Patent Application
20100092842
The invention relates to ceramic materials and in particular to the making of dense layers of ceramic materials. Embodiments of the invention may be used to make dense layers of ceramic materials such as yttria stabilized zirconia (YSZ). Other embodiments may be applied to make layers of other ceramics. Such layers have application, inter alia, as electrodes for solid oxide fuel cells.
Fuel cells convert chemical energy of suitable fuels into electrical energy without combustion and with little or no emission of pollutants. Fuel cells may be produced on a wide variety of scales in terms of both energy output and physical dimensions. Fuel cells can be used to generate electrical power in any of a wide variety of applications including powering vehicles, auxiliary power units (APUs) and cogeneration of power and heat for residential and business uses.
Solid Oxide Fuel Cells (SOFCs) are solid-state fuel cells that typically operate at high temperatures. SOFCs can be highly efficient. One application of SOFCs is in stationary power generation, including both large-scale central power generation, and distributed generation in individual homes and businesses. High operation temperatures provide fast reaction kinetics and high ionic conductivity, and therefore high efficiency, but also create technological challenges related to materials design and cell processing.
An SOFC includes an electrolyte layer that conducts ions but is not electronically conductive. The electrolyte layer separates cathode and anode sides of the fuel cell. It is important that the electrolyte not be penetrated by pores that could permit mixing of cathode and anode reactant gases. Mixing of cathode and anode reactant gases can lead to internal losses and an overall decrease in efficiency. It is desirable that the electrolyte layer be thin to achieve high efficiency.
Yttria stabilized zirconia (YSZ) is commonly used as an electrolyte material for Solid Oxide Fuel Cells (SOFCs), due to its pure ionic conductivity and chemical stability. Standard electrolyte fabrication techniques for solid oxide fuel cell electrolytes involve wet ceramic techniques such as tape-casting or screen printing. Such techniques typically require high-temperature sintering (typically at temperatures above 1300° C.). The complex multi-step processing procedures are time consuming. Providing infrastructure to support manufacturing of SOFCs by such procedures can involve significant capital costs.
Plasma spraying is a technique that can be applied to deposit layers of a wide range of materials on suitable substrates. However, it is difficult to produce plasma sprayed layers that are both thin (<about 10 μm or 20 μm) and completely dense. The density of plasma sprayed layers may be improved by plasma spraying onto a substrate in a vacuum. However, maintaining vacuum conditions during plasma spraying increases capital and operating costs and erodes the cost benefit obtained by plasma spraying.
Atmospheric plasma spraying (APS) is performed in air. No special atmospheric conditions are required for APS. Consequently, APS is less expensive both in capital and operation cost compared to vacuum plasma spraying. However, when the hot high velocity plasma jet enters the static and relatively cold atmosphere near the substrate, the laminar jet flow experiences turbulent shear due to the velocity differences of the jet and the surrounding atmosphere, thus potentially introducing additional porosity into the coatings compared to that normally obtained by vacuum plasma spraying.
Typical plasma-sprayed ceramic YSZ coatings have porosities ranging from 5% to 15%. Plasma spraying has been proposed for making YSZ coatings for thermal barrier applications. In thermal barrier coatings it is desirable to have relatively high porosity (e.g. porosities of 5% -15%). YSZ thermal barrier coatings (TBCs) may be applied in applications in which it is desirable to provide a large thermal gradient over a YSZ coating only a few hundred micrometers in thickness. Formation of such a thermal gradient is facilitated by the use of porous YSZ coatings, since the thermal conductivity of the coatings decreases as porosity increases.
Various methods have been proposed to improve the density of plasma-sprayed coatings. These include:
Vuoristo, and T. Mäntylä, Thermophysical and microstructural characterization of modified thick yttria stabilized zirconia thermal barrier coatings, in: J. Lecomte-Beckers, M. Carton, F. Schubert, P. Ennis (eds.), Proc. 7th Liege Conf. Mater. Adv. Pow. Eng., Energy Technol., 21, 2002, p 449-463 describes the use of laser glazing for densification;
There remains a need for cost-effective ways to make dense layers of ceramics. There remains a particular need for such ways to make thin dense ceramic layers suitable for use as electrolytes in SOFCs.
One aspect of the invention provides a method for making layers of ceramic materials. The methods comprise plasma spraying a layer of the ceramic onto a substrate; spin-coating the plasma-sprayed layer with a sol; and, firing the spin-coated ceramic layer. The ceramic material may comprise yttria stabilized zirconia (YSZ), rare-earth doped ceria (RDC), alumina-stabilized zirconia (ASZ) or other ceramic materials suitable for the intended application. RDCs include samaria-doped ceria (SDC), gadolinia-doped ceria (GDC), and ceria doped with other rare-earth elements or combinations of rare-earth elements. In some embodiments, the ceramic layer is an electrolyte layer for a solid oxide fuel cell. The plasma spraying may comprise atmospheric plasma spraying. In some embodiments the firing is performed in situ during the operation (or preparation for operation) of a cell incorporating a ceramic layer.
Another aspect of the invention provides a method for enhancing the electrochemical performance of a device that includes a ceramic layer. The method may be applied to enhance the electrochemical properties of an interface between a ceramic or cermet layer and another layer. For example, the method may be applied to enhance the electrochemical properties of an interface between an electrolyte layer and an electrode layer in a solid oxide fuel cell. The method comprises applying to a solid layer by spin coating a sol having a material composition similar to that of the layer and subsequently firing the layer. The ceramic layer may comprise a layer that has been applied by plasma spraying or a layer that has been formed by a process other than plasma spraying. The ceramic layer may comprise a YSZ layer, RDC layer, or ASZ layer, for example.
Methods as described herein may be applied in various applications including making fuel cell electrolytes and other layers and thermal barrier layers. Materials as described herein may have various applications including applications as fuel cell electrolytes and thermal barrier coating structures.
Other aspects of the invention provide ceramic materials having enhanced properties and fuel cell structures and fuel cells which incorporate such materials. Materials according to the invention and materials made according to methods of the invention have a wide range of applications including application as:
Further aspects of the invention and features of specific embodiments of the invention are described below.
The accompanying drawings illustrate non-limiting embodiments of the invention.
Throughout the following description, specific details are set forth in order to provide a more thorough understanding of the invention. However, the invention may be practiced without these particulars. In other instances, well known elements have not been shown or described in detail to avoid unnecessarily obscuring the invention. Accordingly, the specification and drawings are to be regarded in an illustrative, rather than a restrictive, sense.
Thin dense layers of ceramic may be made by a process 20, as shown in
In block 22, process 20 plasma sprays a layer of a ceramic onto a suitable substrate. The ceramic may, for example, comprise YSZ or another ceramic material such as:
Such ceramics have a range of applications including applications in solid oxide fuel cells.
The plasma spraying may comprise, for example, vacuum plasma spraying or atmospheric plasma spraying. The as-sprayed ceramic layer typically is somewhat porous. In some embodiments, the as-plasma-sprayed ceramic layer has a porosity in excess of 5% or 10%. By carefully optimizing plasma spraying parameters it may be possible to produce as-sprayed ceramic layers having porosities of 5% or less.
In block 24 the ceramic layer is spin-coated with a sol. The sol may comprise particles having a composition that is the same as or similar to that of the ceramic layer.
The sol dries in block 26. Block 26 may involve heating the ceramic layer to assist in driving off a solvent from the sol. Drying each spin-coated layer of sol is considered advantageous as solvent can be removed more easily from thinner films.
As indicated by line 28 blocks 24 and 26 may optionally be repeated. In some embodiments, the number of spin-coated layers applied to the ceramic layer is few enough that the sol infiltrates pores in the ceramic layer without forming a distinct sol layer on top of the ceramic layer. In the demonstration embodiment discussed below, it was found that a distinct sol layer began to form after deposition of about 5 or 10 spin-coated sol layers. The number of sol layers that can be applied without forming a distinct layer on top of the ceramic layer will depend on factors such as the initial porosity of the ceramic layer and the characteristics of the sol. In other embodiments, a sufficient number of spin-coated layers is applied to form a distinct layer of the sol. The processing time can be reduced by applying fewer spin-coated layers.
After block 30 determines that enough layers of sol have been spin coated onto the ceramic layer, the layer is fired in block 32. Firing may be performed at a temperature that is lower than the temperatures commonly employed in making YSZ layers by wet ceramic processes. For example, in some embodiments the firing temperature in block 32 is less than 800° C. (less than 750° C. or 700° C. or 300° C. in some embodiments).
Because the firing in block 32 can occur at a relatively low temperature, the substrate may comprise materials that would be unacceptably degraded at higher sintering temperatures. For example, the substrate may incorporate metal components or layers.
In a demonstration embodiment of the invention, NiO-YSZ substrates were produced by tape casting NiO-YSZ anode supports on a mylar sheet. A pore former was included in the NiO-YSZ anode supports. The substrates were produced from a slurry. A slurry was produced by mixing and ball milling the slurry mixture components listed in Table 1.
The ethanol, toluene, and fish oil were ball milled for over 15 hours before adding the powders. The full mixture was then ball milled for 24 hours. Prior to tape casting a 1.2 mm thick tape in a class 1000 clean room, the slurry was degassed in vacuum for 30 minutes. The resulting tape was dried at room temperature for 72 hours, followed by 12 hours of drying at 60° C. Round one-inch diameter substrates approximately 1 mm thick were made for receiving plasma-sprayed YSZ coatings by cutting circles from the tape (allowing for shrinkage during firing). Tape sintering shrinkage was found to be 16.7%, 20.1%, and 26.3% for tapes sintered at 1250° C., 1350° C., and 1400° C., respectively. The discs of dried tape were out-gassed and then pre-sintered at 1000° C., followed by a sintering and ironing step at either 1250° C., 1350° C., or 1400° C. Ironing the substrates under load at the sintering temperature made the substrates flat to facilitate plasma spraying.
YSZ layers were plasma sprayed onto the substrates using an Axial III™ torch (available from Northwest Mettech Corp. of North Vancouver, Canada) mounted on a 2 axis robot. The NiO-YSZ substrates were mounted on a 300 mm diameter drum. The sample holder allowed for a 0.5 inch diameter disc area to be sprayed through a mask in front of the substrate. 5 μm to 25 μm fused and crushed feedstock powders (Sulzer Metco, Seattle, USA) were fed through a vibrating hopper (CPF-2HP, 11.5 cm inner diameter, vibration on maximum) feeding the powder at a constant rate into a constant carrier gas flow under the plasma spraying conditions set out in Table 2.
A sol was prepared by mixing the materials listed in column #1 of Table 3. After adding each material, the solution was stirred at 200 rpm for 30 minutes without heating. After all materials were added, the solution was stirred for 12 hours. A discussion of making sols is provided in M. Keshmiri, O. Kesler, Acta Materialia, 54 (2006) 4149-4157, which is hereby incorporated herein by reference.
The resulting sol is an organic-based YSZ sol. The primary particle size in the sol was on the order of 200 nm. However, these particles may tend to clump into large aggregates having sizes on the order of 60 μm. It is generally desirable that the particles in the sol be smaller than the openings of pores in the ceramic layer so that the particles can enter and seal the pores. It is generally desirable that the particles have substantially the same material composition as the ceramic layer.
Preferably, the solid powder loading of a composite sol (i.e. a sol that will produce a layer having a given chemical composition that has suspended in it particles having a chemical composition the same as that of the layer) does not exceed about 1-2 wt %. Higher solid loading can tend to produce cracked layers during spin coating and drying.
Spin coating was performed using a model WS-400B-6NPP/Lite/10K spin coater (available from Laurell Technologies Corporation of North Wales, Pa.) on the plasma sprayed YSZ layers. The substrates were spun at 3000 rpm for 2 minutes. While the substrates were spinning, 1000 μl of sol was pipetted onto the substrate in ten 100 μl volumes of sol. One 100 μl volume of sol was delivered every five seconds using a pipette. The samples were then transferred to a hot plate set to 300° C. This procedure was repeated to achieve multiple layer coatings.
After spin-coating with one or more layers of sol, the samples were heated to 500° C. or 650° C. for one hour.
The concentration of the sol can be varied. The optimum sol concentration will depend to some degree on the porosity of the ceramic layer and the sizes of the pores in the ceramic layer. The demonstration embodiment used a sol having the material composition set out in column #1 of Table 3. Sols having greater concentration and lower concentrations, as set out in column #3 and #2 of Table 3 respectively, were used in comparison studies.
The composite slurries which included YSZ powder were sonicated for several hours in a water bath at room temperature prior to use to break down agglomerates. The data points in
Further improvements (i.e. reductions) in gas permeability may be achieved by one or more of:
The inventors have determined that the application of spin-coated layers to a ceramic layer can improve the properties of the layers for use in fuel cells apart from any benefit obtained by sealing. It is thought that this improvement may result from a change in the surface morphology of the ceramic layer. Where the ceramic layer is used as a fuel cell electrolyte, it has been found that the application of spin-coated layers tends to reduce the polarization resistance of the fuel cell.
The electrochemical characteristics of a device including a ceramic or cermet layer (such as a YSZ layer) may be improved by a process comprising applying to the ceramic or cermet material one or more layers of a sol having a material composition that is the same as or similar to that of the ceramic or cermet material by spin-coating and then heat treating the spin-coated ceramic or cermet layer. This method may be applied to improve the electrochemical properties of an interface between the ceramic or cermet layer and another layer. For example, the method may be applied to improve electrochemical properties of an interface between a ceramic layer and an electrode layer (which could, for example, comprise a Sm0.5Sr0.5CoO3−y (SSC)/Sm0.2Ce0.8O3−y SDC layer). The ceramic layer may comprise a layer of YSZ or another suitable ceramic. The ceramic layer may be formed by plasma-spraying, or another thermal spraying process, but this is not mandatory.
Simple solid oxide fuel cells incorporating plasma-sprayed and spin-coated
YSZ electrolytes (made as described in Example 1 above) were made by applying cathode slurries to the electrolytes. The cells had the structure shown in cross-section in
The cells were fabricated by applying composite Sm0.5Sr0.5CoO3−y (SSC)/Sm0.2Ce0.8O3−y (SDC) 40/60wt % cathode slurries to the YSZ electrolytes through a 0.96 cm opening in a polymer mask using a spatula. The cathode was sintered at 900° C. for 4 hours. The parts of the cathode-side surface of each cell not covered by plasma-sprayed electrolyte were sealed with YSZ-thermally matched Ceramabond™ (Aremco) and dried for 1 hour at room temperature, then heated in air for 2 hours at 92° C., 2 hours at 200° C., and 2 hours at 500° C. The cell was then heated to its testing temperature.
Open circuit potential measurements and full cell polarization and impedance tests were performed at 800° C., 750° C., and 700° C., using a Solartron 1260 Frequency Response Analyzer coupled with a Solartron 1470E Multistat (London Scientific, Canada). The impedance response of the system was recorded from 0.1 Hz to 10 kHz.
The improvement in electrochemical performance resulting from the application of the spin-coated sol layers can be seen in the electrochemical impedance spectra and polarization curves shown in
From
The sol gel impregnated cell has an OCV approximately 0.1V less than the theoretical OCV, while the as-plasma-sprayed cell has an OCV 0.46V less than the theoretical OCV at 800° C.
It can be appreciated that there are a wide range of parameters that may be varied to achieve desired results without departing from the invention. For example, the purity of raw materials used, particle shapes, particle sizes, and size distribution of powders used in plasma-spraying, as well as other spraying and process parameters throughout the process can affect the quality of the plasma-sprayed layer. Powders having very small particles are susceptible to vaporisation in the plasma torch and to difficulties with feeding. Powders having very large particles will not fully melt in the plasma, and particles may bounce off the substrate surface if they have remained solid or have re-solidified in-flight. The wide range of feedstocks available for plasma spraying provides the process with the flexibility that is required for the spraying of different SOFC layers that consist of different combinations of materials, with widely varying porosity requirements. This flexibility makes plasma spraying potentially more readily adaptable to the fabrication of SOFCs than other deposition processes that can utilize only one feedstock type. The plasma gas may comprise hydrogen, helium, argon, nitrogen, other suitable gases or mixtures thereof.
Plasma spraying has the potential to be applied to deposit all of the electrochemically active fuel cell layers in a solid oxide fuel cell. Plasma spraying may be used to deposit the electrodes and electrolyte layer on a relatively inexpensive metallic interconnect (IC) support layer, thus reducing the material cost of the fuel cell. The support layer may be made from any suitable metal. Nickel and appropriate stainless steels are suitable metals for some applications.
Since plasma-sprayed layers can be deposited without the necessity of lengthy high-temperature firing steps, the need for parallel production lines for mass production is also decreased. By avoiding high temperature firing steps (e.g. sintering at temperatures in excess of 950° C.) material compatibility problems such as chemical reactions between the materials of adjoining layers at high firing temperatures can be avoided. Oxidation of metallic substrates can also be minimized or avoided by avoiding high-temperature firing steps. The reduction in process steps, processing time, and firing temperatures can reduce production cost, labor intensity and energy usage. Such processes can therefore be both economically and ecologically favorable (e.g. reduced ecological footprint) in comparison to prior processes that are more labor- and energy-intensive.
In
Where a component (e.g. a substrate, plasma spray torch, assembly, anode, electrolyte etc.) is referred to above, unless otherwise indicated, reference to that component (including a reference to a “means”) should be interpreted as including as equivalents of that component any component which performs the function of the described component (i.e., that is functionally equivalent), including components which are not structurally equivalent to the disclosed structure which performs the function in the illustrated exemplary embodiments of the invention.
As will be apparent to those skilled in the art in the light of the foregoing disclosure, many alterations and modifications are possible in the practice of this invention without departing from the spirit or scope thereof. Accordingly, the scope of the invention is to be construed in accordance with the substance defined by the following claims.
This application claims priority from U.S. application No. 60/889209 filed on 9 Feb. 2007 and entitled DENSIFIED CERAMIC MATERIALS AND METHODS FOR MAKING SAME. For purposes of the United States of America, this application claims the benefit under 35 U.S.C. §119 of U.S. application No. 60/889209 filed on 9 Feb. 2007 and entitled DENSIFIED CERAMIC MATERIALS AND METHODS FOR MAKING SAME which is hereby incorporated herein by reference.
| Filing Document | Filing Date | Country | Kind | 371c Date |
|---|---|---|---|---|
| PCT/CA2008/000272 | 2/8/2008 | WO | 00 | 9/9/2009 |
| Number | Date | Country | |
|---|---|---|---|
| 60889209 | Feb 2007 | US |
