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

SOFC anodes impregnated with noble metal catalyst nanoparticles for high fuel utilization

Redox-stable solid oxide fuel cell (SOFC) anodes are developed in order to improve durability at higher fuel utilization, as a possible alternative to conventional Ni-zirconia cermet anodes. Ce0.9Gd0.1O2 (GDC) is utilized as a mixed ionic and electronic conductor (MIEC), in combination with Sr0.9La0.1TiO3 (LST) as an electronic conductor. The stability of noble metals (Rh, Pt, and Pd) is analyzed via thermochemical calculation of stable phases. Noble metal catalyst nanoparticles are incorporated via co-impregnation with GDC. The electrochemical characteristics of SOFC single cells using these anode materials are investigated in highly-humidified H2 at 800 °C. Their stability at high fuel utilization is analyzed. These co-impregnated anodes with highly dispersed noble metal catalysts on the LST-GDC conducting backbones, achieve high I[sbnd]V performance comparable to conventional Ni-cermet anodes. The co-impregnated anodes also achieve considerably high catalytic mass activity. At higher oxygen partial pressure, where the Ni catalyst can be deactivated by oxidation, these noble catalysts are thermochemically stable in the metallic state, and tolerant against oxidation. This class of alternative catalyst, impregnated with low-loading of noble metals could contribute to stable operation in the downstream region of SOFC systems. A simple cost analysis indicates a tolerance of using noble metals, provided their loading is sufficiently low

Exchange current density of reversible solid oxide cell electrodes

Reversible solid oxide cells (r-SOCs) can be operated in either solid oxide fuel cell or solid oxide electrolysis cell mode. They are expected to become important in the support of renewable energy due to their high efficiency for both power generation and hydrogen generation. The exchange current density is one of the most important parameters in the quantification of electrode performance in solid oxide cells. In this study, four different fuel electrodes and two different air electrodes are fabricated using different materials and the microstructures are compared. The temperature, fuel humidification, and oxygen concentration at the air electrode are varied to obtain the apparent exchange current density for the different electrode materials. In contrast to ruthenium-and-gadolinia-doped ceria (Rh-GDC) as well as nickel-and-gadolinia-doped ceria (Ni-GDC) electrodes, significant differences in the apparent exchange current density were observed between electrolysis and fuel cell modes for the nickel-scandia-stabilized zirconia (Ni-ScSZ) cermet. Variation of gas concentration revealed that surface adsorption sites were almost completely vacant for all these electrodes. The apparent exchange current densities obtained in this study are useful as a parameter for simulation of the internal properties of r-SOCs

Improved redox cycling durability in alternative Ni alloy-based SOFC anodes

Repeated reduction and oxidation of metallic nickel in the anodes of solid oxide fuel cell (SOFC) causes volume changes and agglomeration. This disrupts the electron conducting network, resulting in deterioration of the electrochemical performance. It is therefore desirable to develop more robust anodes with high redox stability. Here, new cermet anodes are developed, based on nickel alloyed with Co, Fe, and/or Cr. The stable phases of these different alloys are calculated for oxidizing and reducing conditions, and their electrochemical characteristics are evaluated. Whilst alloying causes a slight decrease in power generation efficiency, the Ni-alloy based anodes have significantly improved redox cycle durability. Microstructural observation reveals that alloying results in the formation of a dense oxide film on the surface of the catalyst particle (e.g. Co-oxide or a complex Fe-Ni-Cr oxide). These oxide layers help suppress oxidation of the underlying nickel catalyst particles, preventing oxidation-induced volume changes/agglomeration, and thereby preserving the electron conducting pathways. As such, the use of these alternative Ni-alloy based cermets significantly improves the redox stability of SOFC anodes

Cold start cycling durability of fuel cell stacks for commercial automotive applications

System durability is crucial for the successful commercialization of polymer electrolyte fuel cells (PEFCs) in fuel cell electric vehicles (FCEVs). Besides conventional electrochemical cycling durability during long-term operation, the effect of operation in cold climates must also be considered. Ice formation during start up in sub-zero conditions may result in damage to the electrocatalyst layer and the polymer electrolyte membrane (PEM). Here, we conduct accelerated cold start cycling tests on prototype fuel cell stacks intended for incorporation into commercial FCEVs. The effect of this on the stack performance is evaluated, the resulting mechanical damage is investigated, and degradation mechanisms are proposed. Overall, only a small voltage drop is observed after the durability tests, only minor damage occurs in the electrocatalyst layer, and no increase in gas crossover is observed. This indicates that these prototype fuel cell stacks successfully meet the cold start durability targets for automotive applications in FCEVs

Accelerated durability testing of fuel cell stacks for commercial automotive applications : a case study

System durability is crucially important for the successful commercialization of fuel cell electric vehicles (FCEVs). Conventional accelerated durability testing protocols employ relatively high voltage to hasten carbon corrosion and/or platinum catalyst degradation. However, high voltages are strictly avoided in commercialized FCEVs such as the Toyota MIRAI to minimize these degradation modes. As such, conventional durability tests are not representative of real-world FCEV driving conditions. Here, modified start-stop and load cycle durability tests are conducted on prototype fuel cell stacks intended for incorporation into commercial FCEVs. Polarization curves are evaluated at beginning of test (BOT) and end of test (EOT), and the degradation mechanisms are elucidated by separating the overvoltages at both 0.2 and 2.2 A cm-2. Using our modified durability protocols with a maximum cell voltage of 0.9 V, the prototype fuel cell stacks easily meet durability targets for automotive applications, corresponding to 15-year operation and 200,000 km driving range. These findings have been applied successfully in the development of new fuel cell systems for FCEVs, in particular the second-generation Toyota MIRAI

DOCK2 is involved in the host genetics and biology of severe COVID-19

「コロナ制圧タスクフォース」COVID-19疾患感受性遺伝子DOCK2の重症化機序を解明 --アジア最大のバイオレポジトリーでCOVID-19の治療標的を発見--. 京都大学プレスリリース. 2022-08-10.Identifying the host genetic factors underlying severe COVID-19 is an emerging challenge. Here we conducted a genome-wide association study (GWAS) involving 2, 393 cases of COVID-19 in a cohort of Japanese individuals collected during the initial waves of the pandemic, with 3, 289 unaffected controls. We identified a variant on chromosome 5 at 5q35 (rs60200309-A), close to the dedicator of cytokinesis 2 gene (DOCK2), which was associated with severe COVID-19 in patients less than 65 years of age. This risk allele was prevalent in East Asian individuals but rare in Europeans, highlighting the value of genome-wide association studies in non-European populations. RNA-sequencing analysis of 473 bulk peripheral blood samples identified decreased expression of DOCK2 associated with the risk allele in these younger patients. DOCK2 expression was suppressed in patients with severe cases of COVID-19. Single-cell RNA-sequencing analysis (n = 61 individuals) identified cell-type-specific downregulation of DOCK2 and a COVID-19-specific decreasing effect of the risk allele on DOCK2 expression in non-classical monocytes. Immunohistochemistry of lung specimens from patients with severe COVID-19 pneumonia showed suppressed DOCK2 expression. Moreover, inhibition of DOCK2 function with CPYPP increased the severity of pneumonia in a Syrian hamster model of SARS-CoV-2 infection, characterized by weight loss, lung oedema, enhanced viral loads, impaired macrophage recruitment and dysregulated type I interferon responses. We conclude that DOCK2 has an important role in the host immune response to SARS-CoV-2 infection and the development of severe COVID-19, and could be further explored as a potential biomarker and/or therapeutic target

Performance and durability of Ni–Co alloy cermet anodes for solid oxide fuel cells

Ni alloys are examined as redox-resistant alternatives to pure Ni for solid oxide fuel cell (SOFC) anodes. Among the various candidate alloys, Ni–Co alloys are selected due to their thermochemical stability in the SOFC anode environment. Ni–Co alloy cermet anodes are prepared by ammonia co-precipitation, and their electrochemical performance and microstructure are evaluated. Ni–Co alloy anodes exhibit high durability against redox cycling, whilst the current-voltage characteristics are comparable to those of pure Ni cermet anodes. Microstructural observation reveals that cobalt-rich oxide layers on the outer surface of the Ni–Co alloy particles protect against further oxidation within the Ni alloy. In long-term durability tests using highly humidified hydrogen gas, the use of a Ni–Co cermet with Gd-doped CeO2 suppresses degradation of the power generation performance. It is concluded that Ni–Co alloy cermet anodes are highly attractive for the development of robust SOFCs