Polymer electrolyte composition, electrolyte membrane, membrane-electrode assembly and fuel cell

1. An electrolyte composition comprising:

a polymer comprising a block-type copolymer,

the block-type copolymer comprising a hydrophilic block and a hydrophobic block, the hydrophilic block comprising a sulfonic acid group;

a first solvent;

a second solvent, wherein the second solvent is water;

wherein the electrolyte composition further comprises a sulfonic acid-water complex formed by reacting the second solvent with the hydrophilic block sulfonic acid group, the complex having a higher solubility than the hydrophobic block with respect to the first solvent, and

wherein the block-type copolymer comprises a repeating unit represented by the following Formula 1 and a repeating unit represented by the following Formula 2:

in Formula 1, a and a′ each separately is an integer larger than 0 and a:a′ is 1,000:1 to 5:1, and

m is an integer from 1 to 10,000, and

in Formulas 1 and 2, A, C, and V are the same as or different from each other, and each independently represented by one of the following Formulas 1-1 to 1-3,

in Formulas 1-1 to 1-3,

X 1 is a direct link, or one of —C(Z 1 )(Z 2 )—, —CO—, —O—, —S—, —SO 2 —, and —Si(Z 1 )(Z 2 )—,

Z 1 and Z 2 are the same as or different from each other, and are each independently one of hydrogen, an alkyl group, a trifluoromethyl group (—CF 3 ), and a phenyl group,

S 1 and S 2 are the same as or different from each other, and are each independently hydrogen; deuterium; a halogen group; a cyano group; a nitrile group; a nitro group; a hydroxyl group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted alkoxy group; a substituted or unsubstituted alkenyl group; a substituted or unsubstituted silyl group; a substituted or unsubstituted boron group; a substituted or unsubstituted amine group; a substituted or unsubstituted alkylamine group; a substituted or unsubstituted aralkylamine group; a substituted or unsubstituted arylamine group; a substituted or unsubstituted heteroarylamine group; a substituted or unsubstituted aryl group; a substituted or unsubstituted fluorenyl group; or a substituted or unsubstituted carbazole group,

b and c are the same as or different from each other, and are each independently an integer of 0 to 4,

S 3 to S 6 are the same as or different from each other, and are each independently hydrogen; deuterium; a halogen group; a cyano group; a nitrile group; a nitro group; a hydroxyl group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted alkoxy group; a substituted or unsubstituted alkenyl group; a substituted or unsubstituted silyl group; a substituted or unsubstituted boron group; a substituted or unsubstituted amine group; a substituted or unsubstituted alkylamine group; a substituted or unsubstituted aralkylamine group; a substituted or unsubstituted arylamine group; a substituted or unsubstituted heteroarylamine group; a substituted or unsubstituted aryl group; a substituted or unsubstituted fluorenyl group; or a substituted or unsubstituted carbazole group,

d, e, f, and g are the same as or different from each other, and are each independently an integer of 0 to 4,

S 7 to S 10 are the same as or different from each other, and are each independently hydrogen; deuterium; a halogen group; a cyano group; a nitrile group; a nitro group; a hydroxyl group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted alkoxy group; a substituted or unsubstituted alkenyl group; a substituted or unsubstituted silyl group; a substituted or unsubstituted boron group; a substituted or unsubstituted amine group; a substituted or unsubstituted alkylamine group; a substituted or unsubstituted aralkylamine group; a substituted or unsubstituted arylamine group; a substituted or unsubstituted heteroarylamine group; a substituted or unsubstituted aryl group; a substituted or unsubstituted fluorenyl group; or a substituted or unsubstituted carbazole group, and

h, i, j, and k are the same as or different from each other, and are each independently an integer of 0 to 4,

in Formula 2,

z and z′ are an integer larger than 0 and z:z′ is 1,000:1 to 5:1,

n is an integer from 1 to 100,000, and

U is represented by one of the following Formulas 2-1 to 2-4,

in Formulas 2-1 to 2-4,

X 2 is a direct link, or —CO— or —SO 2 —,

q and r are the same as or different from each other and are each independently an integer of 0 to 4,

s, t, u, and v are the same as or different from each other and are each independently an integer of 0 to 4,

w and x are the same as or different from each other and are each independently an integer of 0 to 3,

y is an integer of 0 to 4,

T 1 to T 9 are the same as or different from each other, at least one of T 1 to T 9 in Formulas 2-1 to 2-4 is a —SO 3 H or —SO 3 − M + and the other are each independently —SO 3 H, —SO 3 − M + , —COOH, —COO − M + , —PO 3 H 2 , —PO 3 H − M + , or —PO 3 2− 2M + , M is a metallic element, and the others are hydrogen; deuterium; a halogen group; a cyano group; a nitrile group; a nitro group; a hydroxyl group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted alkoxy group; a substituted or unsubstituted alkenyl group; a substituted or unsubstituted silyl group; a substituted or unsubstituted boron group; a substituted or unsubstituted amine group; a substituted or unsubstituted alkylamine group; a substituted or unsubstituted aralkylamine group; a substituted or unsubstituted arylamine group; a substituted or unsubstituted heteroarylamine group; a substituted or unsubstituted aryl group; a substituted or unsubstituted fluorenyl group; or a substituted or unsubstituted carbazole group,

in Formulas 1 and 2, B is represented by one of the following Formulas 3-1 to 3-3,

in Formulas 3-1 to 3-3,

X 3 to X 5 are the same as or different from each other and are each independently a direct link, or —CO— or —SO 2 —,

Y 1 is a direct link, or a C 1 to C 60 alkylene group,

E 1 to E 4 are the same as or different from each other, and are each independently hydrogen; deuterium; a halogen group; a cyano group; a nitrile group; a nitro group; a hydroxyl group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted alkoxy group; a substituted or unsubstituted alkenyl group; a substituted or unsubstituted silyl group; a substituted or unsubstituted boron group; a substituted or unsubstituted amine group; a substituted or unsubstituted alkylamine group; a substituted or unsubstituted aralkylamine group; a substituted or unsubstituted arylamine group; a substituted or unsubstituted heteroarylamine group; a substituted or unsubstituted aryl group; a substituted or unsubstituted fluorenyl group; or a substituted or unsubstituted carbazole group,

α, β, and ψ are the same as or different from each other and are each independently an integer of 0 to 4,

ε is an integer of 0 to 3,

X 6 is a direct link, or —CO— or —SO—,

Y 2 is a direct link, or a Ci to C 60 alkylene group,

E 5 and E 6 are the same as or different from each other, and are each independently hydrogen; deuterium; a halogen group; a cyano group; a nitrile group; a nitro group; a hydroxyl group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted alkoxy group; a substituted or unsubstituted alkenyl group; a substituted or unsubstituted silyl group; a substituted or unsubstituted boron group; a substituted or unsubstituted amine group; a substituted or unsubstituted alkylamine group; a substituted or unsubstituted aralkylamine group; a substituted or unsubstituted arylamine group; a substituted or unsubstituted heteroarylamine group; a substituted or unsubstituted aryl group; a substituted or unsubstituted fluorenyl group; or a substituted or unsubstituted carbazole group,

ζ is an integer of 0 to 3,

θ is an integer of 0 to 4,

X 7 is a direct link, or —CO— or —SO 2 − ,

Y 3 is a direct link, or a C 1 to C 60 alkylene group,

E 7 and E 8 are the same as or different from each other, and are each independently hydrogen; deuterium; a halogen group; a cyano group; a nitrile group; a nitro group; a hydroxyl group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted alkoxy group; a substituted or unsubstituted alkenyl group; a substituted or unsubstituted silyl group; a substituted or unsubstituted boron group; a substituted or unsubstituted amine group; a substituted or unsubstituted alkylamine group; a substituted or unsubstituted aralkylamine group; a substituted or unsubstituted arylamine group; a substituted or unsubstituted heteroarylamine group; a substituted or unsubstituted aryl group; a substituted or unsubstituted fluorenyl group; or a substituted or unsubstituted carbazole group,

λ an integer of 0 to 3,

π is an integer of 0 to 4, and

W is a repeating unit represented by the following [Formula 4] in Formula 1, and a repeating unit represented by the following [Formula 5] in Formula 2,

in Formula 4, m′ is an integer of I to 10,000, and a definition of A and U is the same as that of A and U in Formula 1, and

in Formula 5, n′ is an integer of 1 to 100,000, and a definition of C and V is the same as that of C and V in Formula 2.

2. The composition of claim 1 , wherein the first solvent is at least one selected from the group consisting of N,N′-dimethylacetamide (DMAc), N-methyl pyrrolidone (NMP), dimethyl sulfoxide (DMSO), and N,N-dimethylformamide (DMF).

3. The composition of claim 1 , wherein A, C, and V are the same as or different from each other and are at least one selected from the group consisting of

and

R 1 and R 2 are the same as or different from each other and are each independently a nitro group (—NO 2 ) or a trifluoromethyl group (—CF 3 ).

4. The composition of claim 1 , wherein U is at least one selected from the group consisting of

Q1 and Q2 are the same as or different from each other and at least one of Q 1 and Q 2 is a —SO 3 H or —SO 3 − M + and the other is —SO 3 H, —SO 3 − M + , —COOH, —COO − M + , —PO 3 H 2 , —PO 3 H − M + , or —PO 3 2− 2M + , and M is a metallic element.

5. The composition of claim 1 , wherein B is one selected from the group consisting of

Y 1 to Y 3 are the same as or different from each other and are each independently a direct link, or a C 1 to C 60 alkylene group, and

W is a repeating unit represented by the following [Formula 4] in Formula 1, and a repeating unit represented by the following [Formula 5] in Formula 2,

in Formula 4, m′ is an integer of 1 to 10,000, and a definition of A and U is the same as that of A and U in Formula 1, and

in Formula 5, n′ is an integer of 1 to 100,000, and a definition of C and V is the same as that of C and V in Formula 2.

6. The composition of claim 1 , wherein the sulfonic acid group is SO 3 K.

7. The composition of claim 1 , wherein the weight ratio of the second solvent to the first solvent 3/97 to 8/92.

8. An electrolyte membrane formed of the polymer electrolyte composition of claim 1 .

9. A membrane electrode assembly comprising:

a cathode;

an anode; and

an electrolyte membrane disposed between the cathode and the anode,

wherein the electrolyte membrane is the electrolyte membrane of claim 8 .

10. A polymer electrolyte-type fuel cell comprising:

a stack comprising one or two or more membrane electrode assemblies of claim 9 and a bipolar plate interposed between the membrane electrode assemblies;

a fuel supply unit for supplying fuel to the stack; and

an oxidant supply unit for supplying an oxidant to the stack.

11. An electrolyte composition comprising:

a polymer comprising a block-type copolymer;

the block-type copolymer comprising a hydrophilic block and a hydrophobic block, the hydrophilic block comprising a sulfonic acid group,

wherein the hydrophilic block has a weight average molecular weight from 1,000 to 500,000 (g/mol), and the hydrophobic block has a weight average molecular weight from 1,000 to 500,000 (g/mol);

a first solvent;

a second solvent, wherein the second solvent is water;

wherein a weight ratio of the second solvent to the first solvent 1/99 to 10/90,

wherein the electrolyte composition further comprises a sulfonic acid-water complex formed by reacting the second solvent with the hydrophilic block sulfonic acid group, the complex having a higher solubility than the hydrophobic block with respect to the first solvent,

and

wherein the block-type copolymer comprises a repeating unit represented by the following Formula 1 and a repeating unit represented by the following Formula 2:

in Formula 1, a and a′ each separately is an integer larger than 0 and a:a′ is 1,000:1 to 5:1, and

m is an integer from 1 to 10,000, and

in Formulas 1 and 2, A, C, and V are the same as or different from each other, and each independently represented by one of the following Formulas 1-1 to 1-3,

in Formulas 1-1 to 1-3,

X 1 is a direct link, or one of —C(Z 1 )(Z 2 )—, —CO—, —O—, —S—, —SO 2 —, and —Si(Z 1 )(Z 2 )—,

Z 1 and Z 2 are the same as or different from each other, and are each independently one of hydrogen, an alkyl group, a trifluoromethyl group (—CF 3 ), and a phenyl group,

S 1 and S 2 are the same as or different from each other, and are each independently hydrogen; deuterium; a halogen group; a cyano group; a nitrile group; a nitro group; a hydroxyl group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted alkoxy group; a substituted or unsubstituted alkenyl group; a substituted or unsubstituted silyl group; a substituted or unsubstituted boron group; a substituted or unsubstituted amine group; a substituted or unsubstituted alkylamine group; a substituted or unsubstituted aralkylamine group; a substituted or unsubstituted arylamine group; a substituted or unsubstituted heteroarylamine group; a substituted or unsubstituted aryl group; a substituted or unsubstituted fluorenyl group; or a substituted or unsubstituted carbazole group,

b and c are the same as or different from each other, and are each independently an integer of 0 to 4,

S 3 to S 6 are the same as or different from each other, and are each independently hydrogen; deuterium; a halogen group; a cyano group; a nitrile group; a nitro group; a hydroxyl group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted alkoxy group; a substituted or unsubstituted alkenyl group; a substituted or unsubstituted silyl group; a substituted or unsubstituted boron group; a substituted or unsubstituted amine group; a substituted or unsubstituted alkylamine group; a substituted or unsubstituted aralkylamine group; a substituted or unsubstituted arylamine group; a substituted or unsubstituted heteroarylamine group; a substituted or unsubstituted aryl group; a substituted or unsubstituted fluorenyl group; or a substituted or unsubstituted carbazole group,

d, e, f, and g are the same as or different from each other, and are each independently an integer of 0 to 4,

S 7 to S 10 are the same as or different from each other, and are each independently hydrogen; deuterium; a halogen group; a cyano group; a nitrile group; a nitro group; a hydroxyl group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted alkoxy group; a substituted or unsubstituted alkenyl group; a substituted or unsubstituted silyl group; a substituted or unsubstituted boron group; a substituted or unsubstituted amine group; a substituted or unsubstituted alkylamine group; a substituted or unsubstituted aralkylamine group; a substituted or unsubstituted arylamine group; a substituted or unsubstituted heteroarylamine group; a substituted or unsubstituted aryl group; a substituted or unsubstituted fluorenyl group; or a substituted or unsubstituted carbazole group, and

h, i, j, and k are the same as or different from each other, and are each independently an integer of 0 to 4,

in Formula 2,

z and z′ are an integer larger than 0 and z:z′ is 1,000:1 to 5:1,

n is an integer from 1 to 100,000, and

U is represented by one of the following Formulas 2-1 to 2-4,

in Formulas 2-1 to 2-4,

X 2 is a direct link, or —CO— or —SO 2 —,

q and r are the same as or different from each other and are each independently an integer of 0 to 4,

s, t, u, and v are the same as or different from each other and are each independently an integer of 0 to 4,

w and x are the same as or different from each other and are each independently an integer of 0 to 3,

y is an integer of 0 to 4,

T 1 to T 9 are the same as or different from each other, at least one of T 1 to T 9 in Formulas 2-1 to 2-4 is a —SO 3 H or —SO 3 − M + and the other are each independently —SO 3 H, —SO 3 − M + , —COOH, —COO − M + , —PO 3 H 2 , —PO 3 H − M + , or —PO 3 2− 2M + , M is a metallic element, and the others are hydrogen; deuterium; a halogen group; a cyano group; a nitrile group; a nitro group; a hydroxyl group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted alkoxy group; a substituted or unsubstituted alkenyl group; a substituted or unsubstituted silyl group; a substituted or unsubstituted boron group; a substituted or unsubstituted amine group; a substituted or unsubstituted alkylamine group; a substituted or unsubstituted aralkylamine group; a substituted or unsubstituted arylamine group; a substituted or unsubstituted heteroarylamine group; a substituted or unsubstituted aryl group; a substituted or unsubstituted fluorenyl group; or a substituted or unsubstituted carbazole group,

in Formulas 1 and 2, B is represented by one of the following Formulas 3-1 to 3-3,

in Formulas 3-1 to 3-3,

X 3 to X 5 are the same as or different from each other and are each independently a direct link, or —CO— or —SO 2 —,

Y 1 is a direct link, or a C 1 to C 60 alkylene group,

E 1 to E 4 are the same as or different from each other, and are each independently hydrogen; deuterium; a halogen group; a cyano group; a nitrile group; a nitro group; a hydroxyl group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted alkoxy group; a substituted or unsubstituted alkenyl group; a substituted or unsubstituted silyl group; a substituted or unsubstituted boron group; a substituted or unsubstituted amine group; a substituted or unsubstituted alkylamine group; a substituted or unsubstituted aralkylamine group; a substituted or unsubstituted arylamine group; a substituted or unsubstituted heteroarylamine group; a substituted or unsubstituted aryl group; a substituted or unsubstituted fluorenyl group; or a substituted or unsubstituted carbazole group,

α, β, and ψ are the same as or different from each other and are each independently an integer of 0 to 4,

ε is an integer of 0 to 3,

X 6 is a direct link, or —CO— or —SO—,

Y 2 is a direct link, or a Ci to C 60 alkylene group,

E 5 and E 6 are the same as or different from each other, and are each independently hydrogen; deuterium; a halogen group; a cyano group; a nitrile group; a nitro group; a hydroxyl group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted alkoxy group; a substituted or unsubstituted alkenyl group; a substituted or unsubstituted silyl group; a substituted or unsubstituted boron group; a substituted or unsubstituted amine group; a substituted or unsubstituted alkylamine group; a substituted or unsubstituted aralkylamine group; a substituted or unsubstituted arylamine group; a substituted or unsubstituted heteroarylamine group; a substituted or unsubstituted aryl group; a substituted or unsubstituted fluorenyl group; or a substituted or unsubstituted carbazole group,

ζ is an integer of 0 to 3,

θ is an integer of 0 to 4,

X 7 is a direct link, or —CO— or —SO 2 − ,

Y 3 is a direct link, or a C 1 to C 60 alkylene group,

E 7 and E 8 are the same as or different from each other, and are each independently hydrogen; deuterium; a halogen group; a cyano group; a nitrile group; a nitro group; a hydroxyl group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted alkoxy group; a substituted or unsubstituted alkenyl group; a substituted or unsubstituted silyl group; a substituted or unsubstituted boron group; a substituted or unsubstituted amine group; a substituted or unsubstituted alkylamine group; a substituted or unsubstituted aralkylamine group; a substituted or unsubstituted arylamine group; a substituted or unsubstituted heteroarylamine group; a substituted or unsubstituted aryl group; a substituted or unsubstituted fluorenyl group; or a substituted or unsubstituted carbazole group,

λ an integer of 0 to 3,

π is an integer of 0 to 4, and

W is a repeating unit represented by the following [Formula 4] in Formula 1, and a repeating unit represented by the following [Formula 5] in Formula 2,

in Formula 4, m′ is an integer of I to 10,000, and a definition of A and U is the same as that of A and U in Formula 1, and

in Formula 5, n′ is an integer of 1 to 100,000, and a definition of C and V is the same as that of C and V in Formula 2.