Proton exchange membrane materials for the advancement of direct methanol fuel-cell technology
View Patent ↗A new class of hybrid organic-inorganic materials, and methods of synthesis, that can be used as a proton exchange membrane in a direct methanol fuel cell. In contrast with Nafion® PEM materials, which have random sulfonation, the new class of materials have ordered sulfonation achieved through self-assembly of alternating polyimide segments of different molecular weights comprising, for example, highly sulfonated hydrophilic PDA-DASA polyimide segment alternating with an unsulfonated hydrophobic 6FDA-DAS polyimide segment. An inorganic phase, e.g., 0.5–5 wt % TEOS, can be incorporated in the sulfonated polyimide copolymer to further improve its properties. The new materials exhibit reduced swelling when exposed to water, increased thermal stability, and decreased O 2 and H 2 gas permeability, while retaining proton conductivities similar to Nafion®. These improved properties may allow direct methanol fuel cells to operate at higher temperatures and with higher efficiencies due to reduced methanol crossover.
1. A sulfonated polyimide copolymer, comprising alternating polyimide segments, having the following chemical structure:
2. The sulfonated polyimide copolymer of claim 1 wherein a FTIR-ATR spectrum of said copolymer is characterized by:
a) the absence of a polyamic acid peak at about 1670 cm −1 , indicating substantial completion of imidization reactions; and
b) the presence of a sulfonic acid peak at 1159 cm −1 .
3. A method of making a sulfonated polyimide copolymer, comprising the steps of:
a) combining and reacting a stoichiometric amount of 4,4′ hexafluorisopropylidene diphtalic anhydride (6FDA) and 4,4′-diaminosulfone aniline (DAS) in the presence of a catalyst and a solvent to produce a first solution comprising an unsulfonated hydrophobic 6FDA-DAS polyimide;
b) combining and reacting a stoichiometric amount of pyromellitic dianhydride (PDA) and 2,4-diaminobenzosulfonic acid (DASA) in the presence of the catalyst and the solvent to produce a second solution comprising a sulfonated PDA-DASA polyimide; and then
c) combining and reacting the fist solution comprising the 6FDA-DAS polyimide with the second solution comprising the PDA-DASA polyimide to produce a third solution comprising a 6FDA-DAS-PDA-DASA sulfonated polyimide copolymer comprising alternating polyimide segments.
4. The method of claim 3 , wherein the reaction in step a) is performed at about 80 C.
5. The method of claim 3 , wherein the reaction in step b) is performed at about 80 C.
6. The method of claim 3 , wherein the catalyst is triethylamine (TEA).
7. The method of claim 3 , wherein the reaction in step c) is performed at about 130 C.
8. The method of claim 3 , wherein the solvent comprises 1-methyl-2-pyrollidinone (NMP).
9. The method of claim 3 , further comprising using Carother's equation to control the final molecular weight of the polyimide 6FDA-DAS-PDA-DASA by changing the reactants stoichiometry of dianhydrides (6FDA and PDA) and diamines (DAS and DASA) to a ratio of 1:1.
10. The method of claim 8 , wherein the solvent additionally comprises 1,3-dichlorobenzene (DCB).
11. The method of claim 10 , wherein the molar ratio of NMP to DCB in the solvent is 4:1.
12. The method of claim 10 , further comprising removing water formed during cyclodehydration of the compound as shown below by forming a low boiling point azeotrope with the DCB during step c)
13. The method of claim 10 , further comprising distilling out the low boiling point azeotrope by utilizing an Allhin condenser and a Dean-Stark trap during step c).
14. The method of claim 13 , further comprising maintaining a constant solvent volume during step c) by replacing azeotroped DCB with new DCB via the Dean-Stark trap.
15. The method of claim 3 , wherein the reaction in step c) is performed for at least about 24 hours.
16. The method of claim 3 , wherein the reactions in steps a) and b) are each performed for at least about 16 hours.
17. The method of claim 3 , further comprising after step c):
d) cooling the third solution comprising 6FDA-DAS-PDA-DASA sulfonated polyimide copolymer to room temperature;
e) filtering the cooled third solution with a 0.8 micron nylon filter; and
f) precipitating the 6FDA-DAS-PDA-DASA into methanol to produce a solid precipitate that subsequently can be re-dissolved and cast on glass plates to produce thin films.
18. The method of claim 17 , further comprising after step f) casting of a film of 6FDA-DAS-PDA-DASA sulfonated polyimide copolymer PEM from a solution of N-methyl-2-pyrrolidone (NMP) and the copolymer PEM onto a hot plate heated to about 60 C, followed by drying in a vacuum oven at about 120 C for at least 24 hours.
19. A sulfonated polyimide copolymer produced according to the process of claim 3 .
20. The sulfonated polyimide copolymer of claim 19 , wherein the concentration of DASA is about 20 mol %.
21. The sulfonated polyimide copolymer of claim 20 , wherein the amount of swelling resulting when the copolymer is exposed to water is less than or equal to about 3 wt % swelling.
22. The sulfonated polyimide copolymer of claim 20 , wherein the temperature at which a 5% weight loss occurs is greater than about 480 C.
23. The sulfonated polyimide copolymer of claim 20 , wherein T g , as measured by Dynamic Mechanical Thermal Analysis (DMTA), is greater than or equal to about 410 C.
24. The sulfonated polyimide copolymer of claim 19 , wherein the concentration of DASA is about 40 mol %.
25. The sulfonated polyimide copolymer of claim 24 , wherein the H 2 gas permeability is equal to or less than about 70 barrers, and the O 2 gas permeability is equal to or less than bout 6 barrers.
26. The sulfonated polyimide copolymer of claim 24 , wherein the temperature at which a 5% weight loss occurs is greater than about 440 C.
27. The sulfonated polyimide copolymer of claim 24 , wherein T g , as measured by Dynamic Mechanical Thermal Analysis (DMTA), is greater than or equal to about 300 C.
28. The sulfonated polyimide copolymer of claim 24 , wherein the electrical conductivity is greater than or equal to about 1.2×10 −3 S/cm.
29. The sulfonated polyimide copolymer of claim 19 , wherein the concentration of DASA is about 60 mol %.
30. The sulfonated polyimide copolymer of claim 29 , wherein the electrical conductivity is greater than or equal to about 5×10 −2 S/cm.
31. The sulfonated polyimide copolymer of claim 19 , wherein the concentration of DASA is from about 20 mol % to about 60 mol %.
32. The sulfonated polyimide copolymer of claim 19 , further comprising an inorganic phase comprising about 0.5 wt % to about 5.0 wt % tetraethylyorthosilicate (TEOS).
33. The method of claim 17 , further comprising:
a) providing a polymer solution A comprising a 6FDA-DAS-PDA-DASA sulfonated polyimide copolymer produced according to claim 17 ;
b) providing a sol solution B comprising TEOS;
c) combining the polymer solution A with the sol solution B and mixing until a homogenous solution C results, comprising the hybrid organic-inorganic material.
34. The method of claim 33 , further comprising forming a film of the hybrid organic-inorganic material by casting solution C on a heated plate to make the film, and then baking the film in a vacuum oven.
35. The method of claim 33 , wherein the plate is heated to at least 60 C, and the vacuum oven is heated to at least 150 C.
36. The method of claim 33 , wherein polymer solution A comprises a solution of 6FDA-DAS-PDA-DASA sulfonated polyimide copolymer and NMP, wherein the concentration of copolymer is about 15 wt %.
37. The method of claim 33 , wherein sol solution B comprises a mixture of TEOS, ethanol, water and 1.0 M HCL in the molar ratio of 1:3.8:9.8:0.01.
38. The method of claim 17 , further comprising placing a piece of the 6FDA-DAS-PDA-DASA sulfonated polyimide copolymer into a diluted TEOS and solution for a period of time sufficient for the TEOS to be imbibed into the piece of 6FDA-DAS-PDA-DASA sulfonated polyimide copolymer.
39. The method of claim 38 , wherein the diluted TEOS sol solution comprises a mixture of TEOS, ethanol, water, and 1.0 M HCL in the molar ratio of 1:3.8:9.8:0.01.
40. The method of claim 38 , wherein the concentration of TEOS in the hybrid organic-inorganic material is about 1.3 wt % to about 1.6 wt % TEOS.