years. Robust anodes immune to carbon deposition are a prerequisite for direct hydrocarbon SOFC. In this paper, direct hydrocarbon SOFC anode materials are classified into three general categories: Ni‐cermet, Cu‐cermet, and oxide‐based anodes. Oxide anodes are further classified in terms of their crystalline structures, namely fluorite, rutile, tungsten bronze, pyrochlore, perovskite, and double perovskite. Achievements and recent advances on these SOFC anodes are reviewed and discussed. The concluding remarks summarize the pros and cons of direct hydrocarbon SOFC anode materials along with the perspective of future research trends.     

On the Active Surface State of Nickel‐Ceria Solid Oxide Fuel Cell Anodes During Methane Electrooxidation

Solid oxide fuel cells (SOFCs) have grown in recognition as a viable technology able to convert chemical energy directly into electricity, with higher efficiencies than conventional thermal engines. Direct feeding of the SOFCs anode with hydrocarbons from fossil or renewable sources, appears more attractive compared to the use of hydrogen as a fuel. The addition of mixed oxide‐ion/electron conductors, like gadolinium‐doped ceria (GDC), to commonly used nickel‐based anodes is a well–known strategy that significantly enhances the performance of the SOFCs. Here we provide in situ experimental evidence of the active surface oxidation state and composition of Ni/GDC anodes during methane electroxidation using realistic solid oxide electrode assemblies. Ambient pressure X‐ray photoelectron and near edge X‐ray absorption fine structure spectroscopies (APPES and NEXAFS respectively) combined with on line electrical and gas phase measurements, were used to directly associate the surface state and the electrocatalytic performance of Ni/GDC anodes working at intermediate temperatures (700°C). A reduced anode surface (Ce³⁺ and Ni), with an optimum Ni to Ce surface composition, were found to be the most favorable configuration for maximum cell currents. Experimental results are rationalized on the basis of first principles calculations, proposing a detailed mechanism of the cell function.     

Progress and Prospects in Symmetrical Solid Oxide Fuel Cells with Two Identical Electrodes

Symmetrical solid oxide fuel cells (SOFCs) have attracted increasing attention due to their potential for improved thermomechanical compatibility of the electrolyte and the electrodes, reduced fabrication cost, and enhanced immunity to coking and sulfur poisoning. While the electrode materials of symmetrical SOFCs are initially limited to those with stable phase structures under both reducing and oxidizing atmospheres, many novel electrode materials are currently being developed and investigated that may undergo a beneficial phase transition or reduction in a reducing atmosphere, although the same material may be used initially for the construction of both anode and cathode. Here, the advances made in the development of electrode materials and structures for symmetrical SOFCs are summarized, including single‐phase electrodes, multi‐phase (composite) electrodes, and those that are reducible upon exposure to a reducing atmosphere. The electrical conductivity, thermomechanical properties, and redox behavior of these electrode materials, together with their performance and stability in different SOFCs, are discussed and analyzed. The problems associated with different types of symmetrical SOFCs are outlined and the materials that show promise as symmetrical electrodes are highlighted, offering critical insights and useful guidelines for knowledge‐based rational design of better electrodes for commercially viable symmetrical SOFCs.     

Recent Progress in the Development of Anode Materials for Solid Oxide Fuel Cells

The field of research into solid oxide fuel cell (SOFC) anode materials has been rapidly moving forward. In the four years since the last in‐depth review significant advancements have been made in the reduction of the operating temperature and improvement of the performance of SOFCs. This progress report examines the developments in the field and looks to draw conclusions and inspiration from this research. A brief introduction is given to the field, followed by an overview of the principal previous materials. A detailed analysis of the developments of the last 4 years is given using a selection of the available literature, concentrating on metal‐fluorite cermets and perovskite‐based materials. This is followed by a consideration of alternate fuels for use in SOFCs and their associated problems and a short discussion on the effect of synthesis method on anode performance. The concluding remarks compile the significant developments in the field along with a consideration of the promise of future research. The recent progress in the development of anode materials for SOFCs based on oxygen ion conducting electrolytes is reviewed.     

Solid Oxide Fuel Cells: Microstructure of Nanoscaled La0.6Sr0.4CoO3‐δ Cathodes for Intermediate‐Temperature Solid Oxide Fuel Cells (Adv. Energy Mater. 2/2011)

Nanocrystalline La_1‐xSr_xCoO_3‐δ (LSC) thin films with a nominal Sr‐content of x = 0.4 were deposited on Ce_0.9Gd_0.1O_1.95 electrolyte substrates using a low temperature sol‐gel process. The structural and chemical properties of the LSC thin films were studied after thermal treatment, which included a calcination step and a variable, extended annealing time at 700 °C or 800 °C. Transmission electron microscopy combined with selected‐area electron diffraction, energy‐dispersive X‐ray spectrometry, and scanning transmission electron microscopy tomography was applied for the investigation of grain size, porosity, microstructure, and analysis of the local chemical composition and element distribution on the nanoscale. The area specific resistance (ASR) values of the thin film LSC cathodes, which include the lowest ASR value reported so far (ASR_chem = 0.023 Ωcm² at 600 °C) can be interpreted on the basis of the structural and chemical characterization.     

Development and Performance of MnFeCrO4‐Based Electrodes for Solid Oxide Fuel Cells

Important advances have been made in SOFC development utilizing a ceramic framework based upon yttria zirconia (YSZ) electrolytes supported upon porous YSZ electrode skeletons. This ceramic framework is sintered at high temperatures with subsequent impregnation and low temperature processing of the active electrode materials. Here we seek to develop this impregnated electrode concept by investigating a novel scaffold material similar to the main corrosion product of ferritic stainless steel. The chromium rich spinel (MnFeCrO₄) was used as an electrode support material, either alone or impregnated with (La_0.75Sr_0.25)_0.97Cr_0.5Mn_0.5O_3‐δ, La_0.8Sr_0.2FeO_3‐δ, Ce_0.9Gd_0.1O_2‐δ, CeO₂ and/or Pd. In these initial studies it was found that all of the impregnated phases adhere very well to the spinel and considerably enhance performance and stability to a level sufficient for SOFC applications.     

Advances in Cathode Materials for Solid Oxide Fuel Cells: Complex Oxides without Alkaline Earth Metal Elements

Solid oxide fuel cells (SOFCs) represent one of the cleanest and most efficient options for the direct conversion of a wide variety of fuels to electricity. For example, SOFCs powered by natural gas are ideally suited for distributed power generation. However, the commercialization of SOFC technologies hinges on breakthroughs in materials development to dramatically reduce the cost while enhancing performance and durability. One of the critical obstacles to achieving high‐performance SOFC systems is the cathodes for oxygen reduction reaction (ORR), which perform poorly at low temperatures and degrade over time under operating conditions. Here a comprehensive review of the latest advances in the development of SOFC cathodes is presented: complex oxides without alkaline earth metal elements (because these elements could be vulnerable to phase segregation and contaminant poisoning). Various strategies are discussed for enhancing ORR activity while minimizing the effect of contaminant on electrode durability. Furthermore, some of the critical challenges are briefly highlighted and the prospects for future‐generation SOFC cathodes are discussed. A good understanding of the latest advances and remaining challenges in searching for highly active SOFC cathodes with robust tolerance to contaminants may provide useful guidance for the rational design of new materials and structures for commercially viable SOFC technologies.     

Advanced Multi‐Fuelled Solid Oxide Fuel Cells (ASOFCs) Using Functional Nanocomposites for Polygeneration

An advanced multifuelled solid oxide fuel cell (ASOFC) with a functional nanocomposite was developed and tested for use in a polygeneration system. Several different types of fuel, for example, gaseous (hydrogen and biogas) and liquid fuels (bio‐ethanol and bio‐methanol), were used in the experiments. Maximum power densities of 1000, 300, 600, 550 mW cm^?2 were achieved using hydrogen, bio‐gas, bio‐methanol, and bio‐ethanol, respectively, in the ASOFC. Electrical and total efficiencies of 54% and 80% were achieved using the single cell with hydrogen fuel. These results show that the use of a multi‐fuelled system for polygeneration is a promising means of generating sustainable power.     

Micro‐Solid Oxide Fuel Cell Membranes Prepared by Aerosol‐Assisted Chemical Vapor Deposition

Free‐standing electrolyte membranes for low‐temperature micro‐solid oxide fuel cells (micro‐SOFCs) are prepared by aerosol‐assisted chemical vapor deposition (AA‐CVD), a cost‐effective, non‐vacuum thin‐film deposition technique. Thin, yttria‐stabilized zirconia (YSZ) membranes (50–400 nm) as well as bilayer membranes of YSZ and gadolinia‐doped ceria are prepared at temperatures of 600 °C and below. AA‐CVD, which is a gas‐phase deposition method, allows for the synthesis of precursor‐free crystalline layers, thereby limiting the development of tensile stress. High membrane survival rates of around 90% are thus obtained. The columnar structure of the electrolyte ensures high oxygen‐ion conductivity and results in negligible ohmic losses. Using sputtered platinum electrodes, the demonstration of a micro‐SOFC based on AA‐CVD electrolyte is achieved and first power density data of 166 mW cm^‐2 at 410 °C is obtained.     

Effect of Elastic Network of Ceramic Fillers on Thermal Cycle Stability of a Solid Oxide Fuel Cell Stack

Glass‐based seals for planar solid‐oxide fuel‐cell (SOFC) stacks are open to uncontrolled deformation and mechanical damages, limiting both sealing integrity and stack reliability, particularly in thermal cycle operations. If the glass‐based seals work like an elastomer‐based compressive seal, SOFC stacks may survive unprecedented numbers of thermal cycles. A novel composite sealing gasket is successfully developed to mimic the unique features of the elastomer‐based compressive seal by controlling the composition and packing behavior of binary ceramic fillers. A single‐cell SOFC stack undergoes more than 100 thermal cycles with little performance loss, during which the sealing integrity is lost/recovered repeatedly upon cooling and reheating, corresponding to unloading/loading of the elastomer‐based compressive seal. The thermal‐cycle responses of the SOFC stack are explained in sequence by the concurrent events of elastic deformation/recovery of ceramic filler network and corresponding redistribution of sealing glass.     

Nanoscale Compositionally Graded Thin‐Film Electrolyte Membranes for Low‐Temperature Solid Oxide Fuel Cells

Controllable fabrication of compositionally graded Gd_0.1Ce_0.9O_2‐δ and Y_0.16Zr_0.84O_2‐δ electrolytes using co‐sputtering is demonstrated. Self‐supported membranes were lithographically fabricated to employ the new electrolytes into thin film solid oxide fuel cells. Devices integrating such electrolytes demonstrate performance of over 1175 mW cm^?2 and 665 mW cm^?2 at 520 °C using hydrogen and methane as fuel, respectively. The results present a general strategy to fabricate nanoscale functionally graded materials with selective interfacial functionality for energy conversion.     

Strontium Diffusion in Magnetron Sputtered Gadolinia‐Doped Ceria Thin Film Barrier Coatings for Solid Oxide Fuel Cells

Strontium (Sr) diffusion in magnetron sputtered gadolinia‐doped ceria (CGO) thin films is investigated. For this purpose, a model system consisting of a screen printed (La,Sr)(Co,Fe)O_3?δ (LSCF) layer, and thin films of CGO and yttria‐stabilized zirconia (YSZ) is prepared to simulate a solid oxide fuel cell. This setup allows observation of Sr diffusion by observing SrZrO₃ formation using X‐ray diffraction while annealing. Subsequent electron microscopy confirms the results. This approach presents a simple method for assessing the quality of CGO barriers without the need for a complete fuel cell test setup. CGO films with thicknesses ranging from 250 nm to 1.2 μm are tested at temperatures from 850 °C to 1000 °C which yields an in‐depth understanding of Sr diffusion through CGO thin films that may be of high scientific and technical interest for implementation of novel fuel cell materials. Sr is found to diffuse along column/grain boundaries in the CGO films but by modifying the film thickness and microstructure the breaking temperature of the barrier can be increased.     

High‐Performance Silver Cathode Surface Treated with Scandia‐Stabilized Zirconia Nanoparticles for Intermediate Temperature Solid Oxide Fuel Cells

This work introduces a novel silver composite cathode with a surface coating of scandia‐stabilized zirconia (ScSZ) nanoparticles for application in intermediate temperature solid oxide fuel cells (IT‐SOFCs). The ScSZ coating is expected to maximize the triple boundary area of the Ag electrode, ScSZ electrolyte, and oxygen gas, where the oxygen reduction reaction occurs. The coating also protects the porous Ag against thermal agglomeration during fuel cell operation. The ScSZ nanoparticles are prepared by sputtering scandium‐zirconium alloy followed by thermal oxidation on Ag mesh. The performance of the solid oxide fuel cells with a gadolinia‐doped ceria electrolyte support is evaluated. At temperatures <500 °C, our optimized Ag‐ScSZ cathode outperforms the bare Ag cathode and even the platinum cathode, which has been believed to be the best material for this purpose. The highest cell peak power with the Ag‐ScSZ cathode is close to 60 mW cm^?2 at 450 °C, while bare Ag and optimized Pt cathodes produce 38.3 and 49.4 mW cm^?2, respectively. Long‐term current measurement also confirms that the Ag‐ScSZ cathode is thermally stable, with less degradation than bare Ag or Pt.     

Anion Doping: A New Strategy for Developing High‐Performance Perovskite‐Type Cathode Materials of Solid Oxide Fuel Cells

Overcoming the sluggish activity of cathode materials is critical to realizing the wide‐spread application of intermediate‐temperature solid oxide fuel cells. Herein, a new way is reported to tune the performance of perovskite‐type materials as oxygen reduction electrodes by embedding anions (F^?) in oxygen sites. The obtained perovskite oxyfluorides SrFeO_{3?σ ?δ} F_σ and SrFe_0.9Ti_0.1O_{3?σ ?δ} F_σ (σ = 0.05 and 0.10) show improved electrocatalytic activity compared to their parent oxides, achieving area specific resistance values of 0.875, 0.393, and 0.491 Ω cm² for SrFeO_3?δ , SrFeO_2.95?δ F_0.05, and SrFeO_2.90?δ F_0.10, respectively, at 600 °C in air. Such improved performance is a result of the improved bulk diffusion and surface exchange properties due to anion doping. Moreover, favorable stability in performance is also demonstrated for the F^? anion‐doped perovskites as oxygen reduction electrodes at 650 °C for a test period of ≈200 h. A combination of anion doping and cation doping may provide a highly attractive strategy for the future development of cathode materials.