High temperature air purge of solid oxide fuel cell anode electrodes

• US 10,096,840 B1
• Filed: 12/14/2015
• Issued: 10/09/2018
• Est. Priority Date: 12/15/2014
• Status: Active Grant

• Current Assignee: Bloom Energy Corporation
• Original Assignee: Bloom Energy Corporation
• Inventors: Venkataraman, Swaminathan, El Batawi, Emad, Gottmann, Matthias, Armstrong, Tad, Pillai, Manoj, Anantha, Padiadpu Shankara, Radhakrishnan, Vijay, Sharif, Mohamed, Mohan, Pradhiba, Kandiboina, Rakesh
• Primary Examiner(s): Gatewood, Daniel S
• Application Number:
  US14/968,194
• Time in Patent Office: 1,030 Days
• Field of Search: None
• CPC Class Codes: H01M 2008/1293 Fuel cells with solid oxide electrolytes
• CPC Class Codes: H01M 2300/0071 Oxides
• CPC Class Codes: H01M 4/9033 Complex oxides, optionally doped, of the type M1MeO3, M1 being an alkaline earth metal or a rare earth, Me being a metal, e.g. perovskites
• CPC Class Codes: H01M 8/04228 during shut-down
• CPC Class Codes: H01M 8/04231 Purging of the reactants
• CPC Class Codes: H01M 8/04955 Shut-off or shut-down of fuel cells
• CPC Class Codes: H01M 8/2425 High-temperature cells with solid electrolytes
• CPC Class Codes: Y02E 60/50 Fuel cells

Abstract

A method of operating a solid oxide fuel cell (SOFC) system which contains a plurality of SOFCs having cermet anode electrodes includes operating the SOFC system above 760° C. to generate electricity and intentionally oxidizing the cermet anode electrodes at a temperature of at least 760° C. when the SOFC system stops operating to generate electricity.

Claims

1. A method of operating a solid oxide fuel cell (SOFC) system comprising a plurality of SOFCs having cermet anode electrodes, comprising:

operating the SOFC system above 760°

C. to generate electricity; and

intentionally oxidizing the cermet anode electrodes at a temperature of at least 760°

C. when the SOFC system stops operating to generate electricity, wherein;

the plurality of SOFCs are located in a SOFC stack; and

the step of intentionally oxidizing the cermet anode electrodes comprises providing an air purge;

the air purge is provided in response to an emergency stop of the SOFC system; and

the air purge is provided if a measured temperature of the SOFC stack is equal to or greater than 760°

C. after the emergency stop of the SOFC system, and the SOFC system operation is not restarted.

2. The method of claim 1, wherein intentionally oxidizing the cermet anode electrodes comprises converting a metallic phase of the cermet into a metal oxide phase.

3. The method of claim 2, wherein:

the cermet anode electrodes comprise a nickel containing metallic phase and at least one of a doped ceria and a stabilized zirconia ceramic phase; and

converting the metallic phase of the cermet into the metal oxide phase comprises converting the nickel into nickel oxide.

4. The method of claim 3, further comprising re-reducing the anode electrodes after the step of intentionally oxidizing the anode electrodes to convert the nickel oxide back into the nickel.

5. The method of claim 4, wherein the steps of intentionally oxidizing the cermet anode electrodes at a temperature above 760°

C. and re-reducing the anode electrodes maintains a nickel electrically conductive percolation network in the cermet anodes.

6. The method of claim 1, wherein:

the plurality of SOFCs are located in a SOFC stack; and

the step of intentionally oxidizing the cermet anode electrodes at a temperature above 760°

C. comprises intentionally providing an oxidizing agent to the anode electrodes through at least one of a fuel inlet conduit or a fuel outlet conduit of the SOFC stack.

7. The method of claim 1, wherein the air purge is provided within five minutes of the emergency stop of the SOFC system while a SOFC stack temperature is at least 760°

C.

8. The method of claim 1, wherein the air purge is provided while a SOFC stack temperature is 760 to 1100°

C.

9. The method of claim 1, wherein the air purge is provided automatically in response to the emergency stop of the SOFC system.

10. The method of claim 1, wherein the air purge has at least one of a higher air flow rate, pressure or volume than a respective air flow rate, pressure or volume which can be provided by exposing the anode electrodes to 1 atmosphere pressure air ambient.

11. The method of claim 10, wherein the air purge is provided at a pressure above 1 atmosphere by at least one of an air blower, an air pump, a pressurized air storage vessel, or an eductor.

12. The method of claim 11, further comprising:

providing an air inlet stream by at least one of the air blower or the air pump into a CPOx reactor during operation start-up of the SOFC system;

providing a fuel inlet stream into the CPOx reactor during the operation start-up of the SOFC system; and

providing an oxidized fuel inlet stream from the CPOx reactor into the SOFC stack during the operation start-up of the SOFC system;

wherein the air purge is provided by at least one of the air blower and the air pump through the CPOx reactor while the fuel inlet stream is not provided through the CPOx reactor in response to the emergency stop of the SOFC system.

13. A method of restoring electrical conductivity of a solid oxide fuel cell having a cermet anode electrode, comprising:

oxidizing the anode electrode at a temperature below 760°

C. and reducing the anode electrode;

re-oxidizing the anode electrode at a temperature above 760°

C. after reducing the anode electrode; and

re-reducing the anode electrode after re-oxidizing the anode electrode;

wherein;

an electrical contact resistivity of the anode electrode after the step of reducing is lower than the electrical contact resistivity of the anode electrode prior to the step of oxidizing the anode electrode;

the electrical contact resistivity of the anode electrode after the step of re-reducing is higher than the electrical contact resistivity of the anode electrode after the step of reducing;

the steps of oxidizing and re-oxidizing the anode electrode comprise converting a metallic phase of the cermet into a metal oxide phase;

the cermet anode electrode comprises a nickel containing metallic phase and at least one of a doped ceria and a stabilized zirconia ceramic phase;

converting the metallic phase of the cermet into the metal oxide phase comprises converting the nickel into nickel oxide;

the steps of reducing and re-reducing convert the nickel oxide back into the nickel;

the steps of oxidizing and reducing the cermet anode electrode disrupt a nickel electrically conductive percolation network in the cermet anode electrode; and

the steps of re-oxidizing and re-reducing restore the nickel electrically conductive percolation network in the cermet anode electrode.