Physically-based deconvolution of impedance spectra for LSCF-based SOFC

A physically-based model for the interpretation of the impedance spectra of an anode-supported LSCF/GDC/YSZ/Ni:YSZ solid oxide fuel cell is presented in this work. The model locally describes transport and reaction phenomena within the cell components through mass conservation equations. The microstructural properties of the electrodes are predicted through numerical three-dimensional reconstruction of the microstructure, with input parameters obtained from the analysis of SEM pictures of each layer. Simulations show that the model reproduces impedance spectra obtained in different operating conditions with the same set of fitting parameters, comprising material-specific kinetic constants and electrochemical capacitances, which fairly agree with independent literature data and a previous analysis of the spectra through DRT. The model allows for the deconvolution and quantification of the characteristic resistance and frequency of the different physical processes that build up the impedance of the cell. In particular, 7 processes are identified: charge-transfer reactions between LSCF/GDC, GDC/YSZ and Ni/YSZ interfaces appear in the high-frequency range, the medium-frequency feature is due the oxygen reduction reaction and the gas diffusion in the anode, while the low-frequency arc is mainly due to the gas conversion in the anodic channel. An additional low frequency contribution (< 1Hz), not considered in the model, is observed and tentatively attributed to the adsorption of oxygen onto the LSCF surface. Simulation results suggest that more efforts must be dedicated to characterize and improve the oxygen transfer at the LSCF/GDC and GDC/YSZ interfaces. The study shows that a quantitative interpretation of impedance spectra is possible with a reduced number of fitting parameters when a physically-based approach is adopted, making the model an attractive tool for diagnostic purposes

Electrochemical performances and post-operational characterization of a segmented sofc operated under load for 15k hours

In the frame of the ENDURANCE FCH-JU-FP7 project (2014-2017) a segmented cell (20 segments regularly distributed from fuel inlet to fuel outlet) was operated for 15k hours in co-flow at 750\ub0C (average temperature) in hydrogen under load. Each segment was carefully monitored during operation by periodically acquiring the impedance spectra and constantly checking the voltage under current load. After 15k hours of operation the test was stopped and the cell used for further investigations in order to compare the cell evolution with the segment degradation. The overall observation in cross section of the cell has shown a good stability, however some differences were observed in the electrodes that might be related to the local operating conditions: temperature, H2 /H2O ratio in the fuel stream. The gathered results will contribute to increase the understanding the evolution of a SOFC in real operating conditions. Evidences of the effect of temperature, time and fuel pollutants were found

Aging of materials at inlet and outlet fuel manifolds in a SOFC stack

Analyses performed on a stack operated for more than 4000h at 750\ub0C at high fuel utilization (80%) revealed significant differences in aging behaviour of stack components when comparing fuel inlet and fuel outlet areas. Two samples were cut from the fuel inlet and outlet manifolds of the operated SOFC stack. The glass-ceramic sealing material and the interconnect alloy were exposed to a dual atmosphere (external air and internal fuel stream). The fuel composition was dry H2/N2 (60:40 vol. %) at the inlet and H2O/H2/N2 (48:12:40 vol. %) at the outlet. The stack was operated in co-flow configuration, with a large excess of air. It was found that the interfaces between the seal and the alloy were significantly affected by the difference in fuel composition. The sealant exposed to the outgoing air was significantly polluted by chromium generated in the stack and transported by the air stream. These investigations therefore reveal that the long-term evolution of the sealing and of the metallic support depends on the local conditions in the stack, as well as on additional interactions with other degradation phenomena

Bacteriological etiology and treatment of mastitis in Finnish dairy herds

Background: The Finnish dairy herd recording system maintains production and health records of cows and herds. Veterinarians and farmers register veterinary treatments in the system. Milk samples for microbiological analysis are routinely taken from mastitic cows. The laboratory of the largest dairy company in Finland, Valio Ltd., analyzes most samples using real-time PCR. This study addressed pathogen-specific microbiological data and treatment and culling records, in combination with cow and herd characteristics, from the Finnish dairy herd recording system during 2010-2012. Results: The data derived from 240,067 quarter milk samples from 93,529 dairy cows with mastitis; 238,235 cows from the same herds served as the control group. No target pathogen DNA was detected in 12% of the samples. In 49% of the positive samples, only one target species and in 19%, two species with one dominant species were present. The most common species in the samples with a single species only were coagulase-negative staphylococci (CNS) (43%), followed by Staphylococcus aureus (21%), Streptococcus uberis (9%), Streptococcus dysgalactiae (8%), Corynebacterium bovis (7%), and Escherichia coli (5%). On average, 36% of the study cows and 6% of the control cows had recorded mastitis treatments during lactation. The corresponding proportions were 16 and 6% at drying-off. For more than 75% of the treatments during lactation, diagnosis was acute clinical mastitis. In the milk samples from cows with a recorded mastitis treatment during lactation, CNS and S. aureus were most common, followed by streptococci. Altogether, 48% of the cows were culled during the study. Mastitis was reported as the most common reason to cull; 49% of study cows and 18% of control cows were culled because of mastitis. Culling was most likely if S. aureus was detected in the milk sample submitted during the culling year. Conclusions: The PCR test has proven to be an applicable method also for large-scale use in bacterial diagnostics. In the present study, microbiological diagnosis was unequivocal in the great majority of samples where a single species or two species with one dominating were detected. Coagulase-negative staphylococci and S. aureus were the most common species. S. aureus was also the most common pathogen among the culled cows, which emphasizes the importance of preventive measures.Peer reviewe

Impact of Biomass-Derived Contaminants on SOFCs with Ni/Gadolinia-Doped Ceria Anodes

The impact of biomass-derived contaminants on solid-oxide fuel cells (SOFCs) with Ni/gadolinia-doped ceria (GDC) anodes was investigated using electrochemical impedance analysis. Measurements were carried out with symmetric test cells under a single-gas atmosphere. The impact of H2S, HCl, and naphthalene in the gas stream on the performance of Ni/GDC anodes are presented. No significant impact has been observed up to 9 ppm H2S and HCl and 110 ppm naphthalene.Process and EnergyMechanical, Maritime and Materials Engineerin

Parametrical coordinates and microsamples to investigate real SOFCs in operating stacks

One of the issues defining the performance of an SOFC stack is to estimate and check during operation the behavior of all components (i.e. cell, sealant, interconnects). Each component has at least one function which is not strictly related to the power or heat generation but all are strategic due to their contribution to the degradation of the whole stack. The model based approach leads to identify zones of the stack by their operating parameters (e.g. T, j, P) corresponding to an univocal material response. In this paper, an experiment combining the parametrical coordinates with real samples in order to contribute to the study of real stacks is presented. The sample and the experiment itself are cost effective and offer the opportunity to soundly contribute to the assessment of stack components behavior in the "real world". The research was carried out in the frame of the FCH-JU project ENDURANCE