Liquid composition, method for producing it, and method for producing membrane/electrode assembly
To provide a liquid composition with which a catalyst layer and a polymer electrolyte membrane will hardly be broken at the time of their formation and a method for producing the liquid composition; and a method for producing a membrane/electrode assembly by which a catalyst layer and a polymer electrolyte membrane will hardly be broken at the time of their formation. A liquid composition comprising a polymer having ion exchange groups, water and an organic solvent, wherein the average secondary particle size of the polymer having ion exchange groups is from 100 to 3,000 nm, and the primary particle size parameter represented by the product of the average primary particle size (nm) and the ion exchange capacity (meq/g dry resin) of the polymer having ion exchange groups, is from 12 to 20.
1. A liquid composition comprising
a polymer having ion exchange groups,
water, and
an organic solvent,
wherein
the polymer has an average secondary particle size of from 100 to 3,000 nm,
the polymer has a primary particle size parameter represented by a product of an average primary particle size (nm) and ion exchange capacity (meq/g dry resin) of from 12 to 20,
a proportion of water is from 10 to 60 mass % based on the total amount of water and the organic solvent,
the polymer having ion exchange groups has structural units having an ion exchange group and structural units based on a perfluoromenoene monomer having a 5-membered ring or a perfluorodiene monomer capable of forming a 5-membered ring by cyclopolymerization, and
the ion exchange capacity of the polymer having ion exchange groups is from 1.1 to 2.0 meq/g dry resin.
2. The liquid composition according to claim 1 , wherein the organic solvent contains at least one C 1-4 alcohol.
3. The liquid composition according to claim 1 , wherein the polymer is a perfluoropolymer having ion exchange groups.
4. The liquid composition according to claim 1 , wherein
the polymer having ion exchange groups is a polymer obtained by converting precursor groups of polymer (F) into ion exchange groups, and
the polymer (F) is a polymer having structural units based on a perfluoromonomer having a precursor group represented by formula (g1), and the structural units based on a perfluoromonoene monomer having a 5-membered ring or a perfluorodiene monomer capable of forming a 5-membered ring by cyclopolymerization:
Q 1 is a perfluoroalkylene group which optionally has an etheric oxygen atom, Q 2 is a single bond or a perfluoroalkylene group which optionally has an etheric oxygen atom, and Y is a fluorine atom or a monovalent perfluoroorganic group.
5. The liquid composition according to claim 4 , wherein the polymer (F) further has structural units based on tetrafluoroethylene.
6. The liquid composition according to claim 1 , wherein a concentration of the polymer in the liquid composition is from 10 to 26 mass %.
7. A method for producing the liquid composition according to claim 1 , the method comprising:
preparing a mixed liquid containing the polymer, water and the organic solvent, at a concentration of the polymer of from 12 to 30 mass % with a proportion of water of from 10 to 40 mass % based on a total amount of water and the organic solvent; and
stirring the mixed liquid at a shear rate of at least 50 s −1 and heating the mixed liquid to 100 to 150° C. to increase the viscosity of the mixed liquid, and keeping stirring until the viscosity of the mixed liquid is decreased and stabilized.
8. A polymer electrolyte membrane formed from the liquid composition according to claim 1 .
9. A method for producing a polymer electrolyte membrane, the method comprising
applying the liquid composition according to claim 1 to a substrate, and
removing water and the organic solvent.
10. A membrane/electrode assembly for a polymer electrolyte fuel cell, the assembly comprising
an anode having a catalyst layer,
a cathode having a catalyst layer, and
a polymer electrolyte membrane disposed between the anode and the cathode,
wherein at least one catalyst layer of the cathode and the anode is a catalyst layer formed from a mixed liquid of the liquid composition according to claim 1 and a catalyst.
11. A method for producing the membrane/electrode assembly according to claim 10 , the method comprising
mixing the liquid composition and the catalyst to obtain the mixed liquid, and
forming the catalyst layer of at least one of the cathode and the anode by using the mixed liquid.
12. A membrane/electrode assembly for a polymer electrolyte fuel cell, the assembly comprising
an anode having a catalyst layer,
a cathode having a catalyst layer, and
a polymer electrolyte membrane disposed between the anode and the cathode,
wherein the polymer electrolyte membrane is formed from the liquid composition according to claim 1 .
13. A method for producing the assembly according to claim 12 , the method comprising
forming the polymer electrolyte membrane by using the liquid composition.
14. The liquid composition according to claim 1 , obtained by a method comprising:
preparing a mixed liquid containing the polymer, water and the organic solvent, at a concentration of the polymer of from 12 to 30 mass % with a proportion of water of from 10 to 40 mass % based on a total amount of water and the organic solvent; and
stirring the mixed liquid at a shear rate of at least 50 s −1 and heating the mixed liquid to 100 to 150° C. to increase viscosity of the mixed liquid, and keeping stirring until the viscosity of the mixed liquid is decreased and stabilized.
15. The liquid composition according to claim 14 , the method further comprising:
adding an additional dispersion medium to the liquid composition to adjust the concentration of the polymer having ion exchange groups to from 10 to 26 mass %.
16. The liquid composition according to claim 1 , wherein the proportion of water is from 10 to 40 mass % based on the total amount of water and the organic solvent.