Search results for: Tomasz Ingram

Authors: Łukasz Mazur, Kamil Domaradzki, Maciej Bik, Tomasz Brylewski, Aleksander Gil

Abstract:

Interconnects used in solid oxide fuel and electrolyzer cells (SOFCₛ/SOECs) serve several important functions, and therefore interconnect materials must exhibit certain properties. Their thermal expansion coefficient needs to match that of the ceramic components of these devices – the electrolyte, anode and cathode. Interconnects also provide structural rigidity to the entire device, which is why interconnect materials must exhibit sufficient mechanical strength at high temperatures. Gas-tightness is also a prerequisite since they separate gas reagents, and they also must provide very good electrical contact between neighboring cells over the entire operating time. High-chromium ferritic steels meets these requirements to a high degree but are affected by the formation of a Cr₂O₃ scale, which leads to increased electrical resistance. The final criterion for interconnect materials is chemical inertness in relation to the remaining cell components. In the case of ferritic steels, this has proved difficult due to the formation of volatile and reactive oxyhydroxides observed when Cr₂O3 is exposed to oxygen and water vapor. This process is particularly harmful on the cathode side in SOFCs and the anode side in SOECs. To mitigate this, protective-conducting ceramic coatings can be deposited on an interconnect's surface. The area-specific resistance (ASR) of a single interconnect cannot exceed 0.1 m-2 at any point of the device's operation. The rate at which the CrO₃ scale grows on ferritic steels can be reduced significantly via the so-called reactive element effect (REE). Research has shown that the deposition of Gd₂O₃ nanoparticles on the surface of the Crofer 22 APU, already modified using a protective-conducting spinel layer, further improves the oxidation resistance of this steel. However, the deposition of the manganese-cobalt spinel layer is a rather complex process and is performed at high temperatures in reducing and oxidizing atmospheres. There was thus reason to believe that this process may reduce the effectiveness of Gd₂O₃ nanoparticles added as an active element source. The objective of the present study was, therefore, to determine any potential impact by introducing a preoxidation stage after the nanoparticle deposition and before the steel is coated with the spinel. This should have allowed the nanoparticles to incorporate into the interior of the scale formed on the steel. Different samples were oxidized for 7000 h in air at 1073 K under quasi-isothermal conditions. The phase composition, chemical composition, and microstructure of the oxidation products formed on the samples were determined using X-ray diffraction, Raman spectroscopy, and scanning electron microscopy combined with energy-dispersive X-ray spectroscopy. A four-point, two-probe DC method was applied to measure ASR. It was found that coating deposition does indeed reduce the beneficial effect of Gd₂O₃ addition, since the smallest mass gain and the lowest ASR value were determined for the sample for which the additional preoxidation stage had been performed. It can be assumed that during this stage, gadolinium incorporates into and segregates at grain boundaries in the thin Cr₂O₃ that is forming. This allows the Gd₂O₃ nanoparticles to be a more effective source of the active element.

Keywords: interconnects, oxide nanoparticles, reactive element effect, SOEC, SOFC

Procedia PDF Downloads 62

Authors: Łukasz Mazur, Kamil Domaradzki, Bartosz Kamecki, Justyna Ignaczak, Sebastian Molin, Aleksander Gil, Tomasz Brylewski

Abstract:

The rising global power consumption necessitates the development of new energy storage solutions. Prospective technologies include solid oxide electrolyzer cells (SOECs), which convert surplus electrical energy into hydrogen. An electrolyzer cell consists of a porous anode, and cathode, and a dense electrolyte. Power output is increased by connecting cells into stacks using interconnects. Interconnects are currently made from high-chromium ferritic steels – for example, Crofer 22 APU – which exhibit high oxidation resistance and a thermal expansion coefficient that is similar to that of electrode materials. These materials have one disadvantage – their area-specific resistance (ASR) gradually increases due to the formation of a Cr₂O₃ scale on their surface as a result of oxidation. The chromia in the scale also reacts with the water vapor present in the reaction media, forming volatile chromium oxyhydroxides, which in turn react with electrode materials and cause their deterioration. The electrochemical efficiency of SOECs thus decreases. To mitigate this, the interconnect surface can be modified with protective-conducting coatings of spinel or other materials. The high prices of SOEC components -especially the Crofer 22 APU- have prevented their widespread adoption. More inexpensive counterparts, therefore, need to be found, and their properties need to be enhanced to make them viable. Candidates include the Nirosta 4016/1,4016 low-chromium ferritic steel with a chromium content of just 16.3 wt%. This steel's resistance to high-temperature oxidation was improved by depositing Gd₂O₃ nanoparticles on its surface via either dip coating or electrolysis. Modification with CeO₂ or Ce₀.₉Y₀.₁O₂ nanoparticles deposited by means of spray pyrolysis was also tested. These methods were selected because of their low cost and simplicity of application. The aim of this study was to investigate the oxidation kinetics of Nirosta 4016/1,4016 modified using the afore-mentioned methods and to subsequently measure the obtained samples' ASR. The samples were oxidized for 100 h in the air as well as air/H₂O and Ar/H₂/H₂O mixtures at 1073 K. Such conditions reflect those found in the anode and cathode operating space during real-life use of SOECs. Phase and chemical composition and the microstructure of oxidation products were determined using XRD and SEM-EDS. ASR was measured over the range of 623-1073 K using a four-point, two-probe DC technique. The results indicate that the applied nanoparticles improve the oxidation resistance and electrical properties of the studied layered systems. The properties of individual systems varied significantly depending on the applied reaction medium. Gd₂O₃ nanoparticles improved oxidation resistance to a greater degree than either CeO₂ or Ce₀.₉Y₀.₁O₂ nanoparticles. On the other hand, the cerium-containing nanoparticles improved electrical properties regardless of the reaction medium. The ASR values of all surface-modified steel samples were below the 0.1 Ω.cm² threshold set for interconnect materials, which was exceeded in the case of the unmodified reference sample. It can be concluded that the applied modifications increased the oxidation resistance of Nirosta 4016/1.4016 to a level that allows its use as SOEC interconnect material. Acknowledgments: Funding of Research project supported by program "Excellence initiative – research university" for the AGH University of Krakow" is gratefully acknowledged (TB).

Keywords: cerium oxide, ferritic stainless steel, gadolinium oxide, interconnect, SOEC

Procedia PDF Downloads 60