Polymer electrolyte composition, and polymer electrolyte membrane, membrane electrode complex and solid polymer-type fuel cell each produced using same
The present invention provides: a polymer electrolyte composition which can achieve excellent proton conductivity under slightly humidified conditions, excellent mechanical strength and excellent physical durability, has excellent practicality, and can be produced using a nitrogen-containing additive, wherein the nitrogen-containing additive can prevent the elution of the additive under a strongly acidic atmosphere during the operation of a fuel cell, has excellent chemical stability so as to tolerate a strongly acidic atmosphere, can be dissolved in various general-purpose organic solvents, has superior processability, can be mixed with an ionic-group-containing polymer, can prevent the occurrence of phase separation during the formation of a film, and can prevent the formation of an island-in-sea-like phase separation structure or the occurrence of bleeding out during the formation of a film; and a polymer electrolyte membrane, a membrane electrode assembly and a polymer electrolyte fuel cell, each of which is produced using the polymer electrolyte composition. The polymer electrolyte composition according to the present invention comprises at least an ionic-group-containing polymer (A) and a nitrogen-containing additive (B), said polymer electrolyte composition being characterized in that the nitrogen-containing additive (B) is represented by a specific structural formula.
1. A polymer electrolyte composition comprising at least an ionic-group-containing polymer (A) and a nitrogen-containing additive (B), wherein the nitrogen-containing additive (B) comprises a constituent unit at least (C1) or a constituent unit (C2):
in which Ar represents an arylene group, and R 1 represents at least one group selected from among a halogen, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, a carboxyl group, a carboxylate ester group, a phosphino group, a phosphine oxide group, a phosphonic acid group, a phosphoester group, a sulfonic acid group, a sulfate ester group, a hydroxyl group, an amino group, a cyano group and a nitro group, j represents an integer of 0 to 7, k represents an integer of 2 or more, and all R's may be the same or different from one another,
in which Ar represents an arylene group, and R 2 represents at least one group selected from among a halogen, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, a carboxyl group, a carboxylate ester group, a phosphino group, a phosphine oxide group, a phosphonic acid group, a phosphoester group, a sulfonic acid group, a sulfate ester group, a hydroxyl group, an amino group, a cyano group and a nitro group, X represents at least one group selected from among a hydrogen atom, a halogen, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, a carboxyl group, a carboxylate ester group, a phosphino group, a phosphine oxide group, a phosphonic acid group, a phosphoester group, a sulfonic acid group, a sulfate ester group, a hydroxyl group, an amino group, a cyano group and a nitro group, m represents an integer of 0 to 6, n represents an integer of 2 to 4, and all R 2 s and Xs may be the same or different from one another.
2. The polymer electrolyte composition according to claim 1 , wherein the solubility of the nitrogen-containing additive (B) in water at 60° C. and 10% by mass sulfuric acid at 60° C. is 20 mg/L or less.
3. The polymer electrolyte composition according to claim 1 , wherein a molecular weight of the nitrogen-containing additive (B) is 400 or more.
4. The polymer electrolyte composition according to claim 1 , wherein the content of the nitrogen-containing additive (B) is 0.02% by weight or more and 35% by weight or less of the whole polymer electrolyte composition.
5. The polymer electrolyte composition according to claim 1 , wherein the polymer electrolyte composition further contains at least one transition metal selected from among Ce, Mn, Ti, Zr, V, Cr, Mo, W, Ru, Co, Rh, Ir, Ni, Pd, Pt, Ag and Au.
6. The polymer electrolyte composition according to claim 1 , wherein the ionic-group-containing polymer (A) comprises a hydrocarbon-type polymer having an aromatic ring in a main chain.
7. The polymer electrolyte composition according to claim 1 , wherein the ionic-group-containing polymer (A) comprises a block copolymer containing one or more segments (A1) containing an ionic group and one or more segments (A2) not containing an ionic group.
8. The polymer electrolyte composition according to claim 7 , wherein the segment (A1) containing an ionic group and/or the segment (A2) not containing an ionic group comprises an aromatic polyether ketone-type polymer.
9. The polymer electrolyte composition according to claim 7 , wherein the segment (A1) containing an ionic group contains a constituent unit (S1) and the segment (A2) not containing an ionic group contains a constituent unit (S2):
in which Ar 1 to Ar 4 represent an optional divalent arylene group, Ar 1 and/or Ar 2 contains an ionic group, Ar 3 and Ar 4 may contain an ionic group or need not contain an ionic group, Ar 1 to Ar 4 may be optionally substituted, or two or more kinds of arylene groups may be independently used for A 1 to Ar 4 , and * is a bonding site with a part represented by (S1) or other constituent units,
in which Ar 5 to Ar 8 represent an optional divalent arylene group and may be optionally substituted, but they do not contain an ionic group, two or more kinds of arylene groups may be independently used for Ar 5 to Ar 8 , and * is a bonding site with a part represented by (S2) or other constituent units.
10. The polymer electrolyte composition according to claim 1 , wherein the ionic group is a sulfonic acid group.
11. A polymer electrolyte membrane, wherein the polymer electrolyte membrane uses the polymer electrolyte composition according to claim 1 .
12. A membrane electrode assembly, wherein the membrane electrode assembly uses the polymer electrolyte composition according to claim 1 .
13. A polymer electrolyte fuel cell, wherein the polymer electrolyte fuel cell uses the polymer electrolyte composition according to claim 1 .