Supported ceramic membranes and electrochemical cells and cell stacks including the same

• US 20060269813A1
• Filed: 05/31/2005
• Published: 11/30/2006
• Est. Priority Date: 05/31/2005
• Status: Active Grant

• Current Assignee: Nextech Materials, Ltd.
• Original Assignee: Nextech Materials, Ltd.
• Inventors: Sabolsky, Katarzyna, Day, Michael J., Seabaugh, Matthew M., Sabolsky, Edward M.
• Granted Patent: US 7,767,358 B2
• Time in Patent Office: Days
• US Class Current: 429/465
• CPC Class Codes: B01D 2325/02 Details relating to pores or porosity of the membranes
• CPC Class Codes: B01D 2325/0283 Pore size
• CPC Class Codes: B01D 67/0041 by agglomeration of particles in the dry state
• CPC Class Codes: B01D 67/00411 by sintering
• CPC Class Codes: B01D 69/02 characterised by their properties
• CPC Class Codes: B01D 69/12 Composite membranes; Ultra-thin membranes
• CPC Class Codes: B01D 69/1213 Laminated layers
• CPC Class Codes: B01D 69/125 In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
• CPC Class Codes: B01D 71/024 Oxides
• CPC Class Codes: B01D 71/0271 Perovskites
• CPC Class Codes: C04B 2111/00612 as one or more layers of a layered structure
• CPC Class Codes: C04B 2111/00801 Membranes; Diaphragms
• CPC Class Codes: C04B 2111/00853 in electrochemical cells or batteries, e.g. fuel cells
• CPC Class Codes: C04B 35/48 based on zirconium or hafnium oxides, zirconates, zircon or hafnates
• CPC Class Codes: C04B 38/0054 the pores being microsized or nanosized
• CPC Class Codes: C04B 38/0074 expressed as porosity percentage
• CPC Class Codes: C04B 38/0675 Vegetable refuse; Cellulosic materials, e.g. wood chips, cork, peat, paper
• CPC Class Codes: C04B 38/068 Carbonaceous materials, e.g. coal, carbon, graphite, hydrocarbons
• CPC Class Codes: H01M 2008/1293 Fuel cells with solid oxide electrolytes
• CPC Class Codes: H01M 2300/0094 in the form of layered products, e.g. coatings
• CPC Class Codes: H01M 8/1226 : characterised by the supporting layer
• CPC Class Codes: H01M 8/124 : characterised by the process of manufacturing or by the material of the electrolyte
• CPC Class Codes: H01M 8/1253 : the electrolyte containing zirconium oxide
• CPC Class Codes: Y02E 60/50 : Fuel cells
• CPC Class Codes: Y02P 70/50 : Manufacturing or production processes characterised by the final manufactured product

Abstract

A dense ceramic electrolyte membrane supported by symmetrical porous ceramic electrolyte layers. The thin (t<100 microns) electrolyte layer is sandwiched between two fugitive-containing electrolyte support layers that become highly porous after firing. The heat treated fugitive-containing support layers form a skeletal structure of strongly adhered electrolyte with an interpenetrating network of pores that extends well always from the electrolyte surface. The porous layers can be infiltrated with a range of electrode materials or precursors to form a solid oxide fuel cell or other electrochemical cell as well as electrochemical cell stacks. The supported ceramic membrane provides electrochemical performance advantages and reduces warpage during sintering compared to conventional structures.

Claims

1. A supported ceramic membrane, comprising:

a first layer of a fugitive-containing ceramic electrolyte material in the green state;

a layer of a dense ceramic electrolyte material in the green state positioned above the fugitive-containing layer; and

a second layer of the fugitive-containing ceramic electrolyte material positioned above the dense ceramic electrolyte layer;

the tri-layer assembly being laminated and then sintered to form a composite structure, the fugitive-containing ceramic electrolyte layers becoming porous after sintering.

2. The supported ceramic membrane of claim 1, wherein the dense ceramic electrolyte layer has substantially the same thickness as each layer of the porous ceramic electrolyte material formed after sintering.

3. The supported membrane of claim 1, wherein the dense ceramic electrolyte material and the fugitive-containing ceramic electrolyte material each is selected from a stabilized zirconia composition.

4. The supported membrane of claim 3, wherein the dense ceramic electrolyte material and the fugitive-containing ceramic electrolyte material each is selected from a scandia-doped zirconia composition.

5. The supported membrane of claim 4, wherein the dense ceramic electrolyte material is a fully stabilized scandia-doped zirconia composition and the fugitive-containing ceramic electrolyte material is a partially stabilized scandia-doped zirconia composition.

6. The supported membrane of claim 4, wherein the dense ceramic electrolyte material is a partially stabilized scandia-doped zirconia composition and the porous ceramic electrolyte material is a fully stabilized scandia-doped zirconia composition.

7. The supported membrane of claim 1, wherein the dense ceramic electrolyte material is selected from a stabilized zirconia composition and the fugitive containing ceramic electrolyte material is selected from a stabilized ceria composition.

8. The supported membrane of claim 1, wherein the porous ceramic electrolyte layers formed after sintering have a pore volume greater than 50% of the total geometric volume.

9. The supported membrane of claim 1, wherein the porous ceramic electrolyte layers formed after sintering have a pore volume greater than 20% and less than 50% of the total geometric volume.

10. The supported membrane of claim 1, wherein the porous ceramic electrolyte layers formed after sintering of the fugitive-containing ceramic electrolyte material have an average pore size between 100 nanometers and 200 microns.

20. An electrochemical cell, comprising:

the supported ceramic membrane of claim 1;

an anode material deposited on an outer surface of the supported ceramic membrane; and

a cathode material deposited on the opposing outer surface of the supported ceramic membrane.

21. The electrochemical cell of claim 20, wherein

the anode material is selected from a solution comprising a composition selected from a nickel oxide, a nickel oxide/yttria stabilized-zirconia, a nickel salt, a copper salt, a silver salt, a platinum salt, a gold salt, a doped alkaline earth titanate, a lanthanum chromite, precursors thereof, and mixtures thereof;

and a particulate slurry comprising a composition selected from nickel, copper, cobalt, silver, platinum, gold, a nickel alloy, a copper alloy, a silver alloy, a platinum alloy, a gold alloy, a doped alkaline earth titanate, a lanthanum chromite, precursors thereof; and

mixtures thereof; and

the cathode material is selected from a lanthanum manganite, a doped lanthanum manganite, a lanthanide ferrite, a lanthanide cobaltite, precursors thereof, and mixtures thereof.

23. An electrochemical cell stack, comprising:

a first dense electronically conductive plate selected from a nickel chrome superalloy and a ferritic stainless steel;

a first electrochemical cell of claim 20 having an outer surface secured to the first conductive plate;

a second dense electronically conductive plate secured to the opposing outer surface of the first electrochemical cell;

a second electrochemical cell of claim 20 having an outer surface secured to the opposing surface of the second conductive plate; and

a third dense electronically conductive plate secured to the opposing outer surface of the second electrochemical cell.

24. The electrochemical cell stack of claim 23, wherein

the anode material is selected from a solution comprising a composition selected from a nickel oxide, a nickel oxide/yttria stabilized-zirconia, a nickel salt, a copper salt, a silver salt, a platinum salt, a gold salt, a doped alkaline earth titanate, a lanthanum chromite, precursors thereof, and mixtures thereof;

and a particulate slurry comprising a composition selected from nickel, copper, cobalt, silver, platinum, gold, a nickel alloy, a copper alloy, a silver alloy, a platinum alloy, a gold alloy, a doped alkaline earth titanate, a lanthanum chromite, precursors thereof, and mixtures thereof; and

the cathode material is selected from a lanthanum manganite, a doped lanthanum manganite, a lanthanide ferrite, a lanthanide cobaltite, precursors thereof, and mixtures thereof.

25. An electrochemical cell stack, comprising:

n electrochemical cells of claim 20, wherein n≧

2; and

n+1 dense electronically conductive plates each selected from selected from a nickel chrome superalloy and a ferritic stainless steel;

wherein each of n−

1 plates is secured between the anode surface of one of the n electrochemical cells and the cathode surface of another one of the n electrochemical cells and each of the remaining 2 plates is secured to an outer surface of one of the outermost of the n electrochemical cells.

26. The electrochemical cell stack of claim 25 wherein

the anode material is selected from a solution comprising a composition selected from a nickel oxide, a nickel oxide/yttria stabilized-zirconia, a nickel salt, a copper salt, a silver salt, a platinum salt, a gold salt, a doped alkaline earth titanate, a lanthanum chromite, precursors thereof, and mixtures thereof;

and a particulate slurry comprising a composition selected from nickel, copper, cobalt, silver, platinum, gold, a nickel alloy, a copper alloy, a silver alloy, a platinum alloy, a gold alloy, a doped alkaline earth titanate, a lanthanum chromite, precursors thereof; and

mixtures thereof; and

the cathode material is selected from a lanthanum manganite, a doped lanthanum manganite, a lanthanide ferrite, a lanthanide cobaltite, precursors thereof, and mixtures thereof.

37. A method of making an electrochemical cell stack, comprising the steps of:

providing n electrochemical cells of claim 20, wherein n≧

2;

providing n+1 dense electronically conductive plates selected from a nickel chrome superalloy and a ferritic stainless steel;

securing each of n−

1 plates between the anode surface of one of the n electrochemical cells and the cathode surface of another one of the n electrochemical cells;

securing each of the remaining 2 plates to an outer surface of one of the outermost of the n electrochemical cells; and

heating the layered assembly to the operating temperature of the electrochemical cells.

38. The method of claim 37, further comprising the steps of:

selecting an anode material from a solution comprising a composition selected from a nickel oxide, a nickel oxide/yttria stabilized-zirconia, a nickel salt, a copper salt, a silver salt, a platinum salt, a gold salt, a doped alkaline earth titanate, a lanthanum chromite, precursors thereof, and mixtures thereof; and

a particulate slurry comprising a composition selected from nickel, copper, cobalt, silver, platinum, gold, a nickel alloy, a copper alloy, a silver alloy, a platinum alloy, a gold alloy, a doped alkaline earth titanate, a lanthanum chromite, precursors thereof, and mixtures thereof; and

selecting a cathode material from a lanthanum manganite, a doped lanthanum manganite, a lanthanide cobaltite, precursors thereof, and mixtures thereof.

11. A supported ceramic membrane, comprising:

a first outer layer comprising at least one sheet of a fugitive-containing ceramic electrolyte material in the green state;

an inner layer comprising at least one sheet of a dense ceramic electrolyte material in the green state; and

a second outer layer comprising at least one sheet of the fugitive-containing ceramic electrolyte material, the second outer layer having substantially the same thickness as the first outer layer;

the tri-layer assembly being laminated and then sintered to form a composite structure, the fugitive-containing ceramic electrolyte layers becoming porous after sintering.

12. The supported ceramic membrane of claim 11, wherein the inner layer of the dense ceramic electrolyte material has substantially the same thickness as each outer porous layer formed after sintering.

13. The supported membrane of claim 11, wherein the dense ceramic electrolyte material and the fugitive-containing ceramic electrolyte material each is selected from a stabilized zirconia composition.

14. The supported membrane of claim 13, wherein the dense ceramic electrolyte material and the fugitive-containing ceramic electrolyte material each is selected from a scandia-doped zirconia composition.

15. The supported ceramic membrane of claim 14, wherein the dense ceramic electrolyte material is a fully stabilized scandia-doped zirconia composition and the fugitive-containing ceramic electrolyte material is a partially stabilized scandia-doped zirconia composition.

16. The supported membrane of claim 11, wherein the dense ceramic electrolyte material is selected from a stabilized zirconia composition and the fugitive containing material is selected from a stabilized ceria composition.

17. A supported ceramic membrane, comprising:

a first outer layer comprising at least one sheet of a fugitive-containing fully stabilized scandia-doped zirconia composition in the green state;

an inner layer comprising at least one sheet of a dense fully stabilized ceramic electrolyte material in the green state positioned above the fugitive-containing ceramic electrolyte layer; and

a second outer layer comprising at least one sheet of a fugitive-containing fully stabilized scandia-doped zirconia composition in the green state positioned above the dense ceramic electrolyte layer, the second outer layer having substantially the same thickness as the first outer layer;

the tri-layer assembly being laminated and then sintered to form a composite structure, the fugitive-containing ceramic electrolyte layers becoming porous after sintering, the porous layers defining pores having an average size between 100 nanometers and 200 microns.

18. The supported membrane of claim 17, wherein the porous layers have a pore volume greater than 50% of the total geometric volume.

19. The supported membrane of claim 17, wherein the porous layers have a pore volume greater than 20% and less than 50% of the total geometric volume.

22. An electrochemical cell, comprising:

the supported ceramic membrane of claim 17;

an anode material deposited on an outer surface of the supported ceramic membrane, the anode material being selected from

a solution comprising a composition selected from a nickel oxide, a nickel oxide/yttria stabilized-zirconia, a nickel salt, a copper salt, a silver salt, a platinum salt, a gold salt, a doped alkaline earth titanate, a lanthanum chromite, precursors thereof, and mixtures thereof; and

a particulate slurry comprising a composition selected from nickel, copper, cobalt, silver, platinum, gold, a nickel alloy, a copper alloy, a silver alloy, a platinum alloy, a gold alloy, a doped alkaline earth titanate, a lanthanum chromite, precursors thereof, and mixtures thereof; and

a cathode material deposited on the opposing outer surface of the supported ceramic membrane, the cathode material being selected from a lanthanum manganite, a doped lanthanum manganite, a lanthanide ferrite, a lanthanide cobaltite, precursors thereof, and mixtures thereof.

27. An electrochemical cell stack, comprising:

a first dense electronically conductive ceramic plate;

a first tri-layer assembly comprising;

a first layer of a fugitive-containing ceramic electrolyte material in the green state having a surface adjacent to the first dense electronically conductive ceramic plate;

a layer of a dense ceramic electrolyte material in the green state positioned above the fugitive-containing layer; and

a second layer of the fugitive-containing ceramic electrolyte material positioned above the dense ceramic electrolyte material;

a second dense electronically conductive ceramic plate adjacent to the second fugitive-containing layer of the tri-layer assembly;

a second tri-layer assembly comprising;

a first layer of a fugitive-containing ceramic electrolyte material in the green state having a surface adjacent to the opposing surface of the second dense electronically conductive ceramic plate;

a layer of a dense ceramic electrolyte material in the green state positioned above the fugitive-containing layer; and

a second layer of the fugitive-containing ceramic electrolyte material positioned above the dense ceramic electrolyte material; and

a third dense electronically conductive ceramic plate adjacent to the second fugitive-containing layer of the second tri-layer assembly;

the layered assembly being laminated and then sintered to form a composite structure, the fugitive-containing ceramic electrolyte layers becoming porous after sintering, an anode being applied to alternating porous layers formed after sintering and a cathode being applied to the remaining porous layers.

28. The electrochemical cell stack of claim 27, wherein

the anode material is selected from a solution comprising a composition selected from a nickel oxide, a nickel oxide/yttria stabilized-zirconia, a nickel salt, a copper salt, a silver salt, a platinum salt, a gold salt, a doped alkaline earth titanate, a lanthanum chromite, precursors thereof, and mixtures thereof;

and a particulate slurry comprising a composition selected from nickel, copper, cobalt, silver, platinum, gold, a nickel alloy, a copper alloy, a silver alloy, a platinum alloy, a gold alloy, a doped alkaline earth titanate, a lanthanum chromite, precursors thereof, and mixtures thereof; and

the cathode material is selected from a lanthanum manganite, a doped lanthanum manganite, a lanthanide ferrite, a lanthanide cobaltite, precursors thereof, and mixtures thereof.

29. The electrochemical cell stack of claim 28, wherein each of the dense electronically conductive ceramic plates is selected from a lanthanum chromite.

30. An electrochemical cell stack, comprising:

n tri-layer assemblies wherein n≧

2;

each of the tri-layer assemblies comprising

a first layer of a fugitive-containing ceramic electrolyte material in the green state;

a layer of a dense ceramic electrolyte material in the green state positioned above the fugitive-containing layer; and

a second layer of the fugitive-containing ceramic electrolyte material positioned above the dense ceramic electrolyte material; and

n+1 dense electronically conductive ceramic plates;

wherein each of n−

1 plates is secured between the first layer of one of the n tri-layer assemblies and the second layer of one of the n tri-layer assemblies and each of the remaining 2 plates is secured to an outer surface of one of the outermost of the n tri-layer assemblies;

the layered assembly being laminated and then sintered to form a composite structure, the fugitive-containing ceramic electrolyte layers becoming porous after sintering, an anode being applied to alternating porous layers formed after sintering and a cathode being applied to the remaining porous layers.

31. The electrochemical cell stack of claim 30, wherein

the anode material is selected from a solution comprising a composition selected from a nickel oxide, a nickel oxide/yttria stabilized-zirconia, a nickel salt, a copper salt, a silver salt, a platinum salt, a gold salt, a doped alkaline earth titanate, a lanthanum chromite, precursors thereof, and mixtures thereof;

and a particulate slurry comprising a composition selected from nickel, copper, cobalt, silver, platinum, gold, a nickel alloy, a copper alloy, a silver alloy, a platinum alloy, a gold alloy, a doped alkaline earth titanate, a lanthanum chromite, precursors thereof, and mixtures thereof; and

the cathode material is selected from a lanthanum manganite, a doped lanthanum manganite, a lanthanide ferrite, a lanthanide cobaltite, precursors thereof, and mixtures thereof.

32. The electrochemical cell stack of claim 30 wherein each of the dense electronically conductive ceramic plates is selected from a lanthanum chromite.

33. A method of making a supported ceramic membrane, comprising the steps of:

providing a first layer comprising at least one sheet of a fugitive-containing ceramic electrolyte material in the green state;

positioning a second layer comprising at least one sheet of a dense ceramic electrolyte material in the green state above the fugitive-containing layer;

positioning a second layer comprising at least one sheet of a fugitive-containing ceramic electrolyte material in the green state above the dense ceramic electrolyte layer, the second outer layer having substantially the same thickness as the first outer layer; and

laminating and then sintering the tri-layer assembly to form a composite structure, the fugitive-containing ceramic electrolyte layers becoming porous after sintering.

34. The method of claim 33, further comprising the steps of:

selecting the dense ceramic electrolyte material from a stabilized zirconia composition; and

selecting the fugitive-containing ceramic electrolyte material from a stabilized zirconia composition and a stabilized ceria composition.

35. A method of making an electrochemical cell, comprising the steps of:

depositing an anode material on an outer surface of a supported ceramic membrane prepared according to the steps of claim 33;

and

depositing a cathode material on the opposing outer surface of the supported ceramic membrane.

36. The method of claim 35, further comprising the steps of:

selecting an anode material from a solution comprising a composition selected from a nickel oxide, a nickel oxide/yttria stabilized-zirconia, a nickel salt, a copper salt, a silver salt, a platinum salt, a gold salt, a doped alkaline earth titanate, a lanthanum chromite, precursors thereof, and mixtures thereof; and

a particulate slurry comprising a composition selected from nickel, copper, cobalt, silver, platinum, gold, a nickel alloy, a copper alloy, a silver alloy, a platinum alloy, a gold alloy, a doped alkaline earth titanate, a lanthanum chromite, precursors thereof, and mixtures thereof; and

selecting a cathode material from a lanthanum manganite, a doped lanthanum manganite, a lanthanide ferrite, a lanthanide cobaltite, precursors thereof, and mixtures thereof.

39. A method of making an electrochemical cell stack, comprising the steps of:

providing n tri-layer assemblies wherein n≧

2;

each of the tri-layer assemblies comprising

a first layer of a fugitive-containing ceramic electrolyte material in the green state;

a layer of a dense ceramic electrolyte material in the green state positioned above the fugitive-containing layer; and

a second layer of the fugitive-containing ceramic electrolyte material positioned above the dense ceramic electrolyte material;

providing n+1 dense electronically conductive ceramic plates;

securing each of n−

1 plates between the first layer of one of the n tri-layer assemblies and the second layer of one of the n tri-layer assemblies;

securing each of the remaining 2 plates to an outer surface of one of the outermost of the n tri-layer assemblies;

laminating and sintering the layered assembly to form a composite structure, the fugitive-containing ceramic electrolyte layers becoming porous after sintering;

applying an anode material to alternating porous layers formed after sintering; and

applying a cathode material to the remaining porous layers.

40. The method of claim 39, further comprising the steps of:

selecting an anode material from a solution comprising a composition selected from a nickel oxide, a nickel oxide/yttria stabilized-zirconia, a nickel salt, a copper salt, a silver salt, a platinum salt, a gold salt, a doped alkaline earth titanate, a lanthanum chromite, precursors thereof, and mixtures thereof; and

a particulate slurry comprising a composition selected from nickel, copper, cobalt, silver, platinum, gold, a nickel alloy, a copper alloy, a silver alloy, a platinum alloy, a gold alloy, a doped alkaline earth titanate, a lanthanum chromite, precursors thereof, and mixtures thereof; and

selecting a cathode material from a lanthanum manganite, a doped lanthanum manganite, a lanthanide ferrite, a lanthanide cobaltite, precursors thereof, and mixtures thereof.

41. The electrochemical cell stack of claim 39, wherein each of the dense electronically conductive ceramic plates is selected from a lanthanum chromite.