Reinforced electrolyte membrane

• US 9,893,373 B2
• Filed: 05/18/2011
• Issued: 02/13/2018
• Est. Priority Date: 05/25/2010
• Status: Active Grant

• Current Assignee: Johnson Matthey Hydrogen Technologies Limited (Johnson Matthey PLC)
• Original Assignee: 3M Innovative Properties Company (3M Company)
• Inventors: Yandrasits, Michael Andrew, Lee, Ji-Hwa, Yi, Youngdon, Pierpont, Daniel McGregor, Hamrock, Steven Joseph, Schonewill, Mark Albert
• Primary Examiner(s): Slifka, Sarah A
• Application Number:
  US13/699,210
• Publication Number:
  US 20130101918A1
• Time in Patent Office: 2,463 Days
• CPC Class Codes: C08J 2327/16 Homopolymers or copolymers of vinylidene fluoride
• CPC Class Codes: C08J 5/2206 based on organic and/or inorganic macromolecular compounds
• CPC Class Codes: H01M 2300/0082 Organic polymers
• CPC Class Codes: H01M 2300/0094 in the form of layered products, e.g. coatings
• CPC Class Codes: H01M 8/1023 having only carbon, e.g. polyarylenes, polystyrenes or polybutadiene-styrenes
• CPC Class Codes: H01M 8/1039 halogenated, e.g. sulfonated polyvinylidene fluorides
• CPC Class Codes: H01M 8/1051 Non-ion-conducting additives, e.g. stabilisers, SiO2 or ZrO2
• CPC Class Codes: H01M 8/1053 consisting of layers of polymers with at least one layer being ionically conductive
• CPC Class Codes: H01M 8/106 characterised by the chemical composition of the porous support
• CPC Class Codes: H01M 8/1062 characterised by the physical properties of the porous support, e.g. its porosity or thickness
• CPC Class Codes: H01M 8/1067 characterised by their physical properties, e.g. porosity, ionic conductivity or thickness
• CPC Class Codes: H01M 8/1069 characterised by the manufacturing processes
• CPC Class Codes: H01M 8/1081 starting from solutions, dispersions or slurries exclusively of polymers
• 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

An electrolyte membrane having a proton conducting polymer reinforced with a nanofiber mat made from a nanofiber comprising a fiber material selected from polymers and polymer blends; wherein the fiber material has a fiber material proton conductivity; wherein the proton conducting polymer has a proton conducting polymer conductivity; and wherein the fiber material proton conductivity is less than the proton conducting polymer conductivity, and methods of making. In some embodiments, the nanofiber further comprises a proton conducting polymer.

Claims

1. An electrolyte membrane, comprising:

a first proton conducting polymer reinforced with a nanofiber mat;

wherein the nanofiber mat is made from a nanofiber comprising a fiber material selected from the group consisting of (i) PES, (ii) a PES blend, (iii) PEI, (iv) a PEI blend, (v) PBI, (vi) a PBI blend, (vii) PPO, (viii) a PPO blend, (ix) PEEK, (x) a PEEK blend, (xi) PPES, (xii) a PPES blend, (xiii) PEK, (xiv) a PEK blends, and (xv) combinations thereof, and

wherein the nanofiber has an average diameter no greater than 1000 nm; and

wherein the first proton conducting polymer is selected from the group consisting of highly fluorinated ionomer, perfluorinated ionomer, hydrocarbon ionomer, blends and combinations thereof.

2. The electrolyte membrane of claim 1, wherein the fiber material is PES blended with PVDF.

3. The electrolyte membrane of claim 1, wherein the fiber material comprises at least one of:

PES, PEI, PBI, PPO, PEEK, PPES, and PEK blended with a proton conducting polymer.

4. The electrolyte membrane of claim 1, wherein the fiber material is crosslinked.

5. The electrolyte membrane of claim 1, wherein the nanofiber mat has an average basis weight in a range from 3.2 g/m² to 6.5 g/m².

6. The electrolyte membrane of claim 1, wherein the electrolyte membrane has a thickness in the range of from about 10 micrometers to about 50 micrometers.

7. The electrolyte membrane of claim 1, wherein the first proton conducting polymer further comprises a stabilizing additive comprising an element selected from the group consisting of Mn and Ce.

8. The electrolyte membrane of claim 7, wherein the first proton conducting polymer comprises a pendant group having the structure selected from the group consisting of:

—

OCF₂CF₂CF₂CF₂SO₃Y,

—

OCF₂CF(CF₃)OCF₂CF₂SO₃Y, and

—

CF₂SO₂N(Z)SO₂(CF₂)₃SO₃Y,

wherein Y is a hydrogen ion or a cation and Z is a suitable countercation.

9. The electrolyte membrane of claim 8, wherein the first proton conducting polymer has an equivalent weight of 900 or less.

10. The electrolyte membrane of claim 1, wherein the fiber material further comprises a stabilizing additive comprising an element selected from the group consisting of Mn and Ce.

11. A membrane electrode assembly comprising the electrolyte membrane of claim 1.

12. The electrolyte membrane of claim 1, wherein an average thickness of the nanofiber mat is in a range of about 20% to 60% of an average thickness of the electrolyte membrane.

13. The electrolyte membrane of claim 1, wherein the electrolyte membrane comprises the nanofiber mat in a central layer region with a proton conducting polymer layer on either side and wherein the center layer region is smaller than the proton conducting polymer layer.

14. The electrolyte membrane of claim 1, wherein nanofibers in the nanofiber mat are not fused together.

15. The electrolyte membrane of claim 1, wherein the nanofiber mat is made from a nanofiber comprising a fiber material selected from the group consisting of (i) PES, (ii) PEI, (iii) (v) PBI, (iv) PPO, (v) PEEK, (vi) PPES, (vii) PEK, and (viii) combinations thereof.

16. A multilayer electrolyte membrane comprising:

the electrolyte membrane of claim 1, further comprising at least one layer of a second proton conducting polymer adhered to a major surface of the electrolyte membrane, wherein the second proton conducting polymer is selected from the group consisting of highly fluorinated ionomer, perfluorinated ionomer, hydrocarbon ionomer, blends and combinations thereof.

17. A membrane electrode assembly comprising the multilayer electrolyte membrane of claim 16.

18. A method of making an electrolyte membrane, comprising:

(a) providing a nanofiber mat comprising a nanofiber comprising a fiber material, wherein the fiber material comprises a polymer selected from the group consisting of (i) PES, (ii) PES blends, (iii) PEI, (iv) PEI blends, (v) PBI, (vi) PBI blends, (vii) PPO, (viii) PPO blends, (ix) PEEK, (x) PEEK blends, (xi) PPES, (xii) PPES blends, (xiii) PEK, (xiv) PEK blends, and (xv) combinations thereof, wherein the nanofiber has an average diameter no greater than 1000 nm; and

(b) at least partially filling the nanofiber mat with a first proton conducting polymer, wherein the first proton conducting polymer is selected from the group consisting of highly fluorinated ionomer, perfluorinated ionomer, hydrocarbon ionomer, blends and combinations thereof.

19. The method of claim 18 further comprising applying any one of a sizing, a binder, or a polymeric treatment to the nanofiber mat prior to step b).