Electrolyte material, liquid composition and membrane/electrode assembly for polymer electrolyte fuel cell
View Patent ↗To provide a membrane/electrode assembly excellent in the power generation characteristics even under low or no humidity conditions or under high humidity conditions, and an electrolyte material suitable for a catalyst layer of the 5 membrane/electrode assembly, an electrolyte material is used which comprises a polymer (H) having a unit (A) which has an ion exchange group and in which all hydrogen atoms (excluding H + of the ion exchange group) bonded to carbon atoms are substituted by fluorine atoms, a unit (B) which has a 5-membered ring and in which all hydrogen atoms bonded to carbon 10 atoms are substituted by fluorine atoms, and a unit (C) which has neither an ion exchange group nor a ring structure, has an ether bond, and has an ether equivalent of at most 350 as established by the following formula (I) and in which all hydrogen atoms bonded to carbon atoms are substituted by fluorine atoms: Ether equivalent=the molecular weight of the monomer forming the unit ( C )/the 15 number of ether bonds in the monomer forming the unit ( C ) (I).
1. An electrolyte material, which comprises a polymer (H) having
a unit (A) which has an ion exchange group and in which all hydrogen atoms (excluding H + of the ion exchange group) bonded to carbon atoms are substituted by fluorine atoms,
a unit (B) which has a 5-membered ring and in which all hydrogen atoms bonded to carbon atoms are substituted by fluorine atoms, and
a unit (C) which has neither an ion exchange group nor a ring structure, has an ether bond, and has an ether equivalent of at most 350 as established by the following formula (I) and in which all hydrogen atoms bonded to carbon atoms are substituted by fluorine atoms:
Ether equivalent=the molecular weight of the monomer forming the unit ( C )/the number of ether bonds in the monomer forming the unit ( C ) (I),
wherein at least one type of the unit (A) is a unit having a group represented by the following formula (g1):
wherein Q 21 is a perfluoroalkylene group which may have an etheric oxygen atom, Q 22 is a single bond or a perfluoroalkylene group which may have an etheric oxygen atom, Y 2 is a fluorine atom or a monovalent perfluoro organic group, R f2 is a perfluoroalkyl group which may have an etheric oxygen atom, X 2 is an oxygen atom, a nitrogen atom or a carbon atom, provided that when X 2 is an oxygen atom, b=0, when X 2 is a nitrogen atom, b=1, and when X 2 is a carbon atom, b=2.
2. The electrolyte material according to claim 1 , wherein at least one type of the unit (C) is one member selected from the group consisting of a unit represented by the following formula (u31), a unit represented by the following formula (u32) and a unit represented by the following formula (u33):
wherein v is an integer of from 0 to 3, w is 1 or 2, x is an integer of from 0 to 2, y is 1 or 2, and z is an integer of from 0 to 2.
3. The electrolyte material according to claim 1 , wherein the proportion of the unit (C) is from 1 to 30 mol % in all units (100 mol %) constituting the polymer (H).
4. The electrolyte material according to claim 1 , wherein at least one type of the unit (B) is a unit represented by the following formula (u21):
wherein each of R 11 and R 12 which are independent of each other, is a fluorine atom or a C 1-5 perfluoroalkyl group, and each of R 13 and R 14 which are independent of each other, is a fluorine atom, a C 1-5 perfluoroalkyl group or a C 1-5 perfluoroalkoxy group.
5. The electrolyte material according to claim 4 , wherein each of R 13 and R 14 is a fluorine atom.
6. The electrolyte material according to claim 4 , wherein at least one type of the unit represented by the formula (u21) is a unit represented by the following formula (u21-1):
7. The electrolyte material according to claim 1 , wherein at least one type of the unit (A) is a unit represented by the following formula (u12):
wherein q is 0 or 1.
8. The electrolyte material according to claim 1 wherein each of Q 21 and Q 22 which are independent of each other, is a C 1-6 perfluoroalkylene group which may have an etheric oxygen atom.
9. The electrolyte material according to claim 8 , wherein at least one of Q 21 and Q 22 is a C 1-6 perfluoroalkylene group which has an etheric oxygen atom.
10. The electrolyte material according to claim 1 , wherein the polymer (H) further has a unit derived from tetrafluoroethylene.
11. A liquid composition comprising a dispersion medium and the electrolyte material as defined in claim 1 dispersed in the dispersion medium, wherein the dispersion medium contains an organic solvent having a hydroxy group.
12. A membrane/electrode assembly for a polymer electrolyte fuel cell, which comprises
an anode having a catalyst layer containing a proton conductive polymer,
cathode having a catalyst layer containing a proton conductive polymer, and
polymer electrolyte membrane disposed between the anode and the cathode, wherein the proton conductive polymer contained in the catalyst layer of at least one of the cathode and the anode is the electrolyte material as defined in claim 1 .