Method of fabricating an electrolyte material

Patent metadata

Field	Value
Publication number	US-9663600-B2
Application number	US-201214654451-A
Country	US
Kind code	B2
Filing date	Dec 21, 2012
Priority date	Dec 21, 2012
Publication date	May 30, 2017
Grant date	May 30, 2017

Abstract

A method of fabricating low EW, water insoluble electrolyte materials includes providing a perfluorinated polymer resin that includes perfluorinated carbon-carbon backbone chain and sulfonyl fluoride ended perfluorinated side chains, extending from the perfluorinated backbone chains via an ether linkage, exposing the perfluorinated polymer resin to ammonia gas to convert the sulfonyl fluoride groups to sulfonamide groups, —SO 2 —NH 2 , which reacts with sulfonyl fluoride containing chemical agent(s) to form sulfonimide groups, and at the same time, generates low EW, 3-dimensional cross-linked, water-insoluble perfluorinated polymer electrolyte materials.

First claim

The invention claimed is:

1. A method comprising:
providing a solid perfluorinated polymer resin comprising a perfluorinated carbon-carbon backbone and perfluorinated side chains that extend from the perfluorinated carbon-carbon backbone chain via an ether linkage and terminate in a sulfonyl fluoride group, —SO 2 —F;
forming the solid perfluorinated polymer resin into microsized particles; exposing the microsized particles of the solid perfluorinated polymer resin to ammonia gas to convert the sulfonyl fluoride groups to sulfonamide groups, —SO 2 —NH 2 , thereby producing a perfluorinated polymer in sulfonamide form; and
contacting the perfluorinated polymer in sulfonamide form with one or more chemical agents to convert the sulfonamide groups to sulfonimide groups, —SO 2 —NH—SO 2 —, thereby producing a perfluorinated polymer electrolyte material that is 3-dimensionally cross-linked, has an equivalent weight (EW) of less than 850 g/mol, and is water-insoluble.

2. The method as recited in claim 1 , wherein the solid perfluorinated polymer resin is a linear perfluorinated polymer resin and the providing of the solid perfluorinated polymer resin includes copolymerizing tetrafluoroethylene (TFE) and per-F vinyl ether monomers to produce the linear perfluorinated polymer resin.

3. The method as recited in claim 2 , wherein a molar ratio of TFE to per-F vinyl ether monomers on average in the linear perfluorinated polymer resin is 3:1 or less.

4. The method as recited in claim 1 , wherein the solid perfluorinated polymer resin is a perfluorinated homopolymer resin and the providing of the solid perfluorinated polymer resin includes polymerizing per-F vinyl ether monomers to produce the perfluorinated homopolymer resin.

5. The method as recited in claim 4 , wherein the polymerizing is conducted using an initiator of bis(pentafluoropropionyl) peroxide or bis(heptafluorobutyryl) peroxide, and a fluorinated solvent selected from the group consisting of HFC 43-10 and perfluorohexane.

6. The method as recited in claim 1 , wherein the exposing of the solid perfluorinated polymer resin to the ammonia gas includes adding additional ammonia gas to a reaction vessel containing the solid perfluorinated polymer resin in response to the ammonia gas being consumed by converting the sulfonyl fluoride groups to the sulfonamide groups.

7. The method as recited in claim 6 , further comprising controlling a pressure of the ammonia gas in the reaction vessel to maintain a predetermined pressure while the sulfonyl fluoride groups are converted to the sulfonamide groups.

8. The method as recited in claim 1 , wherein the one or more chemical agents includes F—SO 2 —Rf—SO 2 —F, where Rf is selected from the group consisting of —(CF 2 ) n — where n is 1-6 and —(CF 2 ) n′ —O—(CF 2 ) n′ — where n′ is 1-4.

9. The method as recited in claim 8 , wherein the one or more chemical agents includes F—SO 2 —CF 2 —SO 2 —F.

10. The method as recited in claim 8 , wherein the one or more chemical agents includes F—SO 2 —(CF 2 ) 6 —SO 2 —F.

11. The method as recited in claim 1 , wherein the contacting the perfluorinated polymer in sulfonamide form with a first chemical agent of the one or more chemical agents produces a product polymer, and wherein the method further comprises, after the contacting of the perfluorinated polymer in sulfonamide form with the first chemical agent of the one or more chemical agents, treating the product polymer with more of the first chemical agent of the one or more chemical agents or a second chemical agent of the one or more chemical agents to convert unreacted sulfonamide groups to sulfonimide groups.

12. The method as recited in claim 11 , wherein the converting the unreacted sulfonamide groups includes terminating side chains with sulfonyl fluoride groups, the sulfonyl fluoride groups being converted to sulfonic acid groups.

13. The method as recited in claim 11 , wherein the one or more chemical agents are selected from the group consisting of F—SO 2 —Rf—SO 2 —F, F—SO 2 —(Rf-SI) m -Rf—SO 2 —F, and F—SO 2 —(Rf-SI) m′ -(CF 2 ) m″ —CF 3 , wherein the Rf is independently selected from —(CF 2 ) n — where n is 1-6 and —(CF 2 ) n′ —O—(CF 2 ) n′ — where n′ is 1-4, the SI is —SO 2 —NH—SO 2 —, and m, m′, and m″ are 0-6, respectively.

14. The method as recited in claim 1 , wherein the perfluorinated polymer electrolyte material has an EW of 625 g/mol or less.

15. The method as recited in claim 8 , wherein the one or more chemical agents further comprises NH 2 —SO 2 —Rf′—SO 2 —NH 2 , where Rf′ is selected from the group consisting of —(CF 2 ) n — where n is 1-6 and —(CF 2 ) n′ —O—(CF 2 ) n′ — where n′ is 1-4.

16. The method as recited in claim 15 , wherein the one or more chemical agents includes NH 2 —SO 2 —CF 2 —SO 2 —NH 2 .

17. The method as recited in claim 15 , wherein the one or more chemical agents includes NH 2 —SO 2 —(CF 2 ) 6 —SO 2 —NH 2 .

18. The method as recited in claim 15 , wherein the contacting of the perfluorinated polymer in sulfonamide form with the one or more chemical agents includes adding the F—SO 2 —Rf—SO 2 —F, the NH 2 —SO 2 —Rf′—SO 2 —NH 2 and the perfluorinated polymer in sulfonamide form into a reaction vessel with at least one polar solvent and an amine catalyst.

19. The method as recited in claim 15 , wherein the contacting the perfluorinated polymer in sulfonamide form with the one or more chemical agents includes combining the F—SO 2 —Rf—SO 2 —F and the NH 2 —SO 2 —Rf′—SO 2 —NH 2 in a reaction vessel with an amine catalyst and a solvent to cause a reaction that produces a linear oligomer material with the sulfonyl fluoride end groups, and then combining the perfluorinated polymer in sulfonamide form and the linear oligomer material to convert the sulfonamide groups to the sulfonimide groups, thereby producing the perfluorinated polymer electrolyte material.

20. The method as recited in claim 15 , wherein the contacting of the perfluorinated polymer in sulfonamide form with the F—SO 2 —Rf—SO 2 —F and the NH 2 —SO 2 —Rf′—SO 2 —NH 2 includes combining X moles of the F—SO 2 —Rf—SO 2 —F, Y moles of the NH 2 —SO 2 —Rf—SO 2 —NH 2 , and Z moles of the perfluorinated polymer in sulfonamide form, calculated by sulfonamide groups, according to an equation X/(Y+0.5Z)≧1, where X, Y, and Z are variable, X>0, Y≧0 and Z>0.

21. The method as recited in claim 1 , wherein the perfluorinated polymer electrolyte material has an EW of 700 g/mol or less.

22. A method comprising:
providing a solid perfluorinated homopolymer resin, the providing the solid perfluorinated homopolymer resin comprising polymerizing per-F vinyl ether monomers using an initiator of bis(pentafluoropropionyl) peroxide or bis(heptafluorobutyryl) peroxide to produce the solid perfluorinated homopolymer resin, the solid perfluorinated homopolymer resin comprising a perfluorinated carbon-carbon backbone and perfluorinated side chains that extend from the perfluorinated carbon-carbon backbone chain via an ether linkage and terminate in a sulfonyl fluoride group, —SO 2 —F;
forming the solid perfluorinated homopolymer resin into microsized particles; exposing the microsized particles of the solid perfluorinated homopolymer resin to ammonia gas to convert the sulfonyl fluoride groups to sulfonamide groups, —SO 2 —NH 2 , thereby producing a perfluorinated polymer in sulfonamide form; and
contacting the perfluorinated polymer in sulfonamide form with one or more chemical agents to convert the sulfonamide groups to sulfonimide groups, —SO

Assignees

• Audi Ag
• Toyota Motor Co Ltd
• The Board Of Trustees Of The Univ Of Alabama The Univ Of Alabama
• Univ Alabama

Inventors

• Yang Zhiwei
• Gummalla Mallika
• Hosokawa Yoichi
• Thrasher Joseph S
• Sayler Todd S
• Matsnev Andrej
• Fernandez Richard Edward
• Waterfeld Alfred

Classifications

• H01M8/1088

  Chemical modification, e.g. sulfonation · CPC title

• C08J2327/18

  Homopolymers or copolymers of tetrafluoroethylene · CPC title

• H01M8/1039

  halogenated, e.g. sulfonated polyvinylidene fluorides · CPC title

• C08F214/262 Primary

  with fluorinated vinyl ethers · CPC title

• C08J5/225

  containing fluorine · CPC title