John S. Hardy

Chromium (Cr) poisoning from metallic interconnects (ICs) is widely regarded as a critical degradation pathway in solid oxide cells (SOCs). This study systematically investigates the operational-mode-dependent Cr migration-comparing fuel cell mode (solid oxide fuel cells, SOFCs) vs. electrolysis mode (solid oxide electrolysis cells, SOECs)-from button cells to a scaled-up, large-area configuration. In button cell tests (~1,500 h), SOFC mode showed severe degradation, with an area-specific resistance (ASR) increase of ~180%, driven by deep inward Cr diffusion, Sr-Cr co-segregation, and precipitation of resistive secondary phases extending down to the barrier layer interface. Under both SOEC modes (50% and 90% steam), Cr-induced degradation was negligible, with ASR degradation rates of uncoated IC cells closely matching those of reference cells at each steam content (within ~1% and ~6%, respectively). Further, a scaled-up cell with an uncoated interconnect operated stably under SOEC mode for ~1,000 h, and post-mortem analysis along the flow path confirmed that Cr penetration into the electrode bulk remained predominantly suppressed across the entire active area, with only modest spatial variation toward the outlet. This asymmetry is proposed to arise from a coupled physical and electrochemical mechanism: the continuous outward O₂ flux generated during oxygen evolution reaction (OER) acts as a convective barrier against incoming Cr species, while anodic operation concurrently suppresses electrochemical Cr deposition at active boundaries. These findings broaden material selection tolerances and relax coating requirements for electrolysis-dominated stack configurations.

This project investigated the impact of adding a thin (10 – 50 µm) layer of amorphous glaze to the surface of a TPBAR pellet on its retention of helium, hydrogen (as a surrogate for tritium), and water (as a surrogate for tritiated water). The hypothesis was that the glaze would significantly reduce permeation of hydrogen species with a lesser impact on hindering helium permeation. A non-crystallizing soda-lime-silicate glass, known as SCN-1, was selected for this proof-of-concept study. It was found that continuous glaze layers of the desired thickness could be applied to the pellets with two or more dip coats, depending on the targeted thickness. At 330°C, the glaze was found to have a permeability that was lower than that of the pellet by a factor of ~106, implying that a thin 10 – 50 µm layer can significantly increase pellet retention of hydrogen. Meanwhile, the permeation rate of helium through the glaze was found to be ~20 times higher than that of hydrogen or water. An unanticipated outcome of the study was that unglazed pellets were measured to have hydrogen diffusivities that are a factor of ~105 greater than the diffusivity value used in the TPBAR COMSOL model to achieve observed tritium retention rates. When the higher measured diffusivity was substituted into the model and the model was run with all tritium species in the pellet in the form of T2O at a partial pressure of 20 Pa in equilibrium with LiOT, the resulting retention was 50% after 500 days.

The objective of this project was to demonstrate the suitability of PNNL’s Reactive Air Aluminization (RAA) coatings (US Patent Numbers 10,577,694, 10,378,094, and 9,481,923) for use in high-temperature systems. In particular, PNNL and Utility Global undertook a collaborative effort to explore the applicability of these coatings in Utility Global’s high-temperature hydrogen reactors where they would be used to prepare the sealing surfaces of the reactor technology. Utility Global instructed PNNL regarding their needs relating to further development of glass seal technologies suitable for use in their systems. This effort entailed alkaline earth-based silicate glass development and characterization; evaluation and characterization of reliability and compatibility of the coatings with glass seals, working environments, and substrates; performance demonstrations of representative cells and intermediate cells sealed using the glass seals and/or coatings of interest; and incorporation of the aluminization coatings and glass seals into Utility Global reactors for testing.

Lanthanide nickelate perovskites are known proton conductors at intermediate temperatures (350-600°C). They are attractive targets for proton conducting fuel cells and electrolyzers due to their operational temperature range and their stability in the presence of CO2. These materials have the formula LNiO3, with the lanthanide L = La, Ce, Pr, Nd, or Sm. Sintering is challenging due to phase transformations that occur at lower temperatures than those required for sintering. In this project, a series of lanthanide nickelate perovskites was synthesized via both a precursor solid solution method and the glycine nitrate process. Powders derived from the precursor solid solution method for LaNiO3 and NdNiO3 were sintered at Utility Global Inc. at various temperatures utilizing fast photonic sintering. LaNiO3 was successfully sintered while maintaining the perovskite phase. NdNiO3 underwent a phase transformation at all the conditions tested. The stability of the perovskite phase decreases moving right across the lanthanides in the periodic table, while the expected proton conductivity increases. These results will inform further investigations into lanthanide nickelate perovskites toward the goal of producing a free-standing, sintered, proton-conducting membrane.

To standardize materials and component characterization for next generation hydrogen production and energy generation solid oxide cell (SOC) technologies, test protocols are being established to facilitate comparison across the numerous laboratories and research institutions where SOC development for application in solid oxide fuel cells (SOFCs) and solid oxide electrolyzes cells (SOEC) is conducted. This paper proposes guiding protocols for fundamental electrical properties characterization of SOC materials, including temperature- and oxygen partial pressure (pO₂)-dependent conductivity measurements, and use of the electromotive force for determining the transference numbers, or contributions of each charge carrier (i.e., ions and electrons), to the total conductivity. The protocol for Archimedes density measurements is also provided as an integral technique to both of these methods.

This is the final report of an NSUF project investigating the use of EIS to probe thickness of oxide thickness on irradiated Zr-2 and Zr-4 samples.

In-operando XRD was conducted on anode supported SOFC button cells with LSM-YSZ cathodes operated at varying cathode air compositions under constant current conditions for over 1000 h. 1-hour XRD scans were continuously collected throughout the entire operation duration. By taking the sum of measured intensities from all of the collected patterns, the resulting cumulative XRD count times allowed the identification of minor phases present at concentrations as low as 2 O + 12% CO ₂ on the LSM-YSZ cathode was very similar to the effect of 3% H ₂ O alone, exhibiting performance degradation. Increasing contaminants in the cathode air were found to decrease the performance of the cells. In-operando XRD discovered an increase in MnO concentration and decrease in La ₂ O ₃ . A gradual expansion of the LSM lattice resulting from loss of Sr or O was discovered in the LSM/YSZ cathodes tested in humid cathode air. The inverse relationship between the unit cell volume and operating voltage suggests a possible correlation between Sr segregation and performance degradation in the LSM/YSZ cathodes.

The proposed work will demonstrate the suitability of PNNL Reactive Air Aluminization (RAA) coatings (US Patent Numbers 10,577,694, 10,378,094, and 9,481,923) for use in high-temperature systems. In particular, the Participant and Contractor will explore applicability of these coatings in Participant’s high-temperature hydrogen reactors where they would be used to prepare the sealing surfaces of the reactor technology. Utility Global will also instruct PNNL regarding their needs relating to the further development of glass seal technologies that are suitable for use in their systems. This effort will entail alkaline earth-based silicate glass development and characterization; evaluation and characterization of reliability and compatibility of the coatings with glass seals, working environments, and substrates; performance demonstrations of representative cells and intermediate cells sealed using the glass seals and/or coatings of interest; and incorporation of the aluminization coatings and glass seals into the reactor for full-scale testing.

Ferritic stainless-steel interconnect materials are used in intermediate or high-temperature SOFCs because of their oxidation resistance, high formability, and low cost. Their corrosion resistance is due to the formation of a protective chromium oxide scale during operation. However, the protective oxide layer produces Cr-containing volatile species at SOFC operating temperatures and conditions, which can cause cathode poisoning. Spinel coatings have been developed to prevent cathode poisoning while maintaining an electrically conductive pathway through SOFC stacks. Generally, Mn-Co-O spinel has been the material of choice, but PNNL has developed an Mn-Cu-O spinel protective coating to remove the costly Co and enhance the electrical conductivity. This paper will focus on the electrically conductive coating’s compatibility with LSCF in high-temperature operating environments.

Short alumina fibers were added to LSCo contact material to enhance the contact strength and improve thermal cycle stability. Alumina fiber from 2.5 v% to 20 v% were mixed with LSCo and sintered at elevated temperatures. Sintering study showed retardation in densification of LSCo matrix with increasing alumina content. Sintered bulk strength exhibited similar behavior where strength greatly reduced at high alumina v%. Coefficient of thermal expansion showed consistent results with prediction from rule of mixture. Contact strength using anode supported YSZ bilayer coupons improved greatly with the presence of small amount (2.5-5 v%) alumina fibers and no substantial reduction after 10 deep thermal cycles. Candidate LSCo-Al₂O₃ contact materials was validated in a generic stack test fixture for 1000h at 800^oC followed by 10 thermal cycles. Results of impedance analysis showed substantial improvement in thermal cycle stability as compared to LSCo parent materials.