Engineering topics

Coyle, Christopher A.

Publications and source records attributed to Coyle, Christopher A..

9 records

DOE OSTI2021

Sr and Co Vapor-Phase Transport from LSCF Cathodes

A series of tests were performed to differentiate between surface diffusion and vapor-phase diffusion of chemical species from LSCF cathode material at typical sintering temperatures (up to 1100°C) in SOFC production. A GDC source substrate was printed with LSCF and separated by an air gap from a YSZ target substrate. Various geometries with long surface paths were employed to reduce the possibility of surface transport. Sr and Co were detected on the target substrates via energy dispersive spectroscopy (EDS) and x-ray photoelectron spectroscopy (XPS), including spatially resolved XPS. These results support a vapor-phase transport mechanism for Sr and Co. Sintering conditions and barrier layer requirements may need to be revisited to prevent the formation of undesired strontium zirconate at cathode/electrolyte interface due to vapor-phase transport.

vapor phase transport, SOFC cathode, Sr transport↗

DOE OSTI2019

Mechanofusion for Improved Control of Cermet TPBAR Pellet Microstructure

Mechanofusion is an alternative fabrication technique that has the potential to advance cermet TPBAR pellets by producing LiAlO 2 -Zr core-shell powders that will provide tighter control of targeted microstructural characteristics such as the presence and thickness of Zr surrounding every LiAlO 2 particle in the cermet. Significantly enhanced microstructural control will translate to improved control of material properties and characteristics that affect the in-reactor performance of cermet TPBAR pellets. It was the intention of this work to demonstrate the efficacy of mechanofusion for producing precursor powders for TPBAR pellets, however materials procurement issues prevented this objective from being fully realized. In spite of these issues, in the short amount of time during which appropriate materials were available, it was demonstrated that mechanofusion does indeed have promise for producing the desired structures although the process yet requires optimization.

36 MATERIALS SCIENCE↗

DOE OSTI2019

Tailored Syngas via High Temperature H2O-CO2 Co-Electrolysis

This project has developed a new testing capability at PNNL and has evaluated solid oxide electrolysis cell (SOEC) materials for the ability to co-electrolyze carbon dioxide and steam to produce synthesis gas. CO 2 -H 2 O co-electrolysis, the simultaneous electrochemical reduction of carbon dioxide and steam, was performed on the porous Ni-based electrodes in high temperature SOECs. Experiments were conducted using small button cells and the rate of the electrochemical reactions was measured at 750°C for varied reactant compositions: 10-98%CO 2 and 5-50% H 2 O, also in the presence of some H 2 and CO to ensure reducing environment and avoid Ni oxidation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2018

Evaluation of Cation Migration in Lanthanum Strontium Cobalt Ferrite Solid Oxide Fuel Cell Cathodes via In-Operando X-ray Diffraction

Anode-supported SOFC button cells with LSCF-6428 cathodes were operated at various temperatures under constant current conditions for hundreds of hours in dry or humid (~3% water) cathode air while continuously collecting 1 hour XRD scans throughout the test duration. Additionally, one cell in dry air was held at OCV, and 12% CO2 was added to the humid air for another cell. Long cumulative XRD count times allowed minor phases in concentrations of less than 0.1 wt% to be identified. In humid air, cell performance increased during the first couple of hundred hours. XRD measured a gradual shift of Fe-rich Fe,Co spinel peaks to lower angles while post-mortem SEM discovered nano-nodules on the LSCF surfaces. When 12% CO2 was added to humid air, performance degradation was observed after the initial conditioning response, unlike in tests without CO2, which were stable after conditioning. XRD also measured a shift in the peaks of the major LSCF phase in the test with CO2 indicative of some degree of gradual decomposition. Cells tested at constant current in dry air exhibited fast initial degradation that decelerated over time, while the cell held at OCV maintained a stable voltage. XRD of the cathodes held at OCV at 750 °C and operated at constant current at 700 °C in dry air measured a slower shift of the Fe-rich spinel peaks to lower angles than was seen in tests in humid air, along with a shift in the peaks of a Co-rich Fe,Co spinel to higher angles. Post-mortem SEM of cells exposed to dry air discovered smaller nano-nodules on the LSCF surfaces than had been present in cells tested in humid air. Cells tested at constant current in dry air at 750 °C and 800 °C did not exhibit any gradual changes in the XRD patterns nor were nano-nodules discovered.

Hardy, John S.↗

DOE OSTI2017

Developing Cost-Effective Dense Continuous SDC Barrier Layers for SOFCs

Significantly improved performance during electrochemical testing of a cell with a dense continuous pulsed laser deposited (PLD) samarium doped ceria (SDC) layer spurred investigations into the fabrication of dense continuous SDC barrier layers by means of cost-effective deposition using screen printing which is amenable to industrial production of SOFCs. Many approaches to improve the SDC density have been explored including the use of powder with reduced particle sizes, inks with increased solids loading, and doping with sintering aids (1). In terms of sintering aids, dopants like Mo or binary systems of Mo+Cu or Fe+Co greatly enhance SDC sinterability. In fact, adding dopants to a screen printed, prefired, porous SDC layer made it possible to achieve a dense continuous barrier layer atop the YSZ electrolyte without sintering above 1200°C. Although the objective of fabricating a dense continuous layer was achieved, additional studies have been initiated to improve the cell performance. Underlying issues with constrained sintering and dopant-enhanced ceria-zirconia solid solubility are also addressed in this paper.

Nguyen, Hoang Viet P.↗

DOE OSTI2017

Activity and Stability of (Pr 1-x Nd x ) 2 NiO 4 as Cathodes for Solid Oxide Fuel Cells: Part V. In Situ Studies of Phase Evolution

This study is to complement an early report (the manuscript is attached for review purpose) on the role of interlayer on activity and performance stability in praseodymium nickelates. The aforementioned report showed a remarkable 48% increase in power density while switching from common GDC interlayer to a new interlayer chemistry (PGCO). Furthermore, a stable long-term performance was linked with suppressed reaction between the cathode and PGCO interlayer. In this article, we report in situ studies of the phase evolution. The high energy XRD studies at a synchrotron source showed fully suppressed phase transition in praseodymium nickelates with PGCO interlayer, while the electrodes on the GDC interlayer undergo substantial phase transformation. Furthermore, in operando and post-test XRD analyses shown fully suppressed structural changes in electrodes operated in full cells at 750°C and 0.80 V for 500 hours. SEM-EDS analysis showed that the formation of PrO x at the cathode-interlayer interface may play a role in a decrease of mechanical integrity of the interfaces, due to thermal expansion mismatch, leading to a local stress between the two phases. Furthermore, phase evolution at a narrow interface may propagate toward the electrode bulk, leading to structural changes Q1 and performance degradation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2017

In situ Studies of Phase Evolution in (Pr 1-x Nd x ) 2 NiO 4 Electrodes with Various Interlayer Chemistries

The interest in Pr2NiO4 (PNO) electrode stems from the necessity to develop active and stable oxygen electrodes (1-6) for solid oxide fuel cells (SOFCs) (7-9). PNO is known for its highly active nature (7,8,10), originating from its superior oxygen ion diffusion, surface exchange coefficient (2,7,9-11) and structural flexibility over a wide temperature region (from 500 to 900oC) (3,12). PNO electrode, however, does undergo structural evolution to form a higher order phase (Pr3Ni2O7) and Pr6O11 (PrOx) (8). The structural change has been a major concern because it possibly links with the performance degradation over long-term operation (7,8) Conventional x-ray diffraction (XRD) has been extensively used to investigate the structural evolution in nickelates in the form of powders or planar electrodes (8,10). This method has two major limitations due to its low flux and low resolution: (1) it might overlook the presence of additional phases in the system, which is especially true for praseodymium nickelates where XRD diffraction patterns of higher order phase(s) (e.g. Pr3Ni2O7) may overlap with the parent PNO phase, making quantification challenging (8); and (2) the quantification of phase evolution in electrochemically operated PNO electrode may show major structural change with almost 100% of the parent phase transition from the conventional XRD analysis, while the transmission electron microscopy (TEM) studies clearly show the regions of preserved PNO phase (7).

Dogdibegovic, Emir↗

DOE OSTI2017

LSM/YSZ Button Cell Tests in Cathode Air with Measured Cr Concentrations

A test fixture and methodology was developed for testing anode-supported SOFC button cells downstream from a chromia pellet at a prescribed temperature for qualitative control of Cr volatility. An alumina foam coated with Cr-gettering Na2CO3 was placed downstream from the cell to capture Cr species from the cathode air by reacting to form Na2CrO4. The coating and reaction product are both water soluble, facilitating dissolution from the porous substrate for subsequent ICP analysis to determine the Cr concentration in the resulting solution. The mass of collected Cr is used to calculate the average Cr concentration in the known volume of air used during the test. Cells with LSM/YSZ cathodes were electrochemically tested for 600 to 1000 hours with chromia pellets at varying conditions of temperature and humidity to elicit varying levels of Cr volatility. Molar Cr concentrations of only 40 to 170 ppt caused ~4%/kh degradation.

Hardy, John S.↗

DOE OSTI2017

The Role of Interlayer on the Catalytic Activity and Performance Stability of (Pr 1-x Nd x ) 2 NiO 4 as Cathodes for Solid Oxide Fuel Cells

The use of doped ceria as an interlayer in solid oxide fuel cells (SOFCs) is ubiquitous, which provides a better thermal expansion match and prevents the interaction between cathode (e.g. LSCF) and electrolyte (e.g. YSZ). However, the role of ceria interlayer on the cathode phase durability, catalytic activity, and performance stability remains obscure. This is particularly true in nickelate cathodes (e.g. Pr2NiO4). In this work, the attention will be given to electrochemical properties in nickelate athodes with various interlayers. Two new interlayer designs were investigated including (1) a thin Pr6O11 film deposited on the surface of GDC and (2) a Pr-doped ceria interlayer. The latter design results in a 48% increase in cathode performance; and more importantly, it leads to zero degradation over long-term easurements. This is a tremendous improvement when compared to the performance degradation in cells with a GDC interlayer. The cathode-interlayer reaction was fully suppressed with PGCO, due to the intrinsic Pr enrichment in the interlayer, which contributed to suppressing the phase evolution in the electrode.

Dogdibegovic, Emir↗