IP Library Granted Patent US 8,475,971
Granted Patent B2
US 8,475,971 · App. 10/997,475 · Granted Jul 2, 2013

Membrane treatment method

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Quick Facts
Patent No.
US 8,475,971
App. No.
10/997,475
Granted
Jul 2, 2013
Kind
B2
Abstract

A method of enhancing electrical performance of a membrane for a fuel cell is disclosed. The method includes providing a perfluorosulfonic acid (PFSA) ionomer in an aqueous hydroxylated hydrocarbon aqueous solution. The PFSA dispersion or solution has an acid number the same or higher than an acid number of the membrane. The membrane is immersed in the solution such that the high acid number PFSA dispersion diffuses into the membrane. After immersion, the removed membrane is then dried under tension.

Claims (35)

1. A method of enhancing electrical performance of a polymer electrolyte membrane for a fuel cell, comprising:

providing a preformed perfluorosulfonic acid membrane having a first dry weight and having a first acid number that defines an equivalent weight of sulfonic acid groups in said perfluorosulfonic acid membrane;

providing an aqueous solution comprising a perfluorosulfonic acid ionomer dispersed or dissolved in an aqueous hydroxylated-hydrocarbon, said perfluorosulfonic acid ionomer having a second acid number that defines an equivalent weight of sulfonic acid groups in said perfluorosulfonic acid ionomer, said second acid number of said perfluorosulfonic acid ionomer being at least as high as said first acid number of said perfluorosulfonic acid membrane;

immersing said preformed perfluorosulfonic acid membrane having said first dry weight in said aqueous solution so that said perfluorosulfonic acid ionomer dispersed or dissolved in said aqueous hydroxylated-hydrocarbon diffuses into said perfluorosulfonic acid membrane, said preformed perfluorosulfonic acid membrane swelling during said immersion;

removing said perfluorosulfonic acid membrane from said aqueous solution; and

drying said perfluorosulfonic acid membrane under tension to provide an enhanced perfluorosulfonic acid membrane comprising a second dry weight higher than said first dry weight and that is thinner than said preformed perfluorosulfonic acid membrane.

2. The method of claim 1 wherein said hydroxylated hydrocarbon comprises at least one of methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, tertiary-butanol, mixtures thereof, and mixtures thereof with water.

3. The method of claim 1 wherein said second acid number of said perfluorosulfonic acid ionomer is in the range of between about 0.9 and about 1.6 millequivalents of sulfonic acid groups per gram of perfluorosulfonic acid ionomer.

4. The method of claim 1 wherein said first acid number of said preformed perfluorosulfonic acid membrane, before being immersed in said aqueous solution, is in a range of between about 0.7 and about 1.3 milliequivalents of sulfonic acid per gram of membrane.

5. The method of claim 1 wherein said preformed perfluorosulfonic acid membrane, before being immersed in said aqueous solution, is a composite membrane comprising hydrocarbon ionomers wherein said membrane has an acid number between 1 and 3 milliequivalents of sulfonic acid groups per gram of ionomer.

6. The method of claim 1 wherein said preformed perfluorosulfonic acid membrane, before being immersed in said aqueous solution, is a composite membrane comprising perfluorosulfonic acid ionomers.

7. The method of claim 1 wherein said preformed perfluorosulfonic acid membrane, before being immersed in said aqueous solution, is a composite membrane comprising a blend of hydrocarbon and perfluorosulfonic acid ionomers.

8. The method of claim 1 wherein said preformed perfluorosulfonic acid membrane, before being immersed in said aqueous solution, is a composite membrane comprising hydrocarbon ionomer and perfluorosulfonic acid ionomer films.

9. A method of enhancing electrical performance of a polymer electrolyte membrane for a fuel cell, comprising:

providing a preformed perfluorosulfonic acid membrane having a dry weight and having a first acid number that defines an equivalent weight of sulfonic acid groups in said perfluorosulfonic acid membrane;

imbibing from about 5 to about 50 weight percent of a perfluorosulfonic acid ionomer having said dry weight into said preformed perfluorosulfonic acid membrane, wherein said weight percent is calculated on the basis of the dry weight increase of said preformed perfluorosulfonic acid membrane, said perfluorosulfonic acid ionomer having a second acid number that defines an equivalent weight of sulfonic acid groups in said perfluorosulfonic acid ionomer, and said second acid number of said perfluorosulfonic acid ionomer being higher than said first acid number of said perfluorosulfonic acid membrane; and

drying said perfluorosulfonic acid membrane under tension to provide an enhanced perfluorosulfonic acid membrane that is thinner than said preformed perfluorosulfonic acid membrane.

10. The method of claim 9 wherein said hydroxylated hydrocarbon comprises at least one of methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, tertiary-butanol, mixtures thereof, and mixtures thereof with water.

11. The method of claim 9 wherein said second acid number of said perfluorosulfonic acid ionomer is in the range of between about 0.9 to about 1.6 milliequivalents of sulfonic acid groups per gram of perfluorosulfonic acid ionomer.

12. The method of claim 9 wherein said first acid number of said preformed perfluorosulfonic acid membrane, before being immersed in said aqueous solution, is in a range of between about 0.7 and about 1.3 milliequivalents of sulfonic acid per gram of membrane.

13. The method of claim 9 wherein said preformed perfluorosulfonic acid membrane, before being immersed in said aqueous solution, is a composite membrane comprising hydrocarbon ionomers comprising at least one of carbon, hydrogen, and potentially oxygen, nitrogen, phosphorus, silicon, and sulfur.

14. The method of claim 9 wherein said preformed perfluorosulfonic acid membrane, before being immersed in said aqueous solution, is a composite membrane comprising perfluorosulfonic acid ionomers.

15. The method of claim 9 wherein said preformed perfluorosulfonic acid membrane, before being immersed in said aqueous solution, is a composite membrane comprising a blend of hydrocarbon and perfluorosulfonic acid ionomers.

16. The method of claim 9 wherein said preformed perfluorosulfonic acid membrane, before being immersed in said aqueous solution, is a composite membrane comprising hydrocarbon ionomer and perfluorosulfonic acid ionomer films.

17. The method of claim 9 comprising imbibing from about 5 to about 20 weight percent of said perfluorosulfonic acid ionomer into said preformed perfluorosulfonic acid membrane by immersing said preformed perfluorosulfonic acid membrane in an aqueous solution comprising the perfluorosulfonic acid ionomer and a hydroxylated-hydrocarbon, wherein said weight percent is calculated on the basis of the dry weight increase of said membrane.

18. A method of enhancing electrical performance of a polymer electrolyte membrane for a fuel cell, comprising:

providing a preformed perfluorosulfonic acid membrane having a first dry weight and having a first acid number that defines an equivalent weight of sulfonic acid groups in said perfluorosulfonic acid membrane;

providing an aqueous solution comprising a perfluorosulfonic acid ionomer dispersed or dissolved in an aqueous hydroxylated-hydrocarbon, said perfluorosulfonic acid ionomer having a second acid number that defines an equivalent weight of sulfonic acid groups in said perfluorosulfonic acid ionomer, said second acid number of said perfluorosulfonic acid ionomer being at least as high as said first acid number of said perfluorosulfonic acid membrane;

immersing said preformed perfluorosulfonic acid membrane having said first dry weight in said aqueous solution so that said perfluorosulfonic acid ionomer dispersed or dissolved in said aqueous hydroxylated-hydrocarbon diffuses into said perfluorosulfonic acid membrane, said preformed perfluorosulfonic acid membrane swelling during said immersion;

removing said perfluorosulfonic acid membrane from said aqueous solution; and

drying said perfluorosulfonic acid membrane under tension to provide an enhanced perfluorosulfonic acid membrane comprising a second dry weight higher than said first dry weight and that is one half the thickness of said preformed perfluorosulfonic acid membrane.

19. A method of enhancing electrical performance of a polymer electrolyte membrane for a fuel cell, comprising:

providing a preformed perfluorosulfonic acid membrane having a dry weight and having a first acid number that defines an equivalent weight of sulfonic acid groups in said perfluorosulfonic acid membrane;

imbibing from about 5 to about 50 weight percent of a perfluorosulfonic acid ionomer having said dry weight into said preformed perfluorosulfonic acid membrane, wherein said weight percent is calculated on the basis of the dry weight increase of said preformed perfluorosulfonic acid membrane, said perfluorosulfonic acid ionomer having a second acid number that defines an equivalent weight of sulfonic acid groups in said perfluorosulfonic acid ionomer, and said second acid number of said perfluorosulfonic acid ionomer being higher than said first acid number of said perfluorosulfonic acid membrane; and

drying said perfluorosulfonic acid membrane under tension to provide an enhanced perfluorosulfonic acid membrane that is one half the thickness of said preformed perfluorosulfonic acid membrane.

Assignments (13)
RELEASE OF SECURITY INTEREST Recorded Nov 7, 2014
From: WILMINGTON TRUST COMPANY
To: GM GLOBAL TECHNOLOGY OPERATIONS LLC
Reel/Frame 034371/0676 →
CHANGE OF NAME Recorded Feb 10, 2011
From: GM GLOBAL TECHNOLOGY OPERATIONS, INC.
To: GM GLOBAL TECHNOLOGY OPERATIONS LLC
Reel/Frame 025780/0936 →
SECURITY AGREEMENT Recorded Nov 8, 2010
From: GM GLOBAL TECHNOLOGY OPERATIONS, INC.
To: WILMINGTON TRUST COMPANY
Reel/Frame 025327/0001 →
RELEASE OF SECURITY INTEREST Recorded Nov 4, 2010
From: UNITED STATES DEPARTMENT OF THE TREASURY
To: GM GLOBAL TECHNOLOGY OPERATIONS, INC.
Reel/Frame 025245/0442 →
RELEASE OF SECURITY INTEREST Recorded Nov 4, 2010
From: UAW RETIREE MEDICAL BENEFITS TRUST
To: GM GLOBAL TECHNOLOGY OPERATIONS, INC.
Reel/Frame 025311/0770 →
SECURITY AGREEMENT Recorded Aug 28, 2009
From: GM GLOBAL TECHNOLOGY OPERATIONS, INC.
To: UAW RETIREE MEDICAL BENEFITS TRUST
Reel/Frame 023162/0001 →
SECURITY AGREEMENT Recorded Aug 27, 2009
From: GM GLOBAL TECHNOLOGY OPERATIONS, INC.
To: UNITED STATES DEPARTMENT OF THE TREASURY
Reel/Frame 023156/0052 →
RELEASE OF SECURITY INTEREST Recorded Aug 21, 2009
From: CITICORP USA, INC. AS AGENT FOR BANK PRIORITY SECURED PARTIES; CITICORP USA, INC. AS AGENT FOR HEDGE PRIORITY SECURED PARTIES
To: GM GLOBAL TECHNOLOGY OPERATIONS, INC.
Reel/Frame 023127/0468 →
RELEASE OF SECURITY INTEREST Recorded Aug 20, 2009
From: UNITED STATES DEPARTMENT OF THE TREASURY
To: GM GLOBAL TECHNOLOGY OPERATIONS, INC.
Reel/Frame 023124/0429 →
SECURITY AGREEMENT Recorded Apr 16, 2009
From: GM GLOBAL TECHNOLOGY OPERATIONS, INC.
To: CITICORP USA, INC. AS AGENT FOR BANK PRIORITY SECURED PARTIES; CITICORP USA, INC. AS AGENT FOR HEDGE PRIORITY SECURED PARTIES
Reel/Frame 022553/0446 →
SECURITY AGREEMENT Recorded Feb 4, 2009
From: GM GLOBAL TECHNOLOGY OPERATIONS, INC.
To: UNITED STATES DEPARTMENT OF THE TREASURY
Reel/Frame 022201/0610 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Jan 13, 2009
From: GENERAL MOTORS CORPORATION
To: GM GLOBAL TECHNOLOGY OPERATIONS, INC.
Reel/Frame 022092/0737 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Jan 24, 2005
From: FULLER, TIMOTHY J.; DOBULIS, BEBA T.
To: GENERAL MOTORS CORPORATION
Reel/Frame 015617/0883 →