Rigidly Bonded Metal Supported Electro-Chemical Stack

Abstract

A design of and the process for forming a rigidly bonded metal supported electro-chemical device stack is provided. The electro-chemical device stack can be a solid oxide fuel cell or solid oxide electrolysis stack. The stack comprises multiple planar cells connected in serial by planar metal interconnects. The cells have metal support layers on both anode and cathode sides. The interconnect has gas channels embedded. Thin ceramic electro-chemical active electrodes and electrolyte are sandwiched between the metal support layers. The cells and interconnects are rigidly bonded to form a rigid body stack. The process comprises the steps of a). forming metal supported electro-chemical device cells with metal supports on both anode and cathode sides, b). sealing the peripherals of porous cell layers with an electrically insulating sealing material such as glass. c). bonding the cells and interconnects through commonly used metal-to-metal bonding methods, such as brazing or laser welding.

Claims

1. A rigidly bonded metal supported electro-chemical device stack comprising: a). a plurality of cells, each cell including, an anode metal support, a ceramic anode over the anode metal support, a ceramic electrolyte over the anode, a ceramic cathode over the electrolyte, and a cathode metal support over the cathode; b). the anode and cathode comprise of porous anode scaffold and cathode scaffold, respectively, and electro-chemically active catalyst particulate coating on the scaffold pore surfaces; c). planer metal interconnects between the cells, bonded to the anode metal support of a first cell and the cathode metal support of a second cell; d). cells and interconnects are substantially parallel to each other and form a planar stack of cells, stacked one on top of another, bonded with interconnects; e). a planar metal interconnect bonded to the top surface of the formed stack, and a planar metal interconnect bonded to the bottom surface of the formed stack; f). an electronically insulating hermetic coating on the peripheral edges of the stack.

2. The stack of claim 1, wherein the anode and cathode metal supports are porous metal layers, preferably ferritic stainless steels, and have porosity between 20% and 50%.

3. The stack of claim 1, wherein the anode and cathode metal supports are of the same material or materials having substantially similar sintering shrinkage and thermal expansion coefficients.

4. The stack of claim 1, wherein anode and cathode metal supports have thicknesses between 0.2 mm and 5 mm, preferably of substantially similar thicknesses.

5. The stack of claim 1, wherein the anode and cathode are porous ceramic layers, and have porosity between 10% and 30%.

6. The stack of claim 1, where the anode scaffold and cathode scaffold are of the same material or materials having substantially similar sintering shrinkage and thermal expansion coefficients.

7. The stack of claim 1, wherein the anode and cathode have thicknesses between 10 μm and 100 μm, preferably of substantially similar thicknesses.

8. The stack of claim 1, wherein the anode metal support, cathode metal support, anode scaffold, and cathode scaffold are of materials having substantially similar sintering shrinkage and thermal expansion coefficients.

9. The stack of claim 1, wherein the electrolyte is non-porous or without open porosity.

10. The stack of claim 1, wherein the electrolyte has thickness between 5 μm and 50 μm.

11. The stack of claim 1, wherein the electrolyte is of the same material or material having substantially similar sintering shrinkage and thermal expansion coefficient as these of anode and cathode scaffolds.

12. The stack of claim 1, wherein the anode scaffold, cathode scaffold, and electrolyte are oxygen ion conductive metal oxides or proton conductive metal oxides.

13. The stack of claim 1, wherein interconnect is metal plate that is non-porous or without open porosity.

14. The stack of claim 1, wherein gas channels are formed within the metal interconnect.

15. The stack of claim 1, wherein the interconnect is of the same material or material having substantially similar thermal expansion coefficient as these of anode and cathode metal supports.

16. The stack of claim 1, wherein the hermetic coating has thickness of not less than 10 μm and not greater than 5 mm.

17. The stack of claim 1, wherein the hermetic coating has a thermal expansion coefficient that is substantially similar as these of anode and cathode metal supports.

18. The stack of claim 1, wherein the hermetic coating material can be either viscous or rigid at operation temperature.

19. The stack of claim 1, wherein the cell and interconnect are hermetically bonded along all exterior gaps between them, preventing gas leakage to outside and inside gas channels.

20. The stack of claim 1, wherein the bonding between cells and interconnects remains rigid at operation temperature.

21. The stack of claim 1, wherein the bonding method and material between cell and interconnect are electrically conductive at operation temperature.

22. A method for forming an electro-chemical device stack comprising first forming cell scaffolds: a). forming a first green cell, the first green cell having a green anode metal support, a green anode over the anode metal support, a green electrolyte over the anode, a green cathode over the electrolyte, and a green cathode metal support over the cathode; b). forming a second green cell, the second green cell having a green anode metal support, a green anode over the anode metal support, a green electrolyte over the anode, a green cathode over the electrolyte, and a green cathode metal support over the cathode; c). forming all other green cells with the same process and structure; d). free sintering the first, the second, and all other green cells into cell scaffolds.

23. The method of claim 22, wherein forming the green cells comprises tape casting or screen printing of the green anode and cathode metal supports, green anode and cathode scaffolds, and green electrolyte to form green cell scaffolds prior to sintering.

24. The method of claim 22, wherein the green anode and cathode metal supports and green anode and cathode scaffolds are formed with pore formers; the green electrolyte is formed without pore former.

25. The method of claim 22, wherein sintering is performed between 1100° and 1500°, in reducing or vacuum environment.

26. The method of claim 22, wherein sintering is performed for 0.5 hours to 10 hours.

27. A method for forming an electro-chemical device stack of claim 22 further includes infiltrating active catalysts into cell scaffolds: a. providing a sintered cell scaffold, having porous anode and cathode metal supports, porous anode and cathode scaffolds, and dense electrolyte; b. providing an anode catalyst precursor and a cathode catalyst precursor; c. infiltrating the anode catalyst precursor through anode electrode metal support; d. infiltrating the cathode catalyst precursor through cathode electrode metal support; e. heating the cell to between 500° C. and 1000° C. for between 10 minutes and 5 hours to convert precursors to catalysts, and henceforth converting cell scaffold to active cell.

28. The method of claim 27, wherein infiltrations are performed in a vacuum between 100-300 mbar.

29. The method of claim 27, wherein operations c), d), and e) are repeated until sufficient amount of the anode catalyst and cathode catalyst are deposited into scaffolds, such as 1-10 times.

30. The method of claim 27, wherein the anode and cathode catalyst precursors comprise metal nitrate solution in sociochemical compositions that are converted to anode and cathode catalysts after heat treatment, respectively.

31. A method for forming an electro-chemical device stack of claim 27 further includes forming a bonded stack: a. providing catalysts infiltered active cells; b. providing interconnects, which can be stainless steel plates with gas channels; c. bonding the first cell with an interconnect, bonding the second cell with the interconnect; d. repeating b) for all other cells and interconnects to form a bonded stack; e. coating the cell peripheral edge surfaces with green ceramic, glass, or glass ceramic; f. firing the formed stack at temperature between 500° and 1000° to convert green coating to hermetic coating; g. if brazing is utilized to bond cell to interconnect, firing the formed bonded stack at appropriate temperature to form hermetic bonding between cells and interconnects.

32. A method for forming an electro-chemical device stack of claim 22 further includes forming a bonded stack scaffold: a. providing sintered cell scaffolds, each having porous anode and cathode metal supports, porous anode and cathode scaffolds, and dense electrolyte; b. providing interconnects, which can be stainless steel plates with gas channels; c. bonding the first cell scaffold with an interconnect, bonding the second cell scaffold with the interconnect; d. repeating b) for all other cell scaffolds and interconnects to form a bonded stack scaffold; e. coating the stack peripheral edge surfaces with green ceramic, glass, or glass ceramic; f. firing the formed bonded stack at temperature between 500° and 1000° to convert green coating to a hermetic coating; g. if brazing is utilized to bond cell scaffold to interconnect, firing the formed stack at appropriate temperature to form hermetic bonding layer between cell scaffolds and interconnects.

33. A method for forming an electro-chemical device stack of claim 32 further includes infiltrating active catalysts into the bonded stack scaffold: a. providing a bonded stack scaffold, having cell scaffolds and interconnects rigidly bonded together; b. providing an anode catalyst precursor and a cathode catalyst precursor; c. infiltrating the anode catalyst precursor into anode electrode layers through stack fuel gas channels in interconnects; d. infiltrating the cathode catalyst precursor through cathode electrode layers through stack air gas channels in interconnects; e. heating the stack to between 500° C. and 1000° C. for between 10 minutes to 5 hours to convert precursors to catalysts, and henceforth convert stack scaffold to active stack.

34. The method of claim 33, wherein infiltrations are performed in a vacuum between 100-300 mbar.

35. The method of claim 33, wherein operations b), c), and d) are repeated until sufficient amounts of the anode catalyst and cathode catalyst are deposited into electrode scaffolds, such as 1-10 times.

36. The method of claim 33, wherein the anode and cathode catalyst precursors comprise metal nitrate solution in sociochemical compositions that are converted to anode and cathode catalysts after heat treatment, respectively.

Description

BRIEF DESCRIPTION OF DRAWINGS

[0030] FIG. 1 shows a conventional SOFC stack design prior art using ceramic anode supported cells.

[0031] FIG. 2 shows a fully bonded metal supported electro-chemical device stack.

[0032] FIG. 3 shows the same stack of FIG. 2 in partially exploded view.

[0033] FIG. 4 shows an example of a flow diagram illustrating a fabricating process for a rigidly bonded metal supported electro-chemical device stack.

DETAILED DESCRIPTION OF THE INVENTION

[0034] Reference will now be made in detail to some specific details of the invention including the stack design and forming processes. Examples of these specific embodiments are illustrated in the accompanying drawings and descriptions. It will be understood that it is not intended to limit the invention to the described embodiment. On the contrary, it is intended to cover alternatives, modifications and equivalents as may be included within the scope of the inventions as defined by the claims. Particular embodiments of the present invention may be implemented without some of all of the provided details. In other instances, well known processes have not been described in detail in order not to unnecessarily obscure the present invention. The term “about” or “approximate” and like are used to indicate that the value modified by the term has an understood range associated with it, where the range can be ±20%, ±10%, ±5%, or ±1%. The term “substantially” is used to indicate that a value is close to a targeted value, where close can mean the value is within 80%, 85%, 90%, 95%, or 99% of the targeted values.

[0035] Typical compositions used in electro-chemical devices such as solid oxide fuel cell or solid oxide electrolysis cell are represented by their commonly used symbols. Some examples are: YSZ— yttria-stabilized zirconia, typically 8 mol % Y (8YSZ), ScSZ-scandia stabilized zirconia, typically 10 mol % Sc, can also contain 1% Ce (10ScSZ, 10Sc1CeSZ), SDC— samaria-dopped ceria, typically 20 mol % Sm, GDC— gadolinium-dopped ceria, typically 20 mol % Gd. LSM —lanthanum strontium manganite, typically 20 mol % La. LSC—lanthanum strontium cobaltite, typically 20% La. LSCF—lanthanum strontium cobalt ferrite, typically 60 mol % La and 20 mol % Co.

[0036] In some embodiments, a SOFC stack described in the present invention has gas channel embedded in interconnects (FIG. 2). Multiple cells (402) are connected in serial by, and bonded with, interconnects (403). End interconnects (401) are bonded to the top and bottom surfaces.

[0037] Each of the cells has an anode metal support, an anode over the anode metal support, an electrolyte over the anode, a cathode over the electrolyte, a cathode metal support over the cathode. The components described according to the embodiments herein are flat layers parallel to each other. The layers can be formed through techniques including, but not limited to, casting, deposition, printing, extruding, laminations, die-pressing, gel casting, spray coating, screen printing, roll compaction, 3D printing, and a combination thereof. In one embodiment, each of the layers can be formed via screen printing. In another embodiment, each of the layers can be formed via tape casting. In another embodiment, each of the layers can be formed via extrusion.

[0038] An electro-chemical device stack can be formed through the following steps (FIG. 4):

[0039] In some embodiments, the electro-chemically active catalysts are infiltrated into individual cells before the cells are assembled into a stack (610). The individually infiltrated cells facilitate easy quality control and inspection at individual cell level before assembly, at the cost of slow production throughput.

[0040] At block (611), form a green cell, comprising: a). forming green anode and cathode metal support layers with binder and pore formers (10-100 μm average size), with post sinter thickness 0.2-5 mm. b). form green anode and cathode layers with binder and pore former (1-20 μm average size), with post sinter thickness of 10-100 μm. c). form green electrolyte layer with the same material or materials of substantially the same sintering shrinkage and thermal expansion coefficient as the electrode layer but without pore formers, with post sinter thickness 5-50 μm. d). laminate layers in the sequence (FIG. 3) of anode metal support layer (502), anode layer (503), electrolyte layer (504), cathode layer (505), and cathode metal support layer (506), to form a green cell. The electrode metal support material can be selected from suitable ferritic stainless steel powders with matching CTE, such as 441, 434, 430, and others. The electrolyte and electrode material can be selected from suitable oxygen iron conductive metal oxide powders such as YSZ, SDC, GDC, ScSZ, ScCeSZ, and others.

[0041] After removing binder by heat treatment at block (612), at block (613), individual green cells are sintered to cell scaffolds. Sintering is performed in vacuum or reducing atmospheric environment that are consistent with stainless steel powder metallurgy known to the person skill in the art. The “scaffold” herein is reference to cell or stack structure having porous electrode backbones, electrode being anode and cathode, but without active catalysts. For example, in one embodiment, sintering is performed in 5% H.sub.2/95% Ar gas, at 1200° C., for 2 hours. Sintered electrolyte should be non-porous or without open porosity. Sintered electrode metal support and electrode scaffolds generally have a high volume of porosity to allow diffusion of gaseous species. According to one embodiment, the percent porosity of the formed electrode metal support is not less than 20-50%. According to another embodiment, the percent porosity of the formed electrodes is not less than 10-30%.

[0042] The absence of catalytic materials, such as LSM or Ni, in the current step of fabrication allows for higher sintering temperature without adverse effects, such as diffusion of Mn into YSZ, or inter-diffusion between Ni, Fe, and Cr, that often are constraints in other SOFC processing methods. The sintering conditions can be specifically designed to be suitable for fully densifying electrolyte.

[0043] At block (614), gas channels are formed in metal interconnect plate. Gas channels can be fabricated by techniques such as stamping, machining, laser cutting, and others, that are known to the person skilled in the art.

[0044] At block (615), a cathode catalyst precursor and an anode catalyst precursor are provided. In some embodiments, the catalyst precursor each comprises metal nitrates, a surfactant, and a solvent. For example, in some embodiments, a cathode catalyst precursor comprises lanthanum nitrate, strontium nitrate, and manganese nitrate in stoichiometric composition ratio for converting to La.sub.0.8Sr.sub.0.2MnO.sub.3-δ catalyst after heat treatment. In another example, in some embodiments, an anode catalyst precursor comprises samarium nitrate, cerium nitrate, and nickel nitrate in stoichiometric composition for converting to Sm.sub.0.2Ce.sub.0.8O.sub.1.9/Ni catalyst after heat treatment. Generally, the nitrates should be dissolved close to the maximum solubility to deliver the most catalyst precursor content in each infiltration. The resulted solutions generally have 1-4 mol/L of catalyst concentration.

[0045] At block (616), anode catalyst precursors are infiltrated into anode scaffold. Cathode catalyst precursors are infiltrated into cathode scaffold. In some embodiments, areas of cell that are not intended to be infiltrated, such as the edges, are protected with a mask such as polymer-based paint or plastic film before infiltration. The masks will be burned away during heat treatment. In some embodiment, a vacuum pressure can be applied before or during the infiltration process to remove air and facilitate precursor solutions penetration into pores.

[0046] At block (617), the catalyst infiltrated stack is heated to about 500° C. to 1000° to convert precursors to nano-particulate catalyst coating on the pore walls of electrode scaffold, converting the cell scaffold to an electro-chemical active SOFC cell. The heat treatment is performed for about 30 minutes to 5 hours. The catalysts in anode and cathode should provide at least one of an electronic conduction pathway, an ionic conduction pathway, and catalytic surfaces, and typically provide all three. In some embodiments the cathode catalyst is selected from a group consisting of lanthanum strontium manganite (LSM), lanthanum strontium cobaltite (LSC), lanthanum strontium ferrite (LSF), samarium strontium cobaltite (SSC), lanthanum strontium cobalt ferrite (LSCF), barium strontium cobalt ferrite (BSCF), samarium strontium cobaltate (SSC), praseodymium nickel oxide (PNO), praseodymium oxide (POx), samarium doped ceria (SDC), gadolinium doped zirconia (GDC), yttria-dopped zirconia (YSZ), and mixtures thereof. In some embodiments, the anode catalyst is selected from a group consisting of nickel strontium titanate, lanthanum strontium titanate, yttrium strontium titanate, niobium titanate, strontium manganese magnesium oxide, nickel and samaria or yttria doped ceria, and mixtures thereof. In some embodiments, composite catalysts can be desirable, recognizing that certain constituent may contribute to one of electronic conductivity, ionic conductivity, and electrocatalysis functions. For example, in one embodiment, an anode catalyst comprises YSZ and Ni. In another embodiment a cathode catalyst comprises LSM and YSZ. In one embodiment, additional Ni is infiltrated to enhance reforming catalytic capability for complex fuels such as natural gas, ammonia, kerosene, methane, propane, ethanol, methanol, propanol and mixtures thereof.

[0047] At block (618), the filtration and heat treatment procedures can be repeated several times until the among of catalysts infiltrated into electrode layers reaching specific targets, such as 20 vol %. In some embodiments, the infiltration and heat treatment are repeated 1-10 times for anode catalyst. In some embodiments, the infiltration and heat treatment are repeated 1-10 times for cathode catalyst. In some embodiments, the formed particles remain smaller than about 50-500 nm. After each heat treatment, excess catalysts are removed from the exterior surfaces to reduce potential impact on electro-chemical performance and allow for good gas transportation into porous layers. For example, this can be done by blowing compressed air on the exterior surfaces.

[0048] At block (619), coat the metal supported cell peripheral edges with green ceramic, glass, or glass ceramic layer by any suitable techniques known in the art. Such as, for example, dip-coating, spray-coating, roller-coating. The coating material should have a thermal expansion coefficient that is substantially similar as, or slightly smaller than, the CTE of electrode metal support material. The coating material in the present invention can remain rigid in SOFC operation temperatures. The choices of material and the process condition would be known to the person skilled in the art.

[0049] At block (620), individual cells are assembled and bonded with interconnects into a fully bonded stack. Multiple cells and interconnects are assembled in serial arrangement whereas interconnect is sandwiched between a cell's anode and the neighboring cell's cathode side. Additional interconnects and end plates are placed on the top and bottom surfaces of the stack structure forming hermetic surfaces. In some embodiment, cells' electrode metal supports and interconnects are bonded by brazing. In some embodiments, cells' electrode metal supports and interconnects are bonded by laser welding. Other metal to metal bonding methods can also be utilized. The bonding should form hermetic sealing around edges, internal manifolds, and other possible gas passages to prevent fuel or air leakage or inter-species mixing.

[0050] At block (621), the stack is heat-treated to an appropriate temperature to convert the cell edge coating layer to hermetic seals. In some embodiment, the heat-treatment of cell edge coating layer can be combined with brazing bonding of cells with interconnects in the same process.

[0051] In some embodiments, the electro-chemically active catalysts are infiltrated into individual cells after cells are assembled into stack (630). The infiltration into an entire stack improves the production throughput by infiltrating multiple cells at the same time. However, this method renders it not possible to test individual cells before assembly and one defective cell would result in the scrap of the entire stack. The procedure is similar to what has been described in procedure (610), hence, only outlines are described below with major difference emphasized.

[0052] Green cells are first formed (611), heat-treated for binder removal (612), and sintered to cell scaffold (613). Interconnects with gas channel built-in are prepared (614).

[0053] Green coating layer, such as electrically insulating glass or ceramics, is applied to peripheral edges of formed cell scaffolds (631).

[0054] At block (632), the cell scaffolds and interconnects are assembled and bonded together. The assembled stack scaffolds is then heat-treated (633) to convert green coating layer to hermetic sealing layer. If brazing is utilized to bond the cell scaffolds and interconnects, its heat-treatment can be combined with the heat-treatment of cell coating layer.

[0055] At block (634), a cathode catalyst precursor and an anode catalyst precursor are provided.

[0056] At block (635), the anode catalyst precursor is infiltrated into the stack through fuel gas channels. The cathode catalyst precursor is infiltrated into the stack through air gas channels. A vacuum pressure can be employed for the infiltration.

[0057] At block (636), the catalyst infiltrated stack is heated to about 500° C. to 1000° to convert precursors to nano-particulate catalyst coating on the pore walls of electrode scaffold, converting the stack scaffold to an electro-chemical active SOFC stack.

[0058] At block (637), the filtration and heat treatment procedures can be repeated several times until the among of catalysts infiltrated into electrode layers reaching specific targets.

[0059] A SOFC stack fabricated by performing the methods described in FIG. 4 comprises multiple cells in serial arrangement connected by interconnects. The cells and interconnect layers are rigidly bonded forming a fully bonded structure. Each cell comprises an anode metal support, an anode, an electrolyte, a cathode, and a cathode metal support. In some embodiments, the anode and cathode metal support are of substantially same thickness and are about 0.2-5 mm thick, or about 0.5-2 mm thick. In some embodiments, the anode and cathode are of substantially same thickness and are about 10-100 μm thick, or about 20 mm-50 μm thick. In some embodiments, the electrolyte is about 5-50 μm thick, or about 5-20 μm thick. In some embodiments, the interconnect is about 0.1-2 mm thick, or about 0.2-1 mm thick.

[0060] The stack further comprises embedded gas channels in interconnects. The peripheral edges of cells are further covered with hermetic seals on the exterior surfaces. Catalysts are infiltrated into porous electrodes through gas channels and porous electrode metal supports.

[0061] Because of the cell and interconnects having the same thermal expansion coefficient, they are bonded together to form a rigidly bonded stack without causing thermal stresses. The metal-to-metal bonding interfaces form hermetic sealing between layers and around gas passages to prevent gas leakage and inter-species mixing. The rigidly bonded stack requires no additional sealing between layers, nor compressive loading on the stack to maintain sealing or electrical contacts, which is a major benefit over conventional stack designs.

[0062] The examples of the embodiments disclosed are not intended to be limiting. They are related to the design and fabrication of solid oxide fuel cell stacks. The method described, however, are applicable to other solid state electrochemical devices such as solid oxide electrolysis cells and regenerative or reversible fuel cell/electrolysis cells.

[0063] The above-disclosed subject matter is to be considered illustrative, and not restrictive, and the appended claims are intended to cover all Such modifications, enhancements, and other embodiments, which fall within the true scope of the present invention. Thus, to the maximum extent allowed by law, the scope of the present invention is to be determined by the broadest permissible interpretation of the following claims and their equivalents, and shall not be restricted or limited by the foregoing detailed description.

[0064] In the foregoing Detailed Description, various features may be grouped together or described in a single embodiment for the purpose of streamlining the disclosure. This disclosure is not to be interpreted as reflecting an intention that the claimed embodiments require more features than are expressly recited in each claim. Rather, as the following claims reflect, inventive subject matter may be directed to less than all features of any of the disclosed embodiments. Thus, the following claims are incorporated into the Detailed Description, with each claim standing on its own as defining separately claimed subject matter.

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