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At least 109 records · Page 6
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

On the nonlinear temperature dependence of residual stresses in solid oxide fuel cells

The residual stresses in a dense yttria-stabilized zirconia (YSZ) layer bonded to a porous NiO-YSZ substrate were measured by X-ray diffraction in air between 25°C and 900°C. In this work, it was found that the residual stresses on the outer surface of the YSZ layer were compressive, that their magnitude increased with decreasing temperature, and that the temperature dependence was nonlinear particularly at temperatures below 600°C. An elastic model that incorporates micromechanics and laminate theory was formulated to successfully predicts the nonlinearity of the temperature dependence of the residual stresses by accounting for the effect of the order-disorder transition experienced by YSZ around 600°C and the magnetic transition of NiO at the Néel temperature around 265°C, on the properties of these materials. The implications of the results for the reliability of solid oxide fuel cells are discussed.

25 ENERGY STORAGE↗
DOE OSTI2023

Capacitive discharge in flash experiments: A discussion of the charged species

Abstract We report on the discharge of the capacitance formed at the electrodes in flash experiments with yttria stabilized zirconia. The experiments were carried out by disconnecting the current, and, instead, short circuiting the electrodes through a resistor. The time dependent voltage across the resistor was measured; the ratio yielded the discharge current. The current decayed exponentially with time, as expected in an RC circuit, which allowed the measurement of the capacitance. Experiments were carried out in two ways. In one case the specimens were flashed within a glove box filled with Ar (< 1 ppm O 2 ): these yielded electronic conductors. In the other case the specimens were flashed in ambient air: while electronically conducting in‐flash these specimens recover their prior insulating behavior as soon as the current is turned off. The stored charge was two orders of magnitude greater in the Ar experiments. Rather unexpectedly, the sign of the voltage expressed at the electrodes was opposite in experiments carried out in air and in Ar. The capacitance measured in the discharge experiments is attributed to the formation of space charge adjacent to the electrodes. In the case of Ar experiments, the capacitance is very large, approaching 1 F; in this case the space charge is expected to be constituted from ions. In the air experiments the specimen becomes insulating, trapping the electrons as a space charge. Hall effect measurements of the carrier density and X‐ray photoelectron spectroscopy characterization of electronically conducting single crystal specimen of cubic zirconia are reported.

Materials Science↗
DOE OSTI2023

Effects of processing parameters on the morphologies of complex sesquioxide thin films

Controlling and predicting the morphology of lanthanide sesquioxides in thin film form is vital to their use in current applications. In the present study, single and codeposited Sm2O3, Er2O3, and Lu2O3 thin films were grown on yttria-stabilized zirconia (8%) substrates by radio frequency magnetron sputtering at room temperature and 500 °C. The effect of two different substrate temperatures and altering the oxide cation on the structural and morphological properties of the films was analyzed. The thin films were characterized by profilometry, scanning electron microscopy, transmission electron microscopy, and x-ray diffraction. The single-component Lu2O3 and Sm2O3 films obtained were of the cubic phase, and the Er2O3 was a mix of cubic and monoclinic phases. It was observed for both the Er2O3 and Lu2O3 films that increasing the substrate temperature to 500 °C resulted in larger grained polycrystalline films. In contrast, large grained polycrystalline films were obtained at both room temperature and 500 °C for Sm2O3 and uneven granularity increased as temperature increased. Codeposition of Lu2O3 and Sm2O3, and Lu2O3 and Er2O3 resulted in a cubic bixbyite phase (the C phase of the lanthanide sesquioxide) solid solution. It was observed that the structure and morphology of the films can be controlled by manipulating deposition parameters. Both substrate temperature and altering the oxide cation contributed to changes in crystallinity and grain structure, which can modify the chemical and physical properties of the films for their applications.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Characterizing Performance of Electrocatalyst Nanoparticles Infiltrated into Ni-YSZ Cermet Anodes for Solid Oxide Fuel Cells

The infiltration of nanoparticle electrocatalysts into solid oxide fuel cell (SOFC) electrodes has been proven to produce a high density of electrochemically active sites, and reduce charge transfer polarization losses for SOFC electrodes. This is crucial for intermediate temperature operation, as these losses increase greatly at lower temperatures. Nickel-yttria stabilized zirconia (NiYSZ) cermets are low-cost, and exhibit excellent stability, but their main disadvantage stems from nickel coarsening and performance loss over their operational lifetimes. Infiltration of electrocatalyst nanoparticles has been shown to mitigate nickel coarsening and the consequent anode degradation. In this study, the effects of these infiltrants are observed in a standard Ni-YSZ electrode. In addition to nickel, mixed ionic and electronic conducting (MIEC) phases were infiltrated into Ni-YSZ scaffolds and their performances were characterized using electrochemical impedance spectroscopy (EIS). Cross-sectional microscopy of fractured cells was used to compare electrode microstructure and particle statistics. A model is proposed for how the nanoparticle electrocatalysts improve the anode performance.

25 ENERGY STORAGE↗
DOE OSTI2021

Investigating the Catalytic Requirements of Perovskite Fuel Electrodes Using Ultra-Low Metal Loadings

Solid Oxide Fuel Cells (SOFC) with La 0.3 Sr 0.7 TiO 3 (LST)–yttria-stabilized ZrO 2 (YSZ) anodes were prepared by impregnation of LST into porous YSZ scaffolds and then modified by Atomic Layer Deposition (ALD) of Ni, Pt, Pd, Fe, Co. and CeO 2 . Weight loadings as low as 0.01% of Pt, Ni, and Pd were sufficient to decrease anode impedances by orders of magnitude for operation in humidified H 2 at 973 K. The effects of CeO 2 , Co, and Fe were less but still significant. Sintering at higher temperatures was important. Furthermore, possible ways of stabilizing the metal particles and implications for developing ceramic anodes are discussed.

25 ENERGY STORAGE↗
DOE OSTI2021

Combined Mixed Potential Electrochemical Sensors and Artificial Neural Networks for the Quantificationand Identification of Methane in Natural Gas Emissions Monitoring

Sensors capable of quantifying methane concentration and discriminating between possible sources are needed for natural gas leak detection where multiple spatially overlapping sources including wetlands and agriculture may be present. We report on the fabrication by an additive manufacturing process of a four electrode La 0.87 Sr 0.13 CrO 3 , Indium Tin Oxide (In 2 O 3 90 wt%, SnO 2 10 wt%), Au, Pt mixed potential electrochemical sensor using yttria-stabilized zirconia (YSZ) as a solid electrolyte to natural gas detection. Artificial neural networks (ANNs) are used to automatically decode the possible source and concentration of methane. The ANNs trained on sensor data are capable of correctly discriminating between three sources of methane emissions from simulated mixtures of emissions from cattle, wetlands, or natural gas with >98% accuracy. Quantification error for methane in mixtures of CH 4 in air, CH 4 + NH3 in air, and simulated natural gas is less than 1.5% ppm when a two-temperature dataset is employed.

03 NATURAL GAS↗
DOE OSTI2021

Lowering the Impedance of Lanthanum Strontium Manganite-Based Electrodes with Lanthanum Oxychloride and Lanthanum Scavenging Chloride Salts

The impact of infiltrating chloride salts on the electrochemical behavior of lanthanum strontium manganite-yttria stabilized zirconia (LSM-YSZ) cathodes was investigated under solid oxide fuel cell operation. Infiltrating a lanthanum chloride solution resulted in the formation of a lanthanum oxychloride (LaOCl) phase. A LaOCl phase also formed by infiltrating an ammonium chloride solution; however, lanthanum was scavenged from the LSM phase to form LaOCl. The third infiltrating solution, a combination of zirconium chloride and yttrium nitrate, formed LaOCl by scavenging lanthanum from LSM and produced YSZ nanoparticles. Electrochemical impedance spectroscopy results suggest that LaOCl improves oxygen adsorption kinetics compared to a baseline LSM-YSZ cathode, reducing the low frequency impedance by 30%. In addition, scavenging lanthanum from LSM improved oxygen ion diffusion polarization as indicated by the observed 40% reduction in high frequency impedance and improved serial ohmic resistance by 19%. Finally, YSZ nanoparticles further reduced the high frequency impedance and ohmic resistance by 45% and 23%, respectively. The findings reveal new strategies for lowering the impedance of LSM-YSZ cathodes.

Taylor, Thomas H.↗
DOE OSTI2023

Understanding Chemo-Mechanical Stability of Protonic Ceramic Cells Through Electronic Conduction in the BaCe 0.7 Zr 0.1 Y 0.1 Yb 0.1 O 3-δ Electrolyte

BaCe 0.7 Zr 0.1 Y 0.1 Yb 0.1 O 3-δ (BCZYYb) is a promising ceramic electrolyte for reversible protonic ceramic cells. It is reported that BCZYYb-based cells show excellent long-term durability, particularly in the electrolysis mode, in contrast to the cells based on the conventional electrolyte yttria-stabilized zirconia. In this study, we investigate the chemo-mechanical stability behavior (a low tendency of delamination) of the BCZYYb-based protonic ceramic cells in terms of local electronic conduction in the electrolyte. The local electronic conductivity of the BCZYYb electrolyte is determined using Pt-probe-embedded cells near each electrode interface. The BCZYYb electrolyte exhibits sufficient p-type conductivity (∼10 −3 S cm −1 ) near the oxygen electrode (corresponding p O 2 : 5.27–21 × 10 −2 atm) and n-type conductivity (∼10 −4 S cm −1 ) near the hydrogen electrode (corresponding p O 2 : 0.99–1.30 × 10 −24 atm) at 600 °C. A standard cell is prepared and tested over long-term in the fuel cell (at positive and negative voltages) and electrolysis modes. The cell exhibits stable performance without delamination or cracks in both operating modes, owing to local electronic conduction.

Electrochemistry↗
DOE OSTI2024

Modeling and Analysis of Polarization Losses in Solid Oxide Fuel Cells with Siloxane Contamination

In this study, the degradation of the solid-oxide fuel cell (SOFC) nickel-yttria stabilized zirconia anode under decamethyltetrasiloxane (L4) contamination is examined with experiments and modeling. A model is developed for the polarization losses based on the charge transfer coefficient,α, and diffusion layer thickness,δ, and fitted to the experimental data to understand how the siloxane degrades the SOFC performance with time. The results of the model indicate that the total polarization losses increase approximately 44% over the course of the 180 min experiment at 350 mA cm −2 . Activation losses dominate the polarization losses initially but decrease in their total contribution while concentration losses increase. Scanning electron microscopy (SEM) with wavelength dispersive X-ray spectroscopy (WDS) elemental mapping indicates that silicon deposition is highest at the outer edge of the anode and forms a barrier layer to fuel diffusion, increasing concentration losses. When the model is applied to other previous D4 and L4 siloxane experiments conducted over a period of 40 h, similar trends in polarization losses are observed. Polarization losses increase more rapidly with D4 compared to L4 siloxane contamination, with concentration losses increasing the fastest with both types of siloxane.

Electrochemistry↗
DOE OSTI2021

Thin-film chemical expansion of ceria based solid solutions: laser vibrometry study

The chemical expansion of Pr 0.1 Ce 0.9 O 2-δ (PCO) and CeO 2-δ thin films is investigated in the temperature range between 600 °C and 800 °C by laser Doppler vibrometry (LDV). It enables non-contact determination of nanometer scale changes in film thickness at high temperatures. The present study is the first systematic and detailed investigation of chemical expansion of doped and undoped ceria thin films at temperatures above 650 °C. The thin films were deposited on yttria stabilized zirconia substrates (YSZ), operated as an electrochemical oxygen pump, to periodically adjust the oxygen activity in the films, leading to reversible expansion and contraction of the film. This further leads to stresses in the underlying YSZ substrates, accompanied by bending of the overall devices. Film thickness changes and sample bending are found to reach up to 10 and several hundred nanometers, respectively, at excitation frequencies from 0.1 to 10 Hz and applied voltages from 0–0.75 V for PCO and 0–1 V for ceria. At low frequencies, equilibrium conditions are approached. As a consequence maximum thin-film expansion of PCO is expected due to full reduction of the Pr ions. The lower detection limit for displacements is found to be in the subnanometer range. At 800 °C and an excitation frequency of 1 Hz, the LDV shows a remarkable resolution of 0.3 nm which allows, for example, the characterization of materials with small levels of expansion, such as undoped ceria at high oxygen partial pressure. As the correlation between film expansion and sample bending is obtained through this study, a dimensional change of a free body consisting of the same material can be calculated using the high resolution characteristics of this system. A minimum detectable dimensional change of 5 pm is estimated even under challenging high-temperature conditions at 800 °C opening up opportunities to investigate electro-chemo-mechanical phenomena heretofore impossible to investigate. The expansion data are correlated with previous results on the oxygen nonstoichiometry of PCO thin films, and a defect model for bulk ceria solid solutions is adopted to calculate the cation and anion radii changes in the constrained films during chemical expansion. The constrained films exhibit anisotropic volume expansion with displacements perpendicular to the substrate plane nearly double that of bulk samples. The PCO films used here generate high total displacements of several 100 nm’s with high reproducibility. Consequently, PCO films are identified to be a potential core component of high-temperature actuators. They benefit not only from high displacements at temperatures where most piezoelectric materials no longer operate while exhibiting, low voltage operation and low energy consumption.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

High-energy X-ray phase analysis of CMAS-infiltrated 7YSZ thermal barrier coatings: Effect of time and temperature

Calcium–magnesium–alumino-silicate (CMAS) particulates enter the aero-engine in a sandy environment, melt and infiltrate into 7 wt% yttria-stabilized zirconia (7YSZ) thermal barrier coatings (TBCs), reducing their lifetime. This leads to chemical degradation in 7YSZ accompanied by tetragonal to monoclinic phase transformation upon cooling. In this work, electron-beam physical vapor deposition coatings were infiltrated with a synthetic CMAS. Here, synchrotron X-ray diffraction measurements show that CMAS infiltration at 1250 °C has about 43% higher monoclinic phase volume fraction (PVF) at the coating surface compared to 1225 °C and remains consistently higher throughout the coating depth. Additionally, the increase in annealing time from 1 to 10 h results in a 31% higher monoclinic phase at the surface. Scanning electron microscopy revealed the presence of globular monoclinic phases corresponding spatially with the above findings. These results resolve the impact of time and temperature on CMAS infiltration kinetics which is important for mitigation.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Coupling between interfacial charge and mechanical deformation at high temperatures in ceramics. Final report

Basic research, under this project, has led to new fundamental discoveries in the effect of electric field (and temperature) on diffusion kinetics, electroluminescence and electronic conductivity in ceramic materials. For example, yttria stabilized zirconia sinters in just seconds well below 1000°C, while, at the same time, exhibiting a highly non-linear rise in conductivity, and intense electroluminescence. The phenomenon has been shown to occur in nearly all ceramics whether they are ionic or electronic conductors, or insulators. The rise in conductivity leads to Joule heating but in-situ measurements with a platinum standard at APS and Brookhaven (NSLS-II) have shown that the temperatures are much below what would have been needed to sinter in a few seconds. We have explored the hypothesis that huge concentrations of Frenkel pairs of vacancies and interstitials are produced. While these point defects accelerate sintering (by the interstitials being transported to the pores and the vacancies to the grain boundaries), they may also produce electron-hole pairs which can impart high electrical conductivity or recombine to emit photons. Many measurements, including in-situ measurements of lattice expansion are consistent with this hypothesis. However, the energy barrier for generating Frenkels in zirconia for example is much larger than can be expected at temperature and electrical fields in these experiments. Most recent work suggests that short wavelength phonons play a critical role in the genesis of the “flash” phenomenon. For example, the Debye temperature has been shown to be the lower bound for initiating flash. Molecular dynamics simulations have shown that large concentrations of Frenkel pairs can form under the proliferation of “optical” phonons at the edge of the Brillouin zone, that is with a wavelength at or below the lattice parameter. This project has led to the development of new experimental techniques as well as a software hardware interface for process and control and data analysis in real time, with a time scale of less than one second. This approach spells a new paradigm in materials science research. It potential impact on high rate manufacturing is self evident.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Integrated Harsh Environment Gas / Temperature Wireless Microwave Acoustic Sensor System for Fossil Energy Applications

There is a significant need for sensors capable of detecting gases, such as H 2 , O 2 , NO x , SO x within harsh environments encountered in power plants, industrial manufacturing, oil and gas exploration, and aerospace applications. This project successfully demonstrated the use of wireless microwave acoustic sensor technology for the detection of gases (H 2 or O 2 ) from ambient temperatures up to 650°C. The work focused on langasite (LGS) based surface acoustic wave resonator (SAWR) sensors as the harsh-environment sensor platform and explored multiple combinations of high-temperature thin films and device structures which were used to increase the sensor platform stability and detection capability at temperatures in the operational range of 150°C to 700°C. Specific material configurations that were investigated include: yttria-stabilized-zirconia (YSZ) decorated with Pt nanoparticles, atomic layer deposited (ALD) Al 2 O 3 , palladium, and Pt/Al 2 O 3 co-deposited electrode alloys. Through the deposition of YSZ at temperatures as high as 850°C and the use of graded alloy concentrations of Pt in the fabrication of the Pt/Al 2 O 3 electrode structures, film stress problems were mitigated, and sensor operation and stability achieved. To test and evaluate SAWR sensor performance for the detection of H 2 and O 2 under the influence of temperature variations, a comprehensive gas sensor control system and test apparatus was created to operate within a laboratory box furnace-controlled environment. In addition to the advancement in thin film materials through the deposition and fabrication techniques mentioned above, the work characterized the performance of sensors containing these films in the presence of oxidizing and reducing gases between 25°C and 700°C. In particular, the work revealed that the exposure of the SAWR sensor surfaces to oxidizing environments significantly improve the sensor response to H 2 , whereas the exposure of the sensor to reducing environments at high temperatures (≈ 500°C) renders the sensor irresponsive to H 2 , requiring sensor surface treatment at high temperatures (above 500°C) to recover the responsiveness to H 2 . The SAWR sensors have been also tested for wireless operation and array operation using multiple orientations to resolve the detection of gases under temperature variations. The work developed at the University of Maine was aided by a collaboration with the NETL Research and Innovation Center, Pittsburgh, PA, where thin film materials and device structures fabricated at UMaine were tested and characterized using NETL gas reactors and surface analysis techniques. SAWR sensors fabricated at UMaine were exposed multiple times to temperatures up to 700°C and H 2 concentrations up to 100% in the NETL facilities to measure the sensor performance. Environetix Technologies Corporation, a UMaine harsh-environment sensor spin-off company, also provided support and assistance in sensor system testing and implementation. The sensor small size and configuration allows flexible sensor placement and embedding of multiple sensor arrays into a variety of components within power systems and other aerospace or industrial settings that need to be interrogated wirelessly. The SAW platform is an attractive option for high-temperature harsh-environment gas sensing applications due to its inherent features, namely small size, capability of battery-free and wireless operation, and cost effective scale production using well-established production techniques from the semiconductor industry. The research findings achieved in this work, particularly advances regarding the fabrication and performance of the SAWR gas sensor platform, can be adapted and transferred to industrial power plants and other harsh environments.

01 COAL, LIGNITE, AND PEAT↗
DOE OSTI2021

Operating Stresses and their Effects on Degradation of LSM-Based SOFC Cathodes

The overall goals of the program were: To understand how selected operational parameters affect the performance of solid oxide fuel cells (SOFCs), with a focus on parameters affecting cathodes (air electrodes) comprised of lanthanum strontium manganite (LSM, (La 1-x Sr x ) 1-y MnO 3±δ ) and yttria-stabilized zirconia (YSZ, (Zr 1–z Y z )O 2±δ ). To relate the observed relationships between operational parameters and cell performance to the microstructural changes that can be observed in the cells after operation.

01 COAL, LIGNITE, AND PEAT↗
DOE OSTI2021

High Temperature Thermal Barrier Coating Evaluation of Yttrium Aluminum Garnet for Gas Turbine Applications

The Solution Precursor Spray Process (SPPS) process has been shown to overcome the durability and property challenges of applying yttrium aluminum garnet (YAG) coating for high temperature thermal barrier coating (TBC) applications (1200°C+) but only limited testing has been performed in representative application environments. In this study, YAG coatings were developed to optimize microstructure and tailor properties for combustion components in an industrial gas turbine. Thermal conductivity, erosion resistance and furnace cycling durability were used to validate YAG properties against the standard yttria-stabilized zirconia coating (YSZ). Graded and multi-layered microstructures were applied to enhance performance while maintaining durability. Further YAG process development was required to replicate coating properties and optimize deposition on more complex fuel injector nozzle and combustion liner components. Rig testing of both components was performed and compared against the baseline YSZ coating validating the high temperature capability and lower thermal conductivity of the SPPS YAG coating. The components in both tests were cycled for a minimum of ten cycles with the fuel injector test targeting a higher operating temperature while the combustor liner operated at standard conditions. A development engine test is planned to further validate performance in a gas turbine engine of this promising material.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Cost-effective Manufacturing and Morphological Stabilization of Nanostructured Cathodes for Commercial Solid Oxide Fuel Cells (SOFCs) [Slides]

The overall goals of the program were to develop methods for preparing and stabilizing SOFC electrodes by infiltration that can be manufactured on a practical scale, then transfer those methods to cells in stacks. Cathodes prepared by infiltration of nanoparticles into a porous scaffold of the electrolyte have demonstrated outstanding electrochemical performance and mechanical strength but are difficult to manufacture due to the large number of infiltration steps required to produce a conductive composite and show poor stability due to sintering of the nanoparticles. At Penn, the main goal was to develop a fabrication method that uses only a small number of infiltration steps. Infiltration with molten salts and electrodeposition were pursued but deemed impractical. A method in which an electronically conductive scaffold consisted of a composite of a mixed conductor, LSF (La 0.9 Sr 0.1 FeO 3 ), with yttria-stabilized zirconia (YSZ) was found to be promising. While some cation mixing between LSF and YSZ was observed during calcination, there was no evidence for new phases in XRD and incorporation of Zr into the perovskite could be minimized by reducing the Sr content of the LSF. To stabilize nanoparticles infiltrated into the LSF-YSZ composite scaffold, the USC team examined the effects of Atomic Layer Deposition with ZrO 2 and infiltrated nanoparticles. Significantly enhanced stability was observed with the infiltrated nanoparticles. The FuelCell Energy team prepared 4”x4” cells in which an LSF-YSZ composite scaffold was cofired with the YSZ electrolyte and infiltrated with LSCF nanoparticles. Apparently because the LSF-YSZ scaffold layer was very thin in this case, the cation mixing that occurred during calcination resulted in a poor scaffold-electrolyte interface which caused reduced performance.

30 DIRECT ENERGY CONVERSION↗
DOE OSTI2021

FCET Solid Oxide Fuel Cell Testing and Development: CRADA 526 [Abstract only]

The purpose of the proposed project is for PNNL to test the performance of prototype solid oxide fuel cells (SOFCs) created by FCET. Such testing will provide FCET with independent performance data that can be communicated to potential clients and/or investors. Additionally, PNNL will collaborate with FCET on design changes to improve fuel cell performance. Intellectual property developed in this way will benefit FCET with improved products to market, and PNNL through royalty revenue. The key technology held by FCET is a process to deposit extremely thin layers of oxide materials, from 10-50 nm in thickness. The range of possible materials that can be deposited with their method is broad, but this project will focus on the yttria-stabilized zirconia (YSZ) electrolytes for SOFCs. Thin, gas tight YSZ membranes have been a long-sought target in SOFC research. The thinner the YSZ, the lower the cell resistance, and the higher performance of the cell (or the lower the operating temperature). 10-50 nm would be a major step change in YSZ thickness from the state of the art. PNNL can team with FCET on future R&D projects and push this technology forward to improve energy efficiency and reduce carbon emissions.

30 DIRECT ENERGY CONVERSION↗