Low equivalent weight ionomer
View Patent ↗An ionomer and a process for forming the ionomer such that the ionomer has (1) low equivalent weight (below 950, preferably between 625 and 850, and most preferably between 675 and 800) and (2) high conductivity (greater than 0.13 S/cm). In another embodiment, the invention is an ionomer having (1) low equivalent weight (below 950, preferably between 625 and 850, and most preferably between 675 and 800) and (2) acceptably low hydration (less than about 120 weight percent). These ionomers are capable of being processed into thin film and are extremely well-suited for low humidity or high temperature fuel cell applications.
1. A membrane comprising a fluorinated ionomer comprising a substantially fluorinated backbone with pendant groups attached thereto, said pendant groups represented by the formula
where X is F or Cl or mixtures thereof; n is an integer equal to one; R f and R f′ are independently selected from the group consisting of F, Cl, perfluoroalkyl radical, and chloroperfluoroalkyl radical; Y is an acid group or a functional group convertible to acid group; a is zero or an integer greater than zero; and b is an integer greater than zero;
wherein said ionomer has the combination of an equivalent weight between about 600 and about 950;
together with a high room temperature ionic conductivity of greater than about 0.13 S/cm when measured on an acid form of a membrane of said ionomer.
2. A membrane comprising a fluorinated ionomer as defined in claim 1 where a is equal to zero; b is equal to 1; n is equal to one; R f and R f′ are both Fluorine and Y is chosen from the group consisting of SO 3 Z; SO 2 N(R 1 R 1′ ), SO 2 NR 1 SO 2 R 2 , CO 2 Z, PO(OR 1 ) 2 ; wherein Z is H, or any combination of ammonium ion, metallic ions or organoammonium ions; R 1 and R 1′ are independently selected from the group consisting of H, an alkyl group with carbon number from 1 to 10, or a partially fluorinated alkyl group with a carbon number of 1-10, and R 2 is a perfluorinated alkyl chain with carbon number from 1 to 8, or a perfluoroalkyl group terminated with Y as it is defined above.
3. A membrane comprising a fluorinated ionomer as defined in claim 2 where Y is SO 3 H.
4. A membrane comprising a fluorinated ionomer as defined in claim 1 where a is equal to zero; b is equal to 1; n is equal to one; R f and R f′ are both F; and Y is chosen from the group consisting of SO 2 W, where W is selected from the group consisting of F, Cl, or Br; and COOR; where R is an alkyl group with carbon number from 1 to 20.
5. A membrane comprising a fluorinated ionomer of claim 4 where Y is SO 2 F.
6. A membrane comprising a porous support and the fluorinated ionomer of claim 1 impregnated within said porous support.
7. A membrane comprising a porous support and the fluorinated ionomer of claim 2 impregnated within said porous support.
8. A membrane comprising a porous support and the fluorinated ionomer of claim 3 impregnated within said porous support.
9. A membrane comprising a porous support and the fluorinated ionomer of claim 4 impregnated within said porous support.
10. A membrane comprising a porous support and the fluorinated ionomer of claim 5 impregnated within said porous support.
11. A membrane as defined in claim 6 wherein said porous support is expanded polytetrafluoroethylene.
12. A membrane as defined in claim 6 wherein said fluorinated ionomer substantially completely impregnates said porous support.
13. A membrane electrode assembly comprising an anode and a cathode sandwiching the membrane of claim 6 .
14. A membrane as defined in claim 7 wherein said porous support is expanded polytetrafluoroethylene.
15. A membrane as defined in claim 7 wherein said fluorinated ionomer substantially completely impregnates said porous support.
16. A membrane as defined in claim 8 wherein said porous support is expanded polytetrafluoroethylene.
17. A membrane as defined in claim 8 wherein said fluorinated ionomer substantially completely impregnates said porous support.
18. A membrane as defined in claim 9 wherein said porous support is expanded polytetrafluoroethylene.
19. A membrane as defined in claim 9 wherein said fluorinated ionomer substantially completely impregnates said porous support.
20. A membrane as defined in claim 10 wherein said porous support is expanded polytetrafluoroethylene.
21. A membrane as defined in claim 10 wherein said fluorinated ionomer substantially completely impregnates said porous support.
22. A membrane comprising a fluorinated ionomer comprising a substantially fluorinated backbone with pendant groups attached thereto, said pendant groups represented by the formula
where X is F or Cl or mixtures thereof n is an integer equal to one; R f and R f′ are independently selected from the group consisting of F, Cl, perfluoroalkyl radical, and chloroperfluoroalkyl radical; Y is an acid group or an acid derivative easily converted to an acid group; a is zero or an integer greater than zero; and b is an integer greater than zero;
wherein said ionomer has the combination of an equivalent weight between about 700 and about 900 together with a low hydration at room temperature that is less than 50%.
23. A membrane comprising a fluorinated ionomer of claim 22 wherein the equivalent weight is about 800 and the degree of hydration is between about 40% and about 45% at room temperature.
24. A membrane comprising a fluorinated ionomer of claim 22 where the equivalent weight is between about 810 and about 860 and the degree of hydration is between about 32% and about 42% at room temperature.
25. A membrane comprising a porous support and the fluorinated ionomer of claim 22 impregnated within said porous support.
26. A membrane comprising a porous support and the fluorinated ionomer of claim 23 impregnated within said porous support.
27. A membrane comprising a porous support and the fluorinated ionomer of claim 24 impregnated within said porous support.
28. A membrane as defined in claim 25 wherein said fluorinated ionomer substantially completely impregnates said porous support.
29. A membrane as defined in claim 26 wherein said fluorinated ionomer substantially completely impregnates said porous support.
30. A membrane as defined in claim 27 wherein said fluorinated ionomer substantially completely impregnates said porous support.
31. A membrane as defined in claim 25 wherein said porous support is expanded polytetrafluoroethylene.
32. A membrane as defined in claim 26 wherein said porous support is expanded polytetrafluoroethylene.
33. A membrane as defined in claim 27 wherein said porous support is expanded polytetrafluoroethylene.
34. A membrane comprising a fluorinated ionomer comprising a substantially fluorinated backbone with pendant groups attached thereto, said pendant groups represented by the formula
where X is F or Cl or mixtures thereof n is an integer equal to one; R f and R f′ are independently selected from the group consisting of F, Cl, perfluoroalkyl radical, and chloroperfluoroalkyl radical; Y is an acid group or an acid derivative easily converted to an acid group; a is zero or an integer greater than zero; and b is an integer greater than zero; wherein said ionomer has the combination of an equivalent weight below about 700 together with a hydration at room temperature that is less than 200%.
35. A membrane comprising a porous support and the fluorinated ionomer of claim 34 impregnated within said porous support.
36. A membrane as defined in claim 35 wherein said fluorinated ionomer substantially completely impregnates said porous support.
37. A membrane as defined in claim 35 wherein said porous support is expanded polytetrafluoroethylene.