# US 9,005,843 B2 · Polymer electrolyte composition

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- Number: US 9,005,843 B2
- Document ID: US9005843B2
- Status: Granted
- Kind: B2
- Application number: 13/410,938
- Filed: 2012-03-02
- Published: 2012-07-05
- Granted: 2015-04-14
- Earliest claimed: 2005-03-20
- Assignees: Ube Industries, Ltd.
- Applicants: Tetsuji Hirano; Nobuharu Hisano; Tatsuya Arai; Masayuki Kinouchi
- Inventors: Tetsuji Hirano; Nobuharu Hisano; Tatsuya Arai; Masayuki Kinouchi
- Web page: https://patentgrep.com/patent/US9005843B2

## CPC

- H01M 8/22: Fuel cells in which the fuel is based on materials comprising carbon or oxygen or hydrogen and other elements; Fuel cells in which the fuel is based on materials comprising only elements other than carbon, oxygen or hydrogen
- C08J 5/2256: {based on macromolecular compounds obtained by reactions other than those involving carbon-to-carbon bonds, e.g. obtained by polycondensation}
- H01B 1/122: {Ionic conductors}
- H01M 8/1027: having carbon, oxygen and other atoms, e.g. sulfonated polyethersulfones [S-PES]
- H01M 8/1032: having sulfur, e.g. sulfonated-polyethersulfones [S-PES]
- H01M 8/1067: characterised by their physical properties, e.g. porosity, ionic conductivity or thickness
- H01M 8/1072: by chemical reactions, e.g. in situ polymerisation or in situ crosslinking
- C08J 2381/06: Polysulfones; Polyethersulfones
- H01M 8/1009: with one of the reactants being liquid, solid or liquid-charged (H01M8/12 takes precedence)
- H01M 2300/0082: Organic polymers
- Y02E 60/50: Fuel cells
- Y02P 70/50: Manufacturing or production processes characterised by the final manufactured product
- H01M: PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- C08J: WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H (working, e.g. shaping, of plastics B29)
- H01B: CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES (selection for magnetic properties H01F1/00; waveguides H01P {; printed circuits H05K})
- Y02E: REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02P: CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS

## Abstract

A polymer electrolyte composition of a sulfonated block copolymer (A) having a hydrophilic segment with a sulfonic acid group and a hydrophobic segment with no sulfonic acid group, each segment having an aromatic ring is its main chain, and an aromatic polymer (B) having no sulfonic acid group with a structural unit that is identical to the structural unit contained in the hydrophobic segment of the sulfonated block copolymer is provided. The ion-exchange capacity of the composition can be in a range of 0.5 mmol/g to 2.9 mmol/g. Electrolyte membranes, membrane/electrolyte assemblies, and electrolyte fuel cells utilizing the polymer electrolyte composition are also provide.

## Claims

### Claim 1

A polymer electrolyte composition comprising a polymer blend of (A) a sulfonated block copolymer and (B) a non-sulfonated aromatic polymer,
(A) the sulfonated block copolymer comprising (i) a hydrophilic segment with sulfonic acid groups, and (ii) a hydrophobic segment with no sulfonic acid groups,
(i) the hydrophilic segment comprising:
(a) a structural unit according to formula (3)
wherein,
D3 is SO2 or CO, each b independently is 0 or 1 and at least one of b is 1, Z is a hydrogen atom or an alkali metal, Y3 is O or S, and Ar2 is a divalent aromatic residue having sulfonic acid groups; and
(b) a structural unit according to formula (4)
wherein,
D4 is SO2 or CO, Y4 is O or S, and Ar3 is a divalent aromatic residue having sulfonic acid groups; and
(ii) the hydrophobic segment comprising an aromatic ring residue in its main chain;
(B) the non-sulfonated aromatic polymer being an aromatic polymer having no sulfonic acid groups and having the same structural unit as the structural unit contained in the hydrophobic segment of said sulfonated block copolymer;
wherein the weight fraction Pb of the non-sulfonated aromatic polymer is in the range of from 0.03 to 0.4 calculated from the following equation:
P
b
=
W
B
W
A
+
W
B
,
wherein WA is the weight of the sulfonated block copolymer (A), and WB is the weight of the non-sulfonated aromatic polymer (B).

### Claim 2 (depends on 1)

The polymer electrolyte composition according to claim 1, wherein the non-sulfonated aromatic polymer (B) is a block copolymer having a segment represented by the same structural unit as that of the hydrophobic segment of the sulfonated block copolymer.

### Claim 3 (depends on 1)

The polymer electrolyte composition according to claim 1, wherein the non-sulfonated aromatic polymer (B) is a polymer represented by the same structural unit as that of the hydrophobic segment of the sulfonated block copolymer.

### Claim 4 (depends on 1)

The polymer electrolyte composition according to claim 1, wherein the sulfonated block copolymer (A) is an aromatic polyether block copolymer having sulfonic acid groups.

### Claim 5 (depends on 1)

The polymer electrolyte composition according to claim 1, wherein the hydrophobic segment (ii) has the structure according to formula (1)
wherein D1 is SO2 or CO, Y1 is O or S, and m is an integer of from 3 to 1,500.

### Claim 6 (depends on 1)

The polymer electrolyte composition according to claim 1, wherein the ion-exchange capacity of the sulfonated block copolymer (A) is in the range of from 0.6 meq/g to 3.0 meq/g, and the ion-exchange capacity of the electrolyte composition is in the range of from 0.5 meq/g to 2.9 meq/g.

### Claim 7 (depends on 1)

The polymer electrolyte composition according to claim 1, wherein the ion-exchange capacity IEC of the hydrophilic segment is 3.6 meq/g or more, and the ion-exchange capacity IEC of the sulfonated block copolymer is in the range of from 0.6 meq/g to 3.0 meq/g;
the IEC calculated from the following equation:
IEC
w
=
IEC
×
W
W
w
wherein IECw is the ion-exchange capacity of the sulfonated block copolymer;
W is the weight of the sulfonated block copolymer; and
WW is the weight of the hydrophilic segment in the sulfonated block copolymer.

### Claim 8 (depends on 1)

The polymer electrolyte composition according to claim 1, wherein
the weight ratio of structural unit (a)/structural unit (b) is in the range of from 10/0 to 1/9.

### Claim 9 (depends on 1)

A polymer electrolyte membrane comprising the polymer electrolyte composition according to claim 1, and having a thickness of from 5 μm to 200 μm.

### Claim 10 (depends on 1)

A membrane/electrode assembly comprising the polymer electrolyte composition according to claim 1.

### Claim 11 (depends on 9)

A membrane/electrode assembly comprising the polymer electrolyte membrane according to claim 9.

### Claim 12 (depends on 1)

A solid polymer electrolyte fuel cell comprising the polymer electrolyte composition according to claim 1.

### Claim 13 (depends on 10)

A solid polymer electrolyte fuel cell comprising the membrane/electrode assembly according to claim 10.

### Claim 14 (depends on 1)

A direct liquid fuel injection-type fuel cell, comprising the polymer electrolyte composition according to claim 1, and comprising alcohol or ether as a fuel.

### Claim 15 (depends on 10)

A direct liquid fuel injection-type fuel cell, comprising the membrane/electrode assembly according to claim 10, and comprising alcohol or ether as a fuel.

### Claim 16 (depends on 1)

The polymer electrolyte composition according to claim 1, wherein each of D3 and D4 is SO2, and each of Y3 and Y4 is O.

### Claim 17 (depends on 1)

The polymer electrolyte composition according to claim 1, wherein the polymer blend is prepared by dissolving together the sulfonated block copolymer (A) and the non-sulfonated aromatic polymer (B) and uniformly blending the composition.

### Claim 18 (depends on 17)

The polymer electrolyte composition according to claim 17, wherein the sulfonated block copolymer (A) and the non-sulfonated aromatic polymer (B) are dissolved together in a solvent capable of dissolving both (A) and (B).

### Claim 19 (depends on 1)

The polymer electrolyte composition according to claim 1, wherein the composition comprises a homogenous polymer blend of (A) and (B).

### Claim 20 (depends on 1)

The polymer electrolyte composition according to claim 1, wherein the hydrophobic segment has the structure according to formula (15)
wherein D5 is CO or SO2; Y5 is O or S; and Ar4 is a divalent aromatic residue.

### Claim 21 (depends on 1)

The polymer electrolyte composition according to claim 1, wherein the hydrophobic segment has the structure according to formula (19)