Anode with remarkable stability under conditions of extreme fuel starvation

• US 8,748,056 B2
• Filed: 10/10/2007
• Issued: 06/10/2014
• Est. Priority Date: 10/18/2006
• Status: Active Grant

• Current Assignee: Bloom Energy Corporation
• Original Assignee: Bloom Energy Corporation
• Inventors: Batawi, Emad El, Hickey, Darren, McElroy, James
• Primary Examiner(s): Gilliam, Barbara
• Assistant Examiner(s): Arciero, Adam A
• Application Number:
  US11/907,204
• Publication Number:
  US 20080096080A1
• Time in Patent Office: 2,435 Days
• Field of Search: None
• US Class Current: 429/484
• CPC Class Codes: H01M 2004/8684 Negative electrodes
• CPC Class Codes: H01M 2008/1293 Fuel cells with solid oxide electrolytes
• CPC Class Codes: H01M 4/861 with a gradient in the porosity
• CPC Class Codes: H01M 4/8642 Gradient in composition
• CPC Class Codes: H01M 4/8652 as mixture
• CPC Class Codes: H01M 4/8657 layered
• CPC Class Codes: H01M 4/8885 Sintering or firing
• CPC Class Codes: H01M 4/9016 Oxides, hydroxides or oxygenated metallic salts
• CPC Class Codes: H01M 4/9066 of metal-ceramic composites or mixtures, e.g. cermets
• 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 solid oxide fuel cell (SOFC) includes a cathode electrode, a solid oxide electrolyte, and an anode electrode having a first portion and a second portion, such that the first portion is located between the electrolyte and the second portion. The anode electrode comprises a cermet comprising a nickel containing phase and a ceramic phase. The first portion of the anode electrode contains a lower porosity and a lower ratio of the nickel containing phase to the ceramic phase than the second portion of the anode electrode.

Claims

1. A solid oxide fuel cell (SOFC), comprising:

a cathode electrode;

a solid oxide electrolyte; and

an anode electrode comprising a first portion comprising a cermet containing a nonzero volume percent of a nickel containing phase and a nonzero volume percent of a ceramic phase comprising doped ceria and a second portion comprising a cermet containing a nonzero volume percent of a nickel containing phase and a nonzero volume percent of a ceramic phase comprising doped ceria, such that the first portion is located between the electrolyte and the second portion;

wherein;

the SOFC is an electrolyte-supported SOFC and the first portion of the anode electrode contains a lower ratio of the nickel containing phase to the ceramic phase than the second portion of the anode electrode;

the first portion of the anode electrode has a thickness of 3 to 30 microns; and

the second portion of the anode electrode has a thickness of 3 to 30 microns.

2. The SOFC of claim 1, wherein the doped ceria phase comprises Sm, Gd or Y doped ceria phase.

3. The SOFC of claim 2, wherein the doped ceria phase composition comprises Ce₍₁₋

x)A_xO₂ where A comprises at least one of Sm, Gd, or Y, and x is greater than 0.1 but less than 0.4.

4. The SOFC of claim 3, wherein the doped ceria phase comprises a Sm doped ceria phase.

5. The SOFC of claim 2, wherein the first portion comprises a first sublayer in contact with the electrolyte and the second portion comprises a second sublayer located over the first sublayer.

6. The SOFC of claim 5, wherein the first sublayer contains a lower porosity than the second sublayer.

7. The SOFC of claim 6, wherein:

the first sublayer contains between 1 and 15 volume percent of the nickel containing phase, between 5 and 30 volume percent pores and remainder the doped ceria phase; and

the second sublayer contains between 20 and 60 volume percent nickel containing phase, between 20 and 60 volume percent pores and remainder the doped ceria phase.

8. The SOFC of claim 6, wherein:

the first sublayer contains between 5 and 25 weight percent of the nickel containing phase and between 75 and 95 weight percent of the doped ceria containing phase; and

the second sublayer contains between 60 and 85 weight percent of the nickel containing phase and between 15 and 40 weight percent of the doped ceria containing phase.

9. The SOFC of claim 8, wherein the nickel containing phase consists essentially of nickel or nickel oxide and the doped ceria containing phase consists essentially of scandia doped ceria.

10. The SOFC of claim 2, wherein:

the first portion comprises a first sublayer in contact with the electrolyte and a second sublayer located over the first sublayer;

the second portion comprises a third sublayer located over the second sublayer and a fourth sublayer located over the third sublayer;

a porosity of the anode electrode increases from the first sublayer to the fourth sublayer;

the nickel containing phase content of the anode electrode increases from the first sublayer to the fourth sublayer;

the first sublayer contains between 1 and 5 volume percent of the nickel containing phase, between 5 and 10 volume percent pores and remainder the doped ceria phase;

the second sublayer contains between 6 and 20 volume percent of the nickel containing phase, between 20 and 40 volume percent pores and remainder the doped ceria phase;

the third sublayer contains between 25 and 35 volume percent of the nickel containing phase, between 30 and 50 volume percent pores and remainder the doped ceria phase; and

the fourth sublayer contains between 35 and 45 volume percent of the nickel containing phase, between 40 and 60 volume percent pores and remainder the doped ceria phase.

11. The SOFC of claim 2, wherein the anode electrode comprises a single layer having a graded composition.

12. The SOFC of claim 11, wherein a volume fraction of the nickel containing phase and a porosity in the anode electrode increases from an interface between the electrolyte and the anode electrode to a surface of the anode electrode distal from the electrolyte.

13. The SOFC of claim 2, wherein the second portion of the anode electrode has a higher porosity than first portion of the anode electrode.

14. The SOFC of claim 2, wherein the anode electrode contains a doped ceria phase rich interface at a three phase boundary with the electrolyte and a nickel phase rich region adjacent to a surface of the anode electrode which is distal from the electrolyte.

15. The SOFC of claim 2, wherein a first region of the anode electrode located adjacent to a fuel inlet contains a lower ratio of the nickel containing phase to the ceramic phase than a second region of the anode electrode located adjacent to a fuel outlet.

16. The SOFC of claim 15, wherein:

a first quadrant of the anode electrode adjacent to the fuel inlet and adjacent to the electrolyte contains a lowest ratio of the nickel containing phase to the ceramic phase in the anode electrode; and

a second quadrant of the anode electrode adjacent to the fuel outlet and distal from the electrolyte contains a highest ratio of the nickel containing phase to the ceramic phase in the anode electrode.

17. The SOFC of claim 2, wherein the electrolyte comprises scandia stabilized zirconia.

18. The SOFC of claim 1, wherein:

the ceramic phase in the first portion of the anode electrode comprises a samaria doped ceria phase having a composition Ce_(1-x)Sm_xO₂ where x is greater than 0.1 but less than 0.4; and

the ceramic phase in the second portion of the anode electrode comprises a samaria doped ceria phase having a composition Ce_(1-x)Sm_xO₂ where x is greater than 0.1 but less than 0.4.