Formation of solid oxide fuel cells by spraying

Abstract

The present embodiment describes a method of forming different layers in a solid oxide fuel cell. The method begins by preparing slurries which are then delivered to a spray nozzle. The slurries are then atomized and sprayed subsequently onto a support to produce a layer which is then dried. In this embodiment different layers can comprise an anode, an electrolyte and a cathode. Also the support can be a metal or a metal oxide which is later removed.

Claims

1. A method of forming different layers m in a solid oxide fuel cell comprising: preparing a slurry; delivering the slurry to a spray nozzle; atomizing and spraying the slurry onto a support to produce a sprayed layer; and drying the sprayed layer; wherein the different layers comprise an anode, an electrolyte and a cathode, the support is a metal or metal oxide which is later removed, and the spraying occurs at a temperature range from 5 C. to about 50 C. wherein the method only sprays one anode layer, one electrolyte layer and one cathode layer and wherein thickness of each layer deposited by single spraying pass ranges from about 50 nm to about 1 m.

2. The method claim 1, wherein the electrolyte is a doped ceria.

3. The method claim 1, wherein the electrolyte is a Sc-doped BZCY.

4. The method claim 1, wherein the electrolyte is a dense stabilized zirconia.

5. The method claim 1, wherein the electrolyte is a porous BZCYYb electrolyte.

6. The method of claim 1, wherein the pressure of the spraying ranges from about 0.5 psi to about 100 psi.

7. The method of claim 1, wherein flow rate of the spraying ranges from about 0.1 ml/min to about 20 ml/min.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) A more complete understanding of the present invention and benefits thereof may be acquired by referring to the follow description taken in conjunction with the accompanying drawings in which:

(2) None.

DETAILED DESCRIPTION

(3) Turning now to the detailed description of the preferred arrangement or arrangements of the present invention, it should be understood that the inventive features and concepts may be manifested in other arrangements and that the scope of the invention is not limited to the embodiments described or illustrated. The scope of the invention is intended only to be limited by the scope of the claims that follow.

(4) The present embodiment describes a method of forming different layers in a solid oxide fuel cell. The method begins by preparing slurries which are then delivered to a spray nozzle. The slurries are then atomized and sprayed subsequently onto a support to produce a layer which is then dried. In this embodiment different layers can comprise an anode, an electrolyte and a cathode. Also the support can be a metal or a metal oxide which is later removed. In one embodiment of the SOFC the anode is typically porous to allow the fuel to flow towards the electrolyte. Anodes are typically chosen for their (1) high electrical conductivity; (2) a thermal expansion that matches those of the adjoining components; (3) the capacity to avoid coke deposition; (4) fine particle size; (5) chemical compatibility with another cell components (electrolyte and interconnector) under a reducing atmosphere at the operating temperature; (6) large triple phase boundary; (7) high electrochemical or catalytic activity for the oxidation of the selected fuel; (8) high porosity (20-40%) adequate for the fuel supply and the reaction product removal; and (9) good electronic and ionic conductive phases. In the current SOFC any known anode electrodes can be utilized. Types of anodes that can be used include Ni/YSZ, Cu/Ni, perovskite structures with a general formula of ABO3. In the perovskite structure the A cations can be group 2, 3, or 10 elements or more specifically cations such as, La, Sr, Ca or Pb. Also in the perovskite structure the B cations can be group 4, 6, 8, 9, or 10 elements or more specifically cations such as Ti, Cr, Ni, Fe, Co or Zr. Other materials that the anode could be include nickel oxide, nickel, yttria stabilized zirconia, scandia stabilized zirconia, gadolinium doped ceria, samarium doped ceria, doped barium zirconate cerate, or combinations thereof.

(5) In one embodiment the anode can be pre-reduced at a temperature from about 400 C. to about 800 C. in a reducing atmosphere containing 1-100% hydrogen or other reducing gas atmospheres.

(6) In one embodiment of the SOFC the cathode is typically porous to allow the oxygen reduction to occur. Any cathode material known to those skilled in the art can be used. One example of cathode materials that are typically used include perovskite-type oxides with a general formula of ABO.sub.3. In this embodiment the A cations can be lower valance cations such as La, Sr, Ca or Pb. The B cations can be metals such as Ti, Cr, Ni, Fe, Co or Zr. Examples of these perovskite-type oxides include LaMnO.sub.3. In one differing embodiment the perovskite can be doped with a group 2 element such as Sr.sup.2+ or Ca.sup.2+. In another embodiment cathodes such as Pr.sub.0.5Sr.sub.0.5FeO.sub.3; Sr.sub.0.9Ce.sub.0.1Fe.sub.0.8Ni.sub.0.2O.sub.3; Sr.sub.0.8Ce.sub.0.1Fe.sub.0.7Co.sub.0.3O.sub.3; LaNi.sub.0.6Fe.sub.0.4O.sub.3; Pr.sub.0.8Sr.sub.0.2Co.sub.0.2Fe.sub.0.8O.sub.3; Pr.sub.0.7Sr.sub.0.3Co.sub.0.2Mn.sub.0.8O.sub.3; Pr.sub.0.8Sr.sub.0.2FeO.sub.3; Pr.sub.0.6Sr.sub.0.4Co.sub.0.8Fe.sub.0.2O.sub.3; Pr.sub.0.4Sr.sub.0.6Co.sub.0.8Fe.sub.0.2O.sub.3; Pr.sub.0.7Sr.sub.0.3Co.sub.0.9Cu.sub.0.1O.sub.3; Ba.sub.0.5Sr.sub.0.5Co.sub.0.8Fe.sub.0.2O.sub.3; Sm.sub.0.5Sr.sub.0.5Co.sub.3; or LaNi.sub.0.6Fe.sub.0.4O.sub.3 can be utilized. Other materials that the cathode could be include lanthanum strontium iron cobalt oxide, doped ceria, strontium samarium cobalt oxide, lanthanum strontium iron oxide, lanthanum strontium cobalt oxide, barium strontium cobalt iron oxide, or combinations thereof.

(7) The electrolyte used in the SOFC is responsible for conducting ions between the electrodes, for the separation of the reacting gases, for the internal electronic conduction blocking, and for forcing the electrons to flow through the external circuit. Some of the typical characteristics that electrolytes typically invoke include (1) an oxide-ion conductivity greater than 10.sup.2 S.Math.cm.sup.1 at the operating temperature; (2) negligible electronic conduction, which means an electronic transport number close to zero; (3) high density to promote gas impermeability; (4) thermodynamic stability over a wide range of temperature and oxygen partial pressure; (5) thermal expansion compatible with that of the electrodes and other cell materials from ambient temperature to cell operating temperature; (6) suitable mechanical properties, with fracture resistance greater than 400 MPa at room temperature; (7) negligible chemical interaction with electrode materials under operation and fabrication conditions to avoid formation of blocking interface phases; (8) ability to be elaborated as thin layers (less than 30 m) and (9) low cost of starting materials and fabrication.

(8) In the current SOFC the electrolyte can be any electrolyte known to those skilled in the art. In one embodiment the electrolyte is a dense stabilized zirconia or a doped ceria. In one embodiment the electrolyte comprises a porous BZCYYb as the backbone and carbonate as the secondary phase within the pores of.

(9) The weight ratio of BZCYYb in the composite electrolyte may vary, as long as the composite electrolyte can reach higher conductivity as well as current density as compared to non-composite electrolyte. In one embodiment, the weight ratio of BZCYYb in the composite electrolyte ranges from 9:1 to 1:1, but more preferably ranges from 50-90% or 70-80%. In another embodiment, the weight ratio of BZCYYb is about 75%.

(10) The weight percentage of carbonate in the composite electrolyte also may vary, as long as the composite electrolyte can maintain physical integrity during operation. In one embodiment, the weight percentage of carbonate in the composite electrolyte ranges from 10 to 50 wt %. In another embodiment, the weight percentage of carbonate in the composite electrolyte ranges from 20 to 30 wt %, in yet another embodiment, the carbonate is about 25%.

(11) In one example of preparing BZCYYb lithium-potassium carbonate is typically made first. Stoichiometrical amount of Li.sub.2CO.sub.3 and K.sub.2CO.sub.3 were mixed in the weight proportion of 45.8:52.5 and milled in a vibratory mill for 1 hour. The mixture was then heated to 600 C. for 2 hours. The heated mixture was then quenched in air to the room temperature and ground. The resulting lithium-potassium carbonate was used later in the preparation of composite electrolyte with BZCYYb.

(12) In one embodiment the BZCYYb powder was prepared by solid-state reaction, but other methods could also be used. Stoichiometric amounts of high-purity barium carbonate, zirconium oxide, cerium oxide, ytterbium oxide and yttrium oxide powders (all from Sigma-Aldrich Chemicals) were mixed by ball milling in ethanol (or other easily evaporated solvent) for 24 h, followed by drying at 80 C. for overnight and calcinations at 1100 C. in air for 10 h. The calcinated powder was ball milled again, followed by another calcination at 1100 C. in air for 10 h to produce single phase BZCYYb.

(13) The resulted BZCYYb powder and the carbonate obtained above were mixed at weight ratio of 75:25 and thoroughly ground again for one hour. The mixture was then heated to 680 C. for 60 minutes until only the carbonate melted and wet the BZCYYb grain boundaries in the mixture. Next, it was quenched (i.e. fast cooling) in air to room temperature. The quenched mixture was ground again to get the composite electrolyte powder.

(14) In another example an alternate way of preparing BZCYYb powder can be described. In this embodiment stoichiometric amounts of high-purity barium carbonate, zirconium oxide, cerium oxide, ytterbium oxide, and yttrium oxide powders (all from Sigma-Aldrich Chemicals) were mixed by ball milling in ethanol for 48 h, followed by drying in an oven and calcination at 1100 C. in air for 10 h. The calcined powder was ball milled again, followed by another calcination at 1100 C. in air for 10 h.

(15) The CeO.sub.2 and ZrO.sub.2 powders with different particle sizes were used to optimize the fabrication procedures. To prepare electrolyte samples for the conductivity measurement, we pressed the calcined powders isostatically into a disk at 274.6 MPa. The green disks had a diameter of 10 mm, with a typical thickness of 1 mm. The disks were then sintered at 1500 C. for 5 h in air (relative density >96%).

(16) In some embodiments a Sc-doped BZCY powder can be prepared. In one example of this embodiment BZCY-Sc with a nominal composition of BaCe.sub.0.7Zr.sub.0.1Y.sub.0.1Sc.sub.0.1O.sub.3- (BZCY-Sc) was synthesized by a conventional solid state reaction (SSR) method. Stoichiometric amount of high-purity barium carbonate, zirconium oxide, cerium oxide, yttrium oxide and scandium oxide powders (BaCO.sub.3:ZrO2:CeO.sub.2:Y.sub.2O.sub.3:Sc.sub.2O.sub.3=167.33:12.32:120.48:22.58:13.79, all from Sigma-Aldrich Chemicals) were mixed by ball milling in ethanol for 24 hours, followed by drying at 80 C. for overnight and calcinations at 1100 C. in air for 10 hours. The calcined powder was ball milled again, followed by another calcination at 1100 C. in air for 10 hours to produce single phase BZCY-Sc.

(17) In the present method, the calcining step is carried out at preferably higher than 1000 C. in air for 10 hours. However, the temperature and the length of calcination can vary, depending on different factors to be considered, such as the particle size chosen. The particle size of the zirconium oxide powder is preferably between 50 nm and 200 nm, and more preferably between 50 nm and 100 nm. The particle size of the cerium oxide powder is preferably between 1 m and 20 m, and more preferably between 5 and 10 m.

(18) In one embodiment the method only sprays one anode layer, one electrode layer and one cathode layer. In another embodiment the method only sprays two anode layers, two electrolyte layers and two cathode layers.

(19) The different layers of the process can by sprayed by preparing a ceramic slurry following by delivering the slurry to a spray nozzle. The slurry is then sprayed and atomized onto a support to form a sprayed layer which is dried. The flow rate of the spraying can range from about 0.1 ml/min to about 20 ml/min. The pressure of the spraying can range from about from about 0.5 psi to about 100 psi. The atomization of the spray can either be ultrasonic or pneumatic.

(20) The layers or each successive layer added by the spraying can be identical to the one before it or different. In a more specific example the material used for the anode support could be different or identical to the material used of the anode functional layer. In one embodiment the thickness of each layer deposited by single spraying pass ranges can range from about 50 nm to about 1 m. In one embodiment each layer sprayed by this method is repeated at least two times. In another embodiment each layer sprayed by this method is repeated at least three times. In one embodiment, the spraying of layers is repeated till the cumulative thickness of the layers on top of the tape casted anode is at least 1 m. In another embodiment the thickness of the deposited layers has a variance of less than one sigma.

(21) In one embodiment a heat treatment can be applied after the spraying of the different layers of the anode support. The temperature of the heat treatment can range between 850 C. to about 1500 C.

(22) As described above the current embodiments describe a method of forming a solid oxide fuel cell. The method begins by preparing an anode which is then delivered to a spray nozzle and applied to the support. From there the sprayed anode is dried. The electrolyte is then sprayed and atomized onto the anode to produce a sprayed electrolyte. From there the sprayed electrolyte is dried. From there the cathode is sprayed onto the dried electrolyte and is allowed to dry. A heat-treatment can be applied after spraying each layer in temperature ranges from about 850 C. to about 1500 C.

(23) In closing, it should be noted that the discussion of any reference is not an admission that it is prior art to the present invention, especially any reference that may have a publication date after the priority date of this application. At the same time, each and every claim below is hereby incorporated into this detailed description or specification as an additional embodiment of the present invention.

(24) Although the systems and processes described herein have been described in detail, it should be understood that various changes, substitutions, and alterations can be made without departing from the spirit and scope of the invention as defined by the following claims. Those skilled in the art may be able to study the preferred embodiments and identify other ways to practice the invention that are not exactly as described herein. It is the intent of the inventors that variations and equivalents of the invention are within the scope of the claims while the description, abstract and drawings are not to be used to limit the scope of the invention. The invention is specifically intended to be as broad as the claims below and their equivalents.