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At least 19 records

Communication—Reactive Sintering of a CoFe 2 O 4 Coating on Ferritic Stainless Steels for SOFC Interconnect Application

A mixed Fe+CoO precursor was successfully utilized to synthesize a dense CoFe 2 O 4 spinel coating on the Crofer 22 APU interconnect via reactive sintering at 900°C for 2 h in air without the use of any reduction treatment. Both the uncoated and coated samples were subject to thermal oxidation at 850°C for 500 h in air. Phase constituents, microstructure, and area specific resistance (ASR) of the uncoated and coated samples before and after the oxidation testing were evaluated. The CoFe 2 O 4 layer effectively reduced the Cr 2 O 3 scale growth and lowered the scale ASR.

25 ENERGY STORAGE↗

Controlled thermal pre-treatment of ZMG232G10® for corrosion mitigation under simulated SOFC interconnect exposure conditions

The IT-SOFC candidate interconnect material ZMG232G10® was thermally pre-treated in air and in H 2 – 3% H 2 O to mitigate dual atmosphere corrosion. Bare and pre-treated steel samples were exposed to a dual atmosphere exposure condition (dry air/metal/4% H 2 – N 2 (bal.) + 3% H 2 O) for 500h at 600°C. Corrosion products and oxide morphology developed on the air-exposed surfaces were analyzed. Pre-treatments of the metal in oxidizing (air) and reducing (H 2 – 3% H 2 O) gas atmospheres provide improved passivation against dual atmosphere corrosion compared to bare steel. Further, the uniform and iron-free oxide scale developed during the pre-treatment of alloy in the low pO 2 H 2 – 3% H 2 O gas atmosphere provides an effective diffusion barrier against the outward transport of cations and oxidation of iron observed under dual atmosphere conditions.

36 MATERIALS SCIENCE↗

Review—(Mn,Co) 3 O 4 -Based Spinels for SOFC Interconnect Coating Application

With the reduction of solid oxide fuel cell (SOFC) operating temperature to the range of 600 °C–800 °C, Cr-containing ferritic alloys have become the preferred interconnect material, which unfortunately are susceptible to continuous scale growth and Cr volatility at the SOFC operating temperatures. The (Mn,Co) 3 O 4 spinel system is widely regarded as the most effective coating for SOFC interconnect protection, due to its high thermal and electrical conductivity, adequate coefficient of thermal expansion, and excellent Cr blocking capability. This article reviews the physical and chemical properties of the (Mn,Co) 3 O 4 -based spinels; different types of coating precursors and deposition techniques; and the effects of spinel composition, quality and thickness on the coating performance. Furthermore, it is concluded that the spinel coating composition, quality, and thickness are more critical than the coating process in affecting the overall coating performance.

08 HYDROGEN↗

Synthesis, Processing and Properties of Calcium- and Nickel-Doped Yttrium Chromates(III) Y{sub 0.8}Ca{sub 0.2}Cr{sub 1−x}Ni{sub x}O{sub 3} (x = 0-0.3) and Studies on Their Potential Application as Coatings for SOFC Interconnects

In the present study, a calcium- and nickel-doped yttrium chromates (YCCN)-based, conductive–protective layers for metallic interconnects used in the intermediate-temperature solid oxide fuel cells (IT-SOFCs) were investigated. Synthesis of Y{sub 0.8}Ca{sub 0.2}Cr{sub 1−x}Ni{sub x}O{sub 3} (x = 0; 0.15 and 0.3) powders was performed using a wet chemistry method with two different complexing agents: ethylenediaminetetraacetic acid and glycine. Based on the result of thermal analysis of obtained precursors, optimal conditions of the calcination process were determined. Powders were then milled, compacted and sintered at different temperatures using free sintering method, into series of dense, polycrystalline sinters. The use of glycine precursor allowed obtaining a single-phase material in all cases. Based on the electrical and sintering properties, the Y{sub 0.8}Ca{sub 0.2}Cr{sub 0.85}Ni{sub 0.15}O{sub 3} material was selected for further studies. It was deposited using cost-effective screen-printing method on the Crofer 22APU ferritic stainless steel. To investigate properties and suitability of the resulting layer/steel system for IT-SOFCs applications, the high-temperature, dual-atmosphere studies were carried out for the first time for ceramic/metallic system, in conditions as close as possible to actual working conditions of the fuel cell. The layer exhibited high stability and good protective properties. The area-specific resistance of the studied ceramic layer/metallic substrate composite was determined, with the obtained value of 0.0366 Ω cm{sup 2} being within the arbitrary limit set for these materials (0.1 Ω cm{sup 2}). The results show that the investigated materials are suitable for the projected application.

36 MATERIALS SCIENCE↗

SOFC interconnect barriers and methods of making same using masks

A novel method to produce thin films spatially disposed on desired areas of workpieces is disclosed. Examples of include the formation of a yttria stabilized zirconia (YSZ) film formed on a desired portion of a stainless steel interconnect for solid oxide fuel cells by Atomic Layer Deposition (ALD). A number of methods to produce the spatially disposed YSZ film structures are described including polymeric and silicone rubber masks. The thin film structures have utility for preventing the reaction of glasses with metals, in particular alkali-earth containing glasses with ferritic stainless steels, allowing high temperature bonding of these materials.

36 MATERIALS SCIENCE↗

Effect of SOFC Interconnect-Coating Interactions on Coating Properties and Performance

The high operating temperature of solid oxide fuel cells (SOFCs) provides good fuel flexibility which expands potential applications, but also creates materials challenges. One such challenge is the interconnect material, which was the focus of this project. In particular, the objective of the project was to understand the interaction between the interconnect alloy and ceramic coatings which are needed to minimize chromium volatilization and the associated chromium poisoning of the SOFC cathode.

36 MATERIALS SCIENCE↗

Surface Treatments for Improved Performance of Spinel-coated AISI 441 Ferritic Stainless Steel

Ferritic stainless steels are promising candidates for IT-SOFC interconnect applications due to their low cost and resistance to oxidation at SOFC operating temperatures. However, steel candidates face several challenges; including long term oxidation under interconnect exposure conditions, which can lead to increased electrical resistance, surface instability, and poisoning of cathodes due to volatilization of Cr. To potentially extend interconnect lifetime and improve performance, a variety of surface treatments were performed on AISI 441 ferritic stainless steel coupons prior to application of a protective spinel coating. The coated coupons were then subjected to oxidation testing at 800 and 850°C in air, and electrical testing at 800°C in air. While all of the surface-treatments resulted in improved surface stability (i.e., increased spallation resistance) compared to untreated AISI 441, the greatest degree of improvement (through 20,000 hours of testing at 800°C and 14,000 hours of testing at 850°C) was achieved by surface blasting.

36 MATERIALS SCIENCE↗

Long-term oxidation behavior of spinel-coated ferritic stainless steel for solid oxide fuel cell interconnect applications

Long-term tests (>8,000 hours) indicate that AISI 441 ferritic stainless steel coated with a Mn-Co spinel protection layer is a promising candidate material system for IT-SOFC interconnect applications. While uncoated AISI 441 showed a substantial increase in area-specific electrical resistance (ASR), spinel-coated AISI 441 exhibited much lower ASR values (11-13 mOhm-cm2). Formation of an insulating silica sublayer beneath the native chromia-based scale was not observed, and the spinel coatings reduced the oxide scale growth rate and blocked outward diffusion of Cr from the alloy substrate. The structure of the scale formed under the spinel coatings during the long term tests differed from that typically observed on ferritic stainless steels after short term oxidation tests. While short term tests typically indicate a dual layer scale structure consisting of a chromia layer covered by a layer of Mn-Cr spinel, the scale grown during the long term tests consisted of a chromia matrix with discrete regions of Mn-Cr spinel distributed throughout the matrix. The presence of Ti in the chromia scale matrix and/or the presence of regions of Mn-Cr spinel within the scale may have increased the scale electrical conductivity, which would explain the fact that the observed ASR in the tests was lower than would be expected if the scale consisted of pure chromia.

Stevenson, Jeffry W.↗

Sol-gel synthesis of Mn1.5Co1.5O4 spinel nano powders for coating applications

Highlights: • Nano powder of Mn/Co spinel, applicable to solid oxide fuel cell, is synthesized. • The sol-gel synthesis of nanocrystalline Mn{sub 1.5}Co{sub 1.5}O{sub 4} spinel is investigated. • Sol-gel annealing temperature, time, and metal-to-citrate ratio are evaluated. • The optimum conditions for producing dual phase of Mn{sub 1.5}Co{sub 1.5}O{sub 4} are achieved. - Abstract: Mn{sub 1.5}Co{sub 1.5}O{sub 4} oxide spinels are widely used as protective coatings for stainless steel interconnects within planar solid oxide fuel cell stacks. Containing both cubic and tetragonal crystalline phases, these Mn/Co oxide spinels exhibit favorable thermal stability and electronic conductivity for the SOFC interconnect application. Slurry-based coating applications of Mn/Co oxides require precursor powders, which can benefit from being nano-structured. In this study, the sol-gel synthesis of nanocrystalline Mn{sub 1.5}Co{sub 1.5}O{sub 4} spinel is investigated. The decomposition of sol-gel precursors, as well as the crystalline phase structures and microstructures of the product Mn{sub 1.5}Co{sub 1.5}O{sub 4} are characterized by differential thermal and thermogravimetric (DTA/TG) analysis, X-ray diffraction (XRD), and transmission electron microscopy (TEM). The effects of various sol-gel annealing temperatures (T), treatment times (t), and citrate-to-metal ratios (Rc) are evaluated. Results suggest that nanocrystalline Mn{sub 1.5}Co{sub 1.5}O{sub 4} spinel can be synthesized around 1050 °C, and that T = 1050 °C, t = 6 h and Rc = 2 are optimum conditions for producing the smallest grain size. Image analysis of TEM results shows that the size of Mn{sub 1.5}Co{sub 1.5}O{sub 4} crystallites increases with increasing temperature, with average particle sizes ranging from ∼70 nm to ∼1 μm. Selected area diffraction pattern (SADP) of Mn{sub 1.5}Co{sub 1.5}O{sub 4} spinel synthesized at 800 °C confirms the dual (cubic/tetragonal) structure of Mn{sub 1.5}Co{sub 1.5}O{sub 4}.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

High Performance Ceramic Interconnect Material for Solid Oxide Fuel Cells (SOFCs): Ca- and Transition Metal-doped Yttrium Chromite

The effect of transition metal substitution on thermal and electrical properties of Ca-doped yttrium chromite was investigated in relation to use as a ceramic interconnect in high temperature solid oxide fuel cells (SOFCs). 10 at% Co, 4 at% Ni, and 1 at% Cu substitution on B-site of 20 at% Ca-doped yttrium chromite led to a close match of thermal expansion coefficient (TEC) with that of 8 mol% yttria-stabilized zirconia (YSZ), and a single phase Y0.8Ca0.2Cr0.85Co0.1Ni0.04Cu0.01O3 remained stable between 25 and 1100 degree C over a wide oxygen partial pressure range. Doping with Cu significantly facilitated densification of yttrium chromite. Ni dopant improved both electrical conductivity and dimensional stability in reducing environments, likely through diminishing the oxygen vacancy formation. Substitution with Co substantially enhanced electrical conductivity in oxidizing atmosphere, which was attributed to an increase in charge carrier density and hopping mobility. Electrical conductivity of Y0.8Ca0.2Cr0.85Co0.1Ni0.04Cu0.01O3 at 900 degree C is 57 S/cm in air and 11 S/cm in fuel (pO2=5×10^-17 atm) environments. Chemical compatibility of doped yttrium chromite with other cell components was verified at the processing temperatures. Based on the chemical and dimensional stability, sinterability, and thermal and electrical properties, Y0.8Ca0.2Cr0.85Co0.1Ni0.04Cu0.01O3 is suggested as a promising SOFC ceramic interconnect to potentially overcome technical limitations of conventional acceptor-doped lanthanum chromites.

30 DIRECT ENERGY CONVERSION↗

Mitigation of Chromium Impurity Effects and Degradation in Solid Oxide Fuel Cells: The Roles of Reactive Transport and Thermodynamics

The principal objectives of this project were to understand the combined role of transport and thermodynamics in chromium poisoning of solid oxide fuel cell (SOFC) cathodes. Specifically, the differences in the chromium poisoning phenomena in predominantly electronic conducting cathodes such as strontium-doped lanthanum manganite (LSM) and mixed conducting cathodes such as strontium-doped lanthanum ferrite (LSF) and lanthanum nickelate (LNO) have been experimentally elucidated. The voltage-current density curves obtained from single cells featuring these cathode materials in the presence of chromium impurity have been analyzed using a suitable electrochemical model. The results clearly show the higher chromium tolerance of LSF and LNO cathodes compared to LSM cathodes. Further, dense protective coatings of copper-manganese spinel oxide applied via electrophoretic deposition (EPD) conformally on ferritic stainless steel current collectors that simulate the interconnection in SOFC stacks have been applied to SOFCs featuring LSM cathodes. Operation over a period of ten days of SOFCs featuring bare and spinel–coated ferritic stainless steel mesh current collectors show that the coatings are highly effectiveto protect against chromium poisoning.

03 NATURAL GAS↗

EFFECT OF METALLIC INTERCONNECT THICKNESS ON ITS LONG-TERM PERFORMANCE IN SOFCS

At the operating environment of solid oxide fuel cells (SOFCs), oxide scale will grow on the ferritic interconnect (IC) surface unavoidably and furfures induce growth stress in oxide scale and along the interface of the oxide scale and IC substrate. A combination of growth stress with thermal stresses may lead to scale delamination/buckling and eventual spallation during SOFC stack cooling, even leading to serious degradation of cell performance. In this paper, the effect of the ferritic IC thickness on the delamination/spallation of the oxide scale was investigated numerically. The predicted results show that the interfacial shear stresses increase with the growth of the oxide scale and also with the thickness of the ferritic substrate; i.e., the thick ferritic substrate can easily lead to scale delamination and spallation.

delamination and spallation↗

Electrically Conductive and Protective Coating for Planar SOFC Stacks

Ferritic stainless steels are preferred interconnect materials for intermediate temperature SOFCs because of their resistance to oxidation, high formability and low cost. However, their protective oxide layer produces Cr-containing volatile species at SOFC operating temperatures and conditions, which can cause cathode poisoning. Electrically conducting spinel coatings have been developed to prevent cathode poisoning and to maintain an electrically conductive pathway through SOFC stacks. However, this coating is not compatible with the formation of stable, hermetic seals between the interconnect frame component and the ceramic cell. Thus, a new aluminizing process has been developed by PNNL to enable durable sealing, prevent Cr evaporation, and maintain electrical insulation between stack repeat units. Hence, two different types of coating need to have stable operation of SOFC stacks. This paper will focus on the electrically conductive coating process. Moreover, an advanced coating process, compatible with a non-electrically conductive coating will be

Choi, Jung-Pyung↗