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

• US 7,767,358 B2
• Filed: 05/31/2005
• Issued: 08/03/2010
• Est. Priority Date: 05/31/2005
• Status: Expired due to Fees

• Current Assignee: Nextech Materials, Ltd.
• Original Assignee: Nextech Materials, Ltd.
• Inventors: Sabolsky, Edward M., Sabolsky, Katarzyna, Day, Michael J., Seabaugh, Matthew M.
• Primary Examiner(s): Ryan; Patrick
• Assistant Examiner(s): Parsons; Thomas H.
• Application Number:
  US11/141,259
• Publication Number:
  US 20060269813A1
• Time in Patent Office: 1,890 Days
• Field of Search: 429/12, 429/30, 429/33, 429/38, 429 40- 42, 429126-127, 429/149, 429/160, 429/188, 429/304, 429321-323, 204/421, 205/200, 205/353, 205/521, 205/532, 252/62.2, 427/115, 501/103, 501/104, 296/233, 296/235
• US Class Current: 429/483
• 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. An electrochemical cell, consisting essentially of:

a first support layer in the form of an anode layer comprising at least one sheet of a porous ceramic electrolyte material having an anode infiltrant in the pores thereof;

an electrolyte layer comprising at least one sheet of a dense ceramic electrolyte material positioned above the anode layer; and

a second support layer in the form of a cathode layer comprising at least one sheet of the porous ceramic electrolyte material positioned above the electrolyte layer and having a cathode infiltrant in the pores thereof.

2. The electrochemical cell of claim 1, wherein

the anode infiltrant comprises 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, 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, or a mixture thereof;

and

the cathode infiltrant material comprises a lanthanum manganite, a doped lanthanum manganite, a lanthanide ferrite, a lanthanide cobaltite, or a mixture thereof.

3. The electrochemical cell of claim 1, wherein the electrolyte layer has substantially the same thickness as the anode layer and the cathode layer.

4. The electrochemical cell of claim 1, wherein the dense ceramic electrolyte material and the porous ceramic electrolyte material each comprise stabilized zirconia composition.

5. The electrochemical cell of claim 4, wherein the dense ceramic electrolyte material and the porous ceramic electrolyte material each comprise scandia-doped zirconia composition.

6. The electrochemical cell of claim 5, wherein the dense ceramic electrolyte material comprises a fully stabilized scandia-doped zirconia composition and the porous ceramic electrolyte material comprises a partially stabilized scandia-doped zirconia composition.

7. The electrochemical cell of claim 5, wherein the dense ceramic electrolyte material comprises a partially stabilized scandia-doped zirconia composition and the porous ceramic electrolyte material comprises a fully stabilized scandia-doped zirconia composition.

8. The electrochemical cell of claim 1, wherein the dense ceramic electrolyte material comprises a stabilized zirconia composition and the porous ceramic electrolyte material comprises a stabilized ceria composition.

9. The electrochemical cell of claim 1, wherein the anode layer ceramic electrolyte material and the cathode layer ceramic electrolyte material each have a pore volume greater than 50% of the total geometric volume.

10. The electrochemical cell of claim 1, wherein the anode layer ceramic electrolyte material and the cathode layer ceramic electrolyte material each have a pore volume greater than 20% and less than 50% of the total geometric volume.

11. The electrochemical cell of claim 1, wherein the anode layer ceramic electrolyte material and the cathode layer ceramic electrolyte material each have an average pore size between 100 nanometers and 200 microns.

12. The electrochemical cell of claim 1, wherein a ratio of the thickness between the anode layer and the electrolyte layer ranges from about 6:

1 to about 1;

1.

13. The electrochemical cell of claim 1, wherein a ratio of the thickness of the cathode layer to the electrolyte layer ranges from about 6:

1 to about 1;

1.

14. The electrochemical cell of claim 1, wherein a ratio of the thickness of the anode layer to the electrolyte layer ranges from about 6:

1 to about 1;

1 and a ratio of the thickness of the cathode layer to the electrolyte layer ranges from about 6;

1 to about 1;

1.

15. The electrochemical cell of claim 1, wherein the anode layer and the cathode layer are each at least 28 μ

m in thickness.

16. The electrochemical cell of claim 15, wherein the electrolyte layer is at least 50 μ

m in thickness.

17. An electrochemical cell stack, comprising:

a first dense electronically conductive plate comprising a nickel chrome superalloy or a ferritic stainless steel;

a first electrochemical cell of claim 1 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 1 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.

18. The electrochemical cell stack of claim 17, wherein

the anode infiltrant comprises 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, 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, or a mixture thereof;

and

the cathode infiltrant material comprises a lanthanum manganite, a doped lanthanum manganite, a lanthanide ferrite, a lanthanide cobaltite, or a mixture thereof.

19. An electrochemical cell stack, comprising:

n electrochemical cells of claim 1, wherein n>

2; and

n+1 dense electronically conductive plates comprising a nickel chrome superalloy or a ferritic stainless steel;

wherein each of n−

1 plates is secured between a surface of the anode layer of one of the n electrochemical cells and a surface of the cathode layer 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.

20. The electrochemical cell stack of claim 19 wherein

the anode infiltrant comprises 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, 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, or a mixture thereof;

and

the cathode infiltrant material comprises a lanthanum manganite, a doped lanthanum manganite, a lanthanide ferrite, a lanthanide cobaltite, or a mixture thereof.

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

providing n electrochemical cells of claim 1, wherein n>

2;

providing n+1 dense electronically conductive plates comprising a nickel chrome superalloy or a ferritic stainless steel;

securing each of n−

1 plates between a surface of the anode layer of one of the n electrochemical cells and a surface of the cathode layer 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.

22. The method of claim 21, wherein:

the anode infiltrant comprises 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, 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, or a mixture thereof; and

the cathode infiltrant material comprises a lanthanum manganite, a doped lanthanum manganite, a lanthanide ferrite, a lanthanide cobaltite, or a mixture thereof.

23. An electrochemical cell, comprising:

a first support layer in the form of an anode layer comprising at least one sheet of a porous ceramic electrolyte material having an anode infiltrant in the pores thereof;

an electrolyte layer comprising at least one sheet of a dense ceramic electrolyte material positioned above the anode layer; and

a second support layer in the form of a cathode layer comprising at least one sheet of the porous ceramic electrolyte material positioned above the electrolyte layer and having a cathode infiltrant in the pores thereof,

wherein the anode layer and the cathode layer are each at least 28 μ

m in thickness and the electrolyte layer is at least 50 μ

m in thickness, the electrolyte layer being sufficiently supported by the anode layer and the cathode layer to provide mechanical integrity for the electrochemical cell.

24. The electrochemical cell of claim 23, wherein the anode layer and the cathode layer are each not greater than 340 μ

m in thickness.

25. The electrochemical cell of claim 23, wherein the electrolyte layer is not greater than 100 μ

m in thickness.

26. An electrochemical cell, comprising:

a first support layer in the form of an anode layer comprising at least one sheet of a porous ceramic electrolyte material having an anode infiltrant in the pores thereof;

an electrolyte layer comprising at least one sheet of a dense ceramic electrolyte material positioned above the anode layer; and

a second support layer in the form of a cathode layer comprising at least one sheet of the porous ceramic electrolyte material positioned above the electrolyte layer and having a cathode infiltrant in the pores thereof,

wherein the electrolyte layer is sufficiently supported by the anode layer and the cathode layer to provide mechanical integrity for the electrochemical cell.