IP Library Granted Patent US 10,446,861
Granted Patent B2
US 10,446,861 · App. 14/981,104 · Granted Oct 15, 2019

Flowing electrolyte fuel cell with improved performance and stability

Inventors: Divyaraj Desai (Sunnyvale, CA); Vedasri Vedharathinam (San Jose, CA); Martin Joseph Sheridan (Redwood City, CA); Ashish V. Pattekar (Cupertino, CA); Craig Eldershaw (Belmont, CA); Rajesh Kumar Padmarajan (Mountain View, CA); Gabriel Iftime (Dublin, CA)
Assignee: Palo Alto Research Center Incorporated
H01M8/04283H01M4/8626H01M8/023H01M8/188H01M8/22H01M8/2455Y02E60/528
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Quick Facts
Patent No.
US 10,446,861
App. No.
14/981,104
Granted
Oct 15, 2019
Kind
B2
Abstract

A flowing electrolyte fuel cell system design (DHCFC-Flow) is provided. The use of a flowing oxygen-saturated electrolyte in a fuel cell offers a significant enhancement in the cell performance characteristics. The mass transfer and reaction kinetics of the superoxide/peroxide/oxide ion (mobile oxygen ion species) in the fuel cell are enhanced by recirculating an oxidizing gas-saturated electrolyte. Recirculating oxygen-saturated electrolyte through a liquid channel enhances the maximal current observed in a fuel cell. The use of a oxygen saturated electrolyte ensures that the reaction kinetics of the oxygen reduction reaction are fast and the use of convection ameliorates concentration gradients and the diffusion-limited maximum current density. The superoxide ion is generated in situ by the reduction of the oxygen dissolved in the gaseous electrolyte. Also, a dual porosity membrane allows the uniform flow of fuel (e.g., methane) on the fuel side, without allowing phase mixing. The capillary pressure for liquid intrusion into the gas phase and vice versa is quite large, estimated to be 1-10 psi. This makes it easier to control the fluctuations in gas/liquid velocity which might otherwise lead to phase mixing and the loss of fuel cell performance. In one variation, a dual-porosity membrane structure is incorporated in the system to allow uniform flow of fuel and prevent mixing of fuel with a liquid electrolyte.

Claims (37)

1. A peroxide or superoxide-ion conducting electrochemical fuel cell system employing the use of a gaseous fuel for electrochemical energy conversion and at least one fuel cell, the at least one fuel cell comprising:

an inlet portion configured to receive liquid electrolyte in an oxygen saturated state;

a flow path configured to facilitate a flow of the liquid electrolyte;

a dual-porosity gas permeable membrane configured to allow uniform flow of the gaseous fuel on a fuel side of the at least one fuel cell and provide a barrier to the liquid electrolyte to prevent phase mixing of the gaseous fuel with the liquid electrolyte; and,

an outlet portion configured to provide an exit for the flowing liquid electrolyte in a depleted state.

2. The system as set forth in claim 1 wherein the liquid electrolyte is saturated with at least one of oxygen or oxygen ions.

3. The system as set forth in claim 1 further comprising a mechanism configured to saturate the liquid electrolyte with oxygen, provide the oxygen-saturated liquid electrolyte to the inlet portion, and receive the oxygen-depleted liquid electrolyte liquid from the outlet portion.

4. The system as set forth in claim 1 wherein oxygen ions are generated in-situ and incorporated into the flow of the liquid electrolyte.

5. The system set forth in claim 1 wherein carbon-containing products of fuel cell reaction (CO x , x=1, 2) are dissolved in the liquid electrolyte and carried away for carbon capture and sequestration.

6. The system as set forth in claim 1 wherein the membrane comprises a porous gas diffuser bonded to a catalyst-coated nanoporous layer.

7. The system as set forth in claim 6 wherein the gas diffuser has pores with diameters in a range of approximately 5-100 microns.

8. The system as set forth in claim 7 wherein the gas diffuser has a thickness of approximately 5 millimeters.

9. The system as set forth in claim 6 wherein the catalyst-coated nanoporous layer has pores with diameters in a range of approximately 5 nanometers to 10 microns.

10. The system as set forth in claim 6 wherein the catalyst-coated nanoporous layer comprises a nanoporous layer having a thickness of approximately 50 microns and a coating layer of approximately 1 micron.

11. The system as set forth in claim 6 wherein the nanoporous layer comprises at least one of an anodized aluminum oxide, a porous polymer including PTFE (polytetrafluoroethylene), expanded or porous PTFE (polytetrafluoroethylene), a polyimide including porous polyimide, or a porous ceramic including porous alumina or porous zirconia.

12. The system as set forth in claim 6 wherein the nanoporous layer is surface treated to be nonwett-able by the electrolyte.

13. The system as set forth in claim 10 wherein the coating layer comprises PTFE (polytetrafluoroethylene) or a non-stick type coating.

14. The system as set forth in claim 1 wherein the electrolyte is an ionic liquid.

15. The system as set forth in claim 14 , wherein the ionic liquid is at least one of 1-ethyl, 3-methyl imidazolium trifluoromethanesulfonate [emim][OTf], 1-ethyl, 3-methyl imidazolium bis(trifluoromethylsulfonylimide) [emim][TFSI], butyl trimethylammonium bis(trifluoromethylsulfonylimide) [btma][TFSI], 1-propyl, 3-methylpyrrolidinium bis(trifluorosulfonylimide) [pmpy][TFSI], 1-butyl, 3-methylpyrrolidinium bis(trifluorosulfonylimide) [bmpy][TFSI], 1-ethyl-3-methylimidazolium dicyanamide [emim][-DCA], 1,2-dimethyl-3-propylimidazolium bis(trifluoromethylsulfonyl)imide [mmpim][TFSI],and 1-ethyl-2,3-dimethylimidazolium bis trifluoromethylsulfonyl)imide.

16. The system as set forth in claim 1 wherein an operating temperature is in a range of approximately 100-400° C.

17. The system as set forth in claim 1 comprising a stack of fuel cells.

18. The system as set forth in claim 17 wherein the stack of fuel cells is electrically connected in a series-parallel combination configuration to achieve the desired voltage and current delivering capability.

19. A peroxide or superoxide-ion conducting electrochemical fuel cell system employing the use of a gaseous fuel for electrochemical energy conversion and at least one fuel cell, the at least one fuel cell comprising:

a fuel inlet;

a fuel outlet;

and,

dual-porosity gas permeable membrane configured to allow uniform flow of the gaseous fuel between the fuel inlet and fuel outlet and provide a barrier to a flowing oxygen saturated liquid electrolyte to prevent phase mixing of the gaseous fuel with the liquid electrolyte.

20. The system as set forth in claim 19 wherein the membrane comprises a porous gas diffuser bonded to a catalyst-coated nanoporous layer.

21. The system as set forth in claim 20 wherein the gas diffuser has pores with diameters in a range of approximately 5-100 microns.

22. The system as set forth in claim 20 wherein the gas diffuser has a thickness of approximately 5 millimeters.

23. The system as set forth in claim 20 wherein the catalyst-coated nanoporous layer has pores with diameters in a range of approximately 5 nanometers to 1 micron.

24. The system as set forth in claim 20 wherein the catalyst-coated nanoporous layer comprises a nanoporous layer having a thickness of approximately 50 microns and a coating layer of approximately 1 micron.

25. The system as set forth in claim 20 wherein the nanoporous layer comprises at least one of an anodized aluminum oxide, a porous polymer including PTFE (polytetrafluoroethylene), expanded or porous PTFE (polytetrafluoroethylene), a polyimide including porous polyimide, or a porous ceramic including porous alumina or porous zirconia.

26. The system as set forth in claim 20 wherein the nanoporous layer is surface treated to be nonwettable by the electrolyte.

27. The system as set forth in claim 24 wherein the coating layer comprises PTFE (polytetrafluoroethylene) or a non-stick type coating.

28. The system as set forth in claim 19 wherein the liquid electrolyte is an ionic liquid.

29. The system as set forth in claim 19 wherein an operating temperature is in a range of approximately 100-400° C.

Assignments (8)
TERMINATION AND RELEASE OF SECURITY INTEREST IN PATENTS RECORDED AT RF 064760/0389 Recorded Feb 13, 2024
From: CITIBANK, N.A., AS COLLATERAL AGENT
To: XEROX CORPORATION
Reel/Frame 068261/0001 →
CONFIRMATORY LICENSE Recorded Nov 17, 2023
From: PALO ALTO RESEARCH CENTER, INCORPORATED
To: U.S. DEPARTMENT OF ENERGY
Reel/Frame 065626/0260 →
CORRECTIVE ASSIGNMENT TO CORRECT THE REMOVAL OF US PATENTS 9356603, 10026651, 10626048 AND INCLUSION OF US PATENT 7167871 PREVIOUSLY RECORDED ON REEL 064038 FRAME 0001. ASSIGNOR(S) HEREBY CONFIRMS THE ASSIGNMENT. Recorded Jun 28, 2023
From: PALO ALTO RESEARCH CENTER INCORPORATED
To: XEROX CORPORATION
Reel/Frame 064161/0001 →
SECURITY INTEREST Recorded Jun 22, 2023
From: XEROX CORPORATION
To: CITIBANK, N.A., AS COLLATERAL AGENT
Reel/Frame 064760/0389 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Jun 20, 2023
From: PALO ALTO RESEARCH CENTER INCORPORATED
To: XEROX CORPORATION
Reel/Frame 064038/0001 →
CONFIRMATORY LICENSE Recorded May 25, 2016
From: PALO ALTO RESEARCH CENTER, INCORPORATED
To: U.S. DEPARTMENT OF ENERGY
Reel/Frame 038806/0571 →
CORRECTIVE ASSIGNMENT TO CORRECT THE FIRST NAME OF THE FIRST ASSIGNOR PREVIOUSLY RECORDED AT REEL: 037368 FRAME: 0702. ASSIGNOR(S) HEREBY CONFIRMS THE ASSIGNMENT. Recorded Jan 6, 2016
From: DESAI, DIVYARAJ; VEDHARATHINAM, VEDASRI; SHERIDAN, MARTIN JOSEPH; PATTEKAR, ASHISH V.; ELDERSHAW, CRAIG; PADMARAJAN, RAJES KUMAR; IFTIME, GABRIEL
To: PALO ALTO RESEARCH CENTER INCORPORATED
Reel/Frame 037447/0482 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Dec 28, 2015
From: DESAI, DIVAYAJ; VEDHARATHINAM, VEDASRI; SHERIDAN, MARTIN JOSEPH; PATTEKAR, ASHISH V.; ELDERSHAW, CRAIG; PADMARAJAN, RAJES KUMAR; IFTIME, GABRIEL
To: PALO ALTO RESEARCH CENTER INCORPORATED
Reel/Frame 037368/0702 →
Continuity (1)
Related Publication 20170187054A1 · Jun 29, 2017