Chemical Compatibility and Electrical Contact of LaNi0.6Co0.4O3–δ (LNC) between Crofer22APU Interconnect and La0.6Sr0.4FeO3 (LSF) Cathode for IT‐SOFC

In order to simulate the contact situation of interconnect/contact layer/cathode in SOFC stacks, contact resistance and chemical compatibility of LaNi_0.6Co_0.4O_3–δ (LNC) as contact layer between Crofer22APU interconnect and La_0.6Sr_0.4FeO₃ (LSF) cathode was investigated at 800 °C in air for more than 1300 h using X‐ray diffraction (XRD), scanning electron microscopy (SEM) set‐up equipped with an energy dispersive X‐ray analyser (EDX) and area specific resistance (ASR) measurements. The XRD analysis reveals that multiple phases were formed during ASR test. The point microanalysis on cross‐section of Fe–Cr/LNC/LSF system, after ASR measurements, shows chromium within the porous contact material mainly concentrated close to interconnect, but no Cr, Ni, or Co was detected in the cathode. It was found between LNC and LSF cathode, a thin and uniform layer which contains Sr, La, Cr, Co, Ni, and Fe. The contact between layers could act as a physical barrier for element migration and thus can suppress degradation of the cathode for these systems. The area specific resistance slope depends on the interactions between the contact material and/or cathode and the interconnect. Co‐containing spinels formed during ASR test can be responsible of the resistance decrease of the system, related to the low degradation of the cell.     

Investigation of Impactors on Cell Degradation Inside Planar SOFC Stacks

The impactors on cell degradation inside planar SOFC stacks were investigated using both coated and uncoated Fe–16Cr alloys as the interconnects under stable operating conditions at 750 °C and thermal cycling conditions from 750 to 200 °C. It was found that cell degradation inside the stack is primarily dependent on the interfacial contact between the cathode current‐collecting layer and the interconnect. Additionally, cell degradation is found to be independent of the high‐temperature oxidation and Cr vaporization of the interconnects during stack operation, as the stacks are well sealed. The coating on the interconnect can further improve the contact between the cell cathode and the interconnect when the latter is properly embedded into the current‐collecting layer.     

Electrochemical properties of A-site deficient SOFC cathodes under Cr poisoning conditions

Under solid oxide fuel cells (SOFCs) operating atmosphere, volatile Cr species are generated over the chromia scale of chromia-forming alloy interconnects, poisoning the cathodes and causing the rapid degradation of the fuel cell performance. In this study, the influence of the cathode composition and A-site deficiency of Perovskite ABO₃ cathodes on their tolerance to Cr poisoning was investigated in detail through the electrochemical polarization and electrochemical impedance spectroscopy (EIS) analysis. Results showed that 5 mol% La-site deficient cathodes, La_0.75Sr_0.2BO_3−δ (B = Mn, Fe), presented a good performance in resistance to Cr poisoning and electrocatalytic activity to oxygen reduction reaction in the presence of alloy interconnects under a constant current density of 0.2 A cm⁻² in oxygen at 1073 K. B-site atom of Perovskite ABO₃ cathodes has a strong influence on the mechanism of Cr deposition and cathodes performance, while proper A-site deficiency can greatly improve the cathodes electrochemical performance and slow down Cr deposition.     

Chromium poisoning for prolonged lifetime of electrodes in solid oxide fuel cells - Review

Solid Oxide Fuel Cells (SOFCs) offer low carbon emission and high efficient energy conversion systems. For the wide commercial distribution of this system, one of the technological issues and challenges is prolonged durability: the SOFC systems should have a long lifetime of more than 10 years. The volatile chromium species poisoning is the key degradation factor to overcome at the functional ceramics of air electrode (cathode)/interlayer/electrolyte interfaces in the SOFC system among many degradation factors. This paper reports recent degradation mechanisms, especially on the chromium (Cr) vapors poisoning at the perovskite oxide cathode. The Cr-concentration levels at cathodes were evaluated from the reported data at small cells and practical cell-stacks. The interactions of volatile Cr species and perovskite oxide cathode surface were evaluated by the chemical reaction of cathode materials with Cr-vapors to form SrCrO₄ and the electrochemical induced Cr-vapors reduction (Cr⁶⁺ to Cr³⁺) to form Cr₂O₃ at (La,Sr,Ca)MnO₃-based and (La,Sr)(Co,Fe)O₃-based materials. Recovery mechanism from Cr-poisoning was reanalyzed at the (La,Sr)(Co,Fe)O₃/ceria-based interlayer/YSZ electrolyte interfaces by Cr-cleaning reaction with the evaporation of Cr₂O₃/SrCrO₄ and nano-meter level cation migration/rearrangement effects with phase separation and new phases formation. This paper is covering not only the elucidation of degradation mechanism but also the fundamentals of physical and chemical analyses on perovskite oxide cathode surface and interfaces. An insight for new materials combination for the next-generation SOFCs is also included.     

Evaluation of Using LaNi0.6Fe0.4O3–δ Contact Layer Between La0.6Sr0.4FeO3 Cathode and Crofer22APU Interconnect for Solid Oxide Fuel Cells

Interconnect‐cathode interfacial adhesion is important for the durability of solid oxide fuel cell (SOFC). Thus, the use of a conductive contact layer between interconnect and cathode could reduce the cell area specific resistance (ASR). The use of La_0.6Sr_0.4FeO₃ (LSF) cathode, LaNi_0.6Fe_0.4O_3–δ (LNF) contact layer and Crofer22APU interconnect was proposed as an alternative cathode side. LNF‐LSF powder mixtures were heated at 800 °C for 1,000 h and at 1,050 °C for 2 h and analyzed by X‐Ray power diffraction (XRD). The results indicated a low reactivity between the materials. The degradation occurring between the components of the half‐cell (LSF/LNF/Crofer22APU) was studied. XRD results indicated the formation of secondary phases, mainly: SrCrO₄, A(B, Cr)O₃ (A = La, Sr; B = Ni, Fe) and SrFe₁₂O₁₉. Scanning electron microscopy with energy dispersive X‐Ray spectroscopy (SEM‐EDX) and the X‐Ray photoelectron spectroscopy (XPS) analyzes confirmed the interaction between LSF/LNF and the metallic interconnect due to the Cr vaporization/migration. An increment of the resistance of ∼0.007 Ω cm² in 1,000 h is observed for (LSF/LNF/Crofer22APU) sample. However, the ASR values of the cell without contact coating, (LSF/Crofer22APU), were higher (0.31(1) Ω cm²) than those of the system with LNF coated interconnect (0.054(7) Ω cm²), which makes the proposed materials combination interesting for SOFC.     

Evaluation of a Single Cell and Candidate Materials with High Water Content Hydrogen in a Generic Solid Oxide Fuel Cell Stack Test Fixture,Part II: Materials and Interface Characterization

A generic solid oxide fuel cell (SOFC) test fixture was developed to evaluate candidate materials under realistic operating conditions. A commercial 50 mm × 50 mm NiO‐YSZ anode‐supported thin YSZ electrolyte cell with lanthanum strontium manganite (LSM)/YSZ cathode was tested to evaluate the stability of candidate materials. The cell was tested in two stages at 800°C: stage I with low (~3% H₂O) humidity and stage II with high (~30% H₂O) humidity hydrogen fuel in constant voltage or constant current mode. Part I of the work, published previously, provided information regarding the generic test fixture design, materials, cell performance, and optical post‐mortem analysis. In part II, detailed microstructure and interfacial characterizations are reported regarding the SOFC candidate materials: (Mn,Co)‐spinel conductive coating, alumina coating for sealing area, ferritic stainless steel interconnect, refractory sealing glass, and their interactions with each other. Overall, the (Mn,Co)‐spinel coating was very effective in minimizing Cr migration. No Cr was identified in the cathode after 1720 h at 800°C. Aluminization of metallic interconnects also proved to be chemically compatible with alkaline‐earth silicate sealing glass. The details of interfacial reaction and microstructure development are discussed.     

Moisture Effect on La0.8Sr0.2MnO3 and La0.6Sr0.4Co0.2Fe0.8O3 Cathode Behaviors in Solid Oxide Fuel Cells

Moisture effect on cathode behaviors is a major issue for solid oxide fuel cells servicing under severe high temperature environments. This work studies the effect of dry air and moist air on La_0.8Sr_0.2MnO₃ (LSM821) and La_0.6Sr_0.4Co_0.2Fe_0.8O₃ (LSCF6428) cathodes at 800 °C by investigating the interfacial reaction and degradation through an AISI 441 interconnect/LSM821 (LSCF6428) electrode/yttria‐stabilized zirconia (YSZ) electrolyte tri‐layer structure. Under the same processing condition, the grain size of the LSCF6428 cathode is smaller than that of the LSM821 cathode. Ohmic resistance and polarization resistance of the cathodes are analyzed by deconvoluting the electrochemical impedance spectroscopy (EIS) results. The LSCF6428 cathode has much smaller resistance than the LSM821 cathode. Moisture produces a larger effect on the ohmic resistance and polarization resistance of the LSM821 cathode than on those of the LSCF6428 cathode. More chromium diffuses from the interconnect to the cathode for both LSM821 and LSCF6428 electrodes thermally treated in moist air. Based on the structure, elemental distribution, and EIS analysis, the interaction mechanisms between the electrodes and the AISI 441 alloy interconnect are proposed.     

Effect of Contact Method between Interconnects and Electrodes on Area Specific Resistance in Planar Solid Oxide Fuel Cells

In this work, interconnect/electrode sheet/interconnect sandwiches are assembled by designing interfacial contact between interconnects and electrodes for planar solid oxide fuel cells (SOFCs). Their area specific resistance (ASR) values of different contact methods under isothermal oxidation and thermal cycling are recorded by four‐point method. The ASR of SUS430/Ni–YSZ/SUS430 anode sandwich with NiO current collecting layer is close to that of anode sandwich without NiO current collecting layer during isothermal operation, but smaller and more stable during thermal cycling. Meanwhile, the lowest ASR is obtained in SUS430/LSM–YSZ/SUS430 cathode sandwich with LSM coated interconnect and LSM current collecting layer among various contact methods between interconnects and cathodes, and remains constant under isothermal oxidation and thermal cycling. Contact resistance between cathodes and interconnects is the main source of the SOFC stack resistance. A real stack with three anode‐supported cells is assembled and tested under thermal cycling to verify the effect of different contact methods between interconnects and electrodes on performance of stack repeating unit. The degradation rate and ASR values of repeating unit inside the stack indicate that the contact between LSM coated interconnect and LSM current collecting layer on cathode side is the optimized contact.     

Effect of Contact between Electrode and Interconnect on Performance of SOFC Stacks

This work investigates the effect of contact between electrodes and alloy interconnects on output performance of solid oxide fuel cell (SOFC) stacks. The measured maximum output power density (p_max) of the unit cell increases from 0.07 to 0.1 W cm^–2 by increasing the tip area of the interconnect from 40 to 60 cm². The p_max increases from 0.07 to 0.15 W cm^–2 upon the addition of nickel foam and Ag mesh on the anode and cathode side, respectively. An additional (La_0.75Sr_0.25)_0.95MO_3–σ cathode current collecting layer is re‐printed on the original cathode current collecting layer, which aims to further improve the performance of the stack and individual cell. The performance of a 3‐cell short stack assembled by the cells with a new cathode current collecting layer is evaluated by measuring the current–voltage curve. The results indicate that the p_max values of the stack and individual cells are enhanced from 0.07 to 0.37 W cm^–2 and 0.15 to 0.5 W cm^–2 at 850 °C, respectively. The performance of the whole stack and individual cells is greatly improved due to the interconnect embedded in the re‐printed new cathode current collecting layer.     

Electrochemical nucleation and growth of copper on chromium-plated electrodes

Nucleation and growth of copper electrodeposited on chromium plated electrodes in copper sulfate electrolytes were examined, focusing on the influence of prior Cr plating conditions on the nucleation density and growth kinetics of the copper electrodeposits. The Cr-plated electrodes were made by electrodeposition of Cr on copper sheets for 2 to 60 s at 0.1 A cm^–2 in CrO₃ 350 g L^–1 + H₂SO₄ 3.5 g L^–1. Copper was then electrodeposited onto the Cr-plated electrode under potentiostatic conditions. Copper initially nucleated and grew according to a three-dimensional diffusion controlled progressive nucleation process, and later according to an instantaneous nucleation process. The period during which copper nucleation is controlled by the diffusion controlled progressive nucleation process decreases with increasing Cr plating time. The nucleation density of copper was extremely high on the 2 s Cr-plated electrode, producing an extremely fine and uniform electrodeposit. However, on the 4 s Cr-plated electrode, the nucleation density of copper significantly reduced to one hundredth of that on the 2 s Cr-plated electrode, and then decreased slightly with increasing Cr plating time (thickness of Cr layer). These results appear to be associated with the IR drop across the Cr layer, including the surface Cr oxide/hydroxide film (termed the cathode film), which significantly reduces the driving force for the electrodeposition of copper under potentiostatic plating conditions.     

Ferritic Cathodes Degradation by Potassium/Chromium Poisoning and Air Humidification

Degradation mechanisms inherent to ferritic LSF‐SDC and LSCF‐GDC cathodes are studied by post‐mortem analysis of cells which suffered the most significant performance deterioration in a set of 18 500 h tests carried out under a specific experimental design. Three cathode processing parameters (composition, thickness, and sintering temperature) were combined with five operation conditions (chromium presence, current density, operating temperature, air flow, and humidification) through this design of experiments based in a L₁₈ Taguchi matrix. In the case of cells exposed to chromium vapors from Crofer 22 APU pieces, those cells which exhibited K₂Cr₂O₇ deposition in the cathode/GDC barrier interface underwent the most aggressive ASR degradation. Similar deposits were also observed on the surface of LSC current collectors. Two cells exposed to highly humidified air (20%) exhibited cathode delamination and GDC barrier deterioration by crack propagation though no foreign elements diffusion to the interface could be detected.     

Electrical Properties,Cation Distributions,and Thermal Expansion of Manganese Cobalt Chromite Spinel Oxides

As the oxidation and chromium volatilization of chromia‐forming alloy interconnects can cause Solid oxide fuel cells (SOFC) cathode poisoning and cell degradation, spinel coatings like Mn_1.5Co_1.5O₄ have been applied as a barrier to oxygen and chromium diffusion. To evaluate their long‐term stability, the properties of the reaction layer between the Mn_1.5Co_1.5O₄ coating and Cr₂O₃ scale formed on the alloy surface need to be characterized. Therefore, compositions of Mn_1.5?0.5xCo_1.5?0.5xCr_xO₄ (x = 0–2) were prepared to investigate their electrical properties, cation distributions, and thermal expansion behavior at high temperature. With increasing Cr content in manganese cobalt spinel oxides, the cubic crystal structure is stabilized and the electrical conductivity and coefficient of thermal expansion both decrease. The cation distributions determined from neutron diffraction show that Cr and Mn have stronger preference for octahedral sites in the spinel structure as compared with Co.     

Degradation of La0.6Sr0.4Co0.2Fe0.8O3–δ–Ce0.8Sm0.2O1.9 Cathodes on Coated and Uncoated Porous Metal Supports

The degradation of composite LSCF‐SDC cathodes on porous 430 stainless steel supports was investigated. Two degradation mechanisms were observed: a multi‐layer oxide scale, believed to consist of Cr₂O₃ and SrCrO₄, formed at the support‐cathode interface, and small amounts of chromium were detected within the cathodes. To reduce degradation, La₂O₃ and Y₂O₃ reactive element oxide coatings were deposited on the internal pore surfaces of the metal supports. The reactive element oxide coatings reduced the amount of volatile chromium that deposited in the cathodes. As a result, the degradation rates of the cathodes on coated supports were significantly lower than the degradation rates of cathodes made on uncoated metal supports. In cathode symmetrical cells, polarization resistance degradation rates as low as 2.56 × 10⁻⁶ Ω cm² h⁻¹ were observed over 100 hours on coated metal supports, compared to an average of 1.23 × 10⁻⁴ Ω cm² h⁻¹ on uncoated supports.     

Shunt current protocol to eliminate reversible degradation of polymer electrolyte membrane fuel cells during constant load operations

The objective of this study is to determine the durability of polymer electrolyte membrane fuel cells (PEMFCs) in constant current operation incorporated with regular recovery protocol for eliminating reversible performance loss of membrane electrode assemblies. Effects of operation ‘shunt current protocol’ on PEMFC durability are studied through analyses of the main degradation mechanism based on results of electrochemical characterizations and post-mortem investigations. The voltage of the protected cell using the shunt current protocol is stably preserved under the applied current density for 700 h with less degradation (4.2% of decay ratio), while the performance of the unprotected cell steadily decreased with time (15.1% over 700 h). The substantial performance deterioration of the unprotected cell is mainly attributed to morphology deterioration of the cathode catalyst layer with oxidation of Pt catalysts and chemical degradation of ionomers caused by generation of excessive water from electrochemical oxygen reduction reactions under high-humidity operating conditions. In contrast, the shunt current protocol plays an important role in sustaining high oxygen activity at the cathode catalyst surface, detaching partially covered OH⁻ species on Pt active sites from water oxidation during cell operation caused by periodically applied shunt current for a very short period of 1 s every 5 h. We hope to provide insight into the operation protocol to extend the lifetime of PEMFCs, minimizing conversion from recoverable performance loss to irreversible (permanent) degradation during operation.     

Modeling of the Area‐specific Resistance of SOFC Cathodes by Application of a Square Grain Model Involving Grain Boundaries

A square grain model is proposed for the calculation of the area‐specific resistance (ASR) of porous cathodes for solid oxide fuel cells (SOFCs) by means of the finite element approach. The grains and pores are represented by squares of equal side length. The grain boundaries are assumed to be thin slabs of uniform thickness. Both blocking conditions for the ionic current and fast transport of oxide ions along the grain boundaries have been taken into account. The results of the simulation suggest that highly active cathode materials could be developed by increasing the grain boundary ionic conductivity. In the case of an average grain size of 0.1 μm, a remarkable decrease of the ASR is predicted, if the ionic conductivity of the grain boundaries exceeds that of the bulk by a factor of 100. The model has been applied to simulate the increase of the ASR due to degradation of La_0.6Sr_0.4CoO_3–δ in dry and humid atmospheres at 600 °C. A rapid increase of the ASR is predicted in H₂O‐containing atmospheres. The effect of Cr‐poisoning on the ASR has been modeled for dry and humid atmospheres at 600 °C. The degradation owing to Cr‐poisoning is most pronounced in atmospheres containing water vapor.     

Toward optimisation of electrolytic reduction of solid chromium oxide to chromium powder in molten chloride salts

Electrochemical reduction of solid Cr₂O₃, in the form of an assembled cathode of porous pellets attached to a current collector, to chromium powder was investigated in molten CaCl₂ and a molten equimolar mixture of CaCl₂ and NaCl. The study focused on the influence of pellets preparation conditions, cell voltages and temperatures on the reduction process. Analyses were reported of the characteristics of the current-time plots of the constant voltage electrolysis under different conditions, cyclic voltammograms of solid Cr₂O₃ in the molten equimolar mixture of CaCl₂ and NaCl, the microstructures and elemental compositions of the reduced pellets. Particularly, attention was given to the intermediate product of the electrolysis, calcium chromites of various stoichiometries, aiming to achieve a better understanding and optimisation of the reduction process.     

Passivity of OC404 steel modified electrochemically with CeO2-Ce2O3 layers in sulfuric acid media

The effect of cerium oxides film, formed electrochemically on OC404 stainless steel (SS), upon the corrosion behavior of steel in 0.1N H₂SO₄ was investigated. The modification of the steel surface by deposition of cerium oxides films was found to improve the steel corrosion resistance. A linear dependence between the stationary corrosion potential of the cerium oxides/SS system and the cerium concentration in the oxide film was established. The shift of the corrosion potential in the positive direction was found to depend on the proceeding of a depolarizing cathode reaction of CeO₂ reduction (instead of the hydrogen depolarizing reaction) occurring on the cathodic zones, formed by this oxide. On the basis of XPS analyses of the samples, subjected to real corrosion under the conditions of self-dissolution, a pronounced drop of the surface concentration of CeO₂ was established. This is a proof of the occurrence of an effective cathode process of CeO₂ reduction to Ce₂O₃, which was then dissolved in H₂SO₄. Data were obtained (XPS) on the composition and structure of the surface film (SEM) after electrodeposition of cerium oxides and after corrosion in the sulfuric acid medium under consideration for time intervals ranging from 50 up to 1000 h. The ICP-AES studies acquired data on the quantity of dissolved elements, forming the passive layer. After exposure to the corrosive medium, the deposited layer showed enrichment in oxides of chromium and aluminium. The passive film on stainless steel, modified in this way, proved to be more stable to the effect of aggressive sulfuric acid medium, compared to the case of natural passive film.     

Formation of ferrospinel layer at the corroded interface between Al2O3-spinel refractory and molten steel in RH refining ladle

Refining ladle is generally the last inclusion-removal vessel before the continuous casting of steel, so, it has a vital effect on the final steel quality. In this work, degradation process of a cement-free Al₂O₃-MgAl₂O₄ refractory in contact with molten steel/slag in the metal bath area of a Ruhrstahl Heraeus (RH) refining ladle was investigated. A reaction product layer with the formation of ferrospinel (hercynite) and Fe-rich phases was observed, suggesting that the interactions/reactions between the refractory lining and the molten steel should also be considered to have a better understanding of overall degradation mechanism of the refractory served under the RH refining conditions. The two types of alumina grains in the refractory, sintered and fused alumina, were attacked in an active way and a passive way, respectively. The effect of the crack generation and steel infiltration on degradation of the refractory was also discussed in detail, based on the microstructural characterizations.     

Fabrication of a miniature twin-fuel-cell on silicon wafer

The fabrication and performance evaluation of a miniature twin-fuel-cell on silicon wafers are presented in this paper. The miniature twin-fuel-cell was fabricated in series using two membrane-electrode-assemblies sandwiched between two silicon substrates in which electric current, reactant, and product flow. The novel structure of the miniature twin-fuel-cell is that the electricity interconnect from the cathode of one cell to the anode of another cell is made on the same plane. The interconnect was fabricated by sputtering a layer of copper over a layer of gold on the top of the silicon wafer. Silicon dioxide was deposited on the silicon wafer adjacent to the copper layer to prevent short-circuiting between the twin cells. The feed holes and channels in the silicon wafers were prepared by anisotropic silicon etching from the back and front of the wafer with silicon dioxide acting as intrinsic etch-stop layer. Operating on dry H₂/O₂ at 25 °C and atmospheric pressure, the measured peak power density was 190.4 mW/cm² at 270 mA/cm² for the miniature twin-fuel-cell using a Nafion 112 membrane. Based on the polarization curves of the twin-fuel-cell and the two single cells, the interconnect resistance between the twin cells was calculated to be in the range from 0.0113 Ω (at 10 mA/cm²) to 0.0150 Ω (at 300 mA/cm²), which is relatively low.     

All-solid-state MoS2/WO3 photoelectrodes as high-efficiency catalysts for reductive/sorptive/recycling of hexavalent chromium

Photoelectrocatalysis (PEC) is an effective approach to eliminate carcinogen hexavalent chromium (Cr(VI)) in wastewater, in which high-performance catalysts are crucial. Herein, controlled growth of thin molybdenum disulphide (MoS₂) nanosheets on self-supported tungsten trioxide (WO₃) created an all-solid-state MoS₂/WO₃ heterojunction serving as electrode and catalyst simultaneously for removing Cr(VI). Countless small and thin MoS₂ nanoflakes build in a huge and porous interface for harvesting lights and adsorbing chromium species. And the highly conductive WO₃ substrate facilitates the transfer of those photoexcited-electron and therefore suppresses the recombination between electrons and holes. Furthermore, assisted by bias potential, electron streams from external circuit render an electron-rich interface at the MoS₂/WO₃ cathode, accelerating the Cr(VI) reduction by PEC. At −1.2 V, the PEC reduction efficiency of Cr(VI) reaches 100% within 30 min, surpassing the pristine WO₃ by 2.7 times. The generated Cr(III) ions can be immobilized on the porous MoS₂/WO₃ cathode through electrostatic attraction, enabling removal of total chromium. More importantly, the Cr(III) anchored to the catalyst can be effortlessly recovered by eluting with clean water, which also refreshes the MoS₂/WO₃ cathode. This study provides a new approach to fabricating photoelectrodes for sustainable PEC reduction and treatment of Cr(VI) containing wastewater.