# US 9,040,209 B2 · Multi-layer polyelectrolyte membranes

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- Number: US 9,040,209 B2
- Document ID: US9040209B2
- Status: Granted
- Kind: B2
- Application number: 13/364,869
- Filed: 2012-02-02
- Published: 2013-08-08
- Granted: 2015-05-26
- Earliest claimed: 2012-02-02
- Assignees: GM Global Technology Operations LLC
- Applicants: Lijun Zou; Scott C. Moose; Timothy J. Fuller
- Inventors: Lijun Zou; Scott C. Moose; Timothy J. Fuller
- Web page: https://patentgrep.com/patent/US9040209B2

## CPC

- H01M 8/1023: having only carbon, e.g. polyarylenes, polystyrenes or polybutadiene-styrenes
- H01M 8/1025: having only carbon and oxygen, e.g. polyethers, sulfonated polyetheretherketones [S-PEEK], sulfonated polysaccharides, sulfonated celluloses or sulfonated polyesters
- H01M 8/1039: halogenated, e.g. sulfonated polyvinylidene fluorides
- H01M 8/1053: consisting of layers of polymers with at least one layer being ionically conductive
- H01M 8/1081: starting from solutions, dispersions or slurries exclusively of 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
- 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 multilayer polyelectrolyte membrane for fuel cell applications includes a first perfluorocyclobutyl-containing layer that includes a polymer having perfluorocyclobutyl moieties. The first layer is characteristically planar having a first major side and a second major side over which additional layers are disposed. The membrane also includes a first PFSA layer disposed over the first major side of the first layer and a second PFSA layer disposed over the second major side of the first layer.

## Claims

### Claim 1

A multilayer polyelectrolyte membrane for a fuel cell, the membrane comprising:
a first perfluorocyclobutyl-containing layer comprising a polymer having perfluorocyclobutyl moieties, the first perfluorocyclobutyl-containing layer having a first major side and a second major side, the first perfluorocyclobutyl-containing layer having a thickness from 2 to 8 microns;
a first perfluorosulfonic acid layer comprising a perfluorosulfonic acid polymer, the first perfluorosulfonic acid layer disposed over the first major side of the first perfluorocyclobutyl-containing layer, the first perfluorosulfonic acid layer having a thickness from 1 to 4 microns;
a second perfluorosulfonic acid layer comprising a perfluorosulfonic acid polymer, the second perfluorosulfonic acid layer disposed over the second major side of the first perfluorocyclobutyl-containing layer, the second perfluorosulfonic acid layer having a thickness from 1 to 4 microns; and
a support contacting at least one of the first perfluorosulfonic acid layer or the second perfluorosulfonic acid layer.

### Claim 2 (depends on 1)

The membrane of claim 1 wherein the support is an expanded polytetrafluoroethylene support.

### Claim 3 (depends on 1)

The membrane of claim 1 wherein the support is at least partially immersed in the perfluorocyclobutyl-containing layer and/or the first perfluorosulfonic acid layer.

### Claim 4 (depends on 1)

The membrane of claim 1 wherein the support is at least partially immersed in the first perfluorosulfonic acid layer.

### Claim 5 (depends on 1)

The membrane of claim 1 wherein the support is at least partially immersed in the second perfluorosulfonic acid layer.

### Claim 6 (depends on 1)

The membrane of claim 1 wherein the first perfluorocyclobutyl-containing layer further includes a fluoroelastomer.

### Claim 7 (depends on 1)

The membrane of claim 1 wherein the perfluorocyclobutyl moieties are:

### Claim 8 (depends on 1)

The membrane of claim 1 wherein the first perfluorosulfonic acid layer comprises polymer segments 1 and 2:
[E1(SO2X)d]—P1-Q1-P2 1
E2-P3-Q2-P4 2
wherein:
E1(SO2X)d is a sulfonated aromatic containing moiety;
E1 is an aromatic containing moiety;
E2 is an unsulfonated aromatic-containing and/or aliphatic-containing moiety;
X is an —OH, a halogen, an ester, or
d is the number of (SO2X)d attached to E1;
P1, P2, P3, P4 are each independently: absent, —O—, —S—, —SO—, —CO—, —SO2—, —NR1H—, NR2—, or —R3—;
R2 is C1-25 alkyl;
R3 is C1-25 alkylene, perfluoroalkylene, perfluoroalkyl ether, or alkylether;
R4 is trifluoromethyl, C1-25 alkyl, or another E1 group; and
Q1, Q2 are each independently a fluorinated cyclobutyl moiety.

### Claim 9 (depends on 1)

The membrane of claim 1 wherein the first perfluorosulfonic acid layer comprises polymer segments 3 and 4:
E2-P3-Q2-P4 4
wherein:
E1, E2 are each independently an aromatic-containing and/or aliphatic-containing moiety;
X is an —OH, a halogen, an ester, or
d is the number of (SO2X)d attached to E1;
P1, P2, P3, P4 are each independently: absent, —O—, —S—, —SO—, —CO—, —SO2—, —NH—, NR2—, or —R3—; and
R2 is C1-25 alkyl;
R3 is C1-25 alkylene, C1-25 perfluoroalkylene, perfluoroalkyl ether, or alkylether;
R4 is trifluoromethyl, C1-25 alkyl, or another E1 group;
R8(SO2X)d is a sulfonated aliphatic or aromatic containing moiety; and
Q1, Q2 are each independently a fluorinated cyclobutyl moiety.

### Claim 10 (depends on 1)

The membrane of claim 1 wherein the first perfluorosulfonic acid layer comprises polymer segments 5 and 6:
E1(SO2X)d—P1-Q1-P2 5
E2-P3-Q2-P4 6
connected by a linking group L1 to form polymer units 7 and 8:
E2-P3-Q2-P4jL1E1(SO2X)d—P1-Q1-P2i 7
E1(SO2X)d—P3-Q2-P4iL1E2-P1-Q1-P2j 8
wherein:
E1(SO2X)d is a sulfonated aromatic-containing moiety;
E2 is an unsulfonated aromatic-containing and/or aliphatic-containing moiety;
L1 is a linking group;
X is an —OH, a halogen, an ester, or
d is a number of (SO2X) functional groups attached to E1;
P1, P2, P3, P4 are each independently absent, —O—, —S—, —SO—, —SO2—, —CO—, —NH—, NR2—, —R3—, and
R2 is C1-25 alkyl;
R3 is C1-25 alkylene or C1-25 perfluoroalkylene;
R4 is trifluoromethyl, C1-25 alkyl, or another E1 group;
Q1, Q2 are each independently a fluorinated cyclobutyl moiety;
i is a number representing repetition of polymer segment 5; and,
j is a number representing repetition of a polymer segment 6.

### Claim 11 (depends on 1)

The membrane of claim 1 wherein the first perfluorosulfonic acid layer comprises polymer segments 9 and 10:
E1(SO2X)d—P1-Q1-P2 9
E2(SO2X)f—P3 10
wherein:
E1, E2 is an aromatic or aliphatic-containing moiety wherein at least one of E1 and E2 include an aromatic group substituted with —SO2X;
X is an —OH, a halogen, an ester, or
d is the number of (SO2X) functional groups attached to E1;
f is the number of (SO2X) functional groups attached to E2;
P1, P2, P3 are each independently absent, —O—, —S—, —SO—, —SO2—, —CO—, —NH—, NR2—, —R3—, and
R2 is C1-25 alkyl;
R3 is C1-25 alkylene, C1-25 perfluoroalkylene, perfluoroalkyl ether, alkyl ether;
R4 is trifluoromethyl, C1-25 alkyl, or another E1 group; and
Q1 is a fluorinated cyclobutyl moiety,
with the proviso that when d is greater than zero, f is zero and when f is greater than zero, d is zero.

### Claim 12 (depends on 1)

A fuel cell incorporating the membrane of claim 1.

### Claim 13 (depends on 1)

The multilayer polyelectrolyte membrane of claim 1 wherein the first perfluorocyclobutyl-containing layer is formed by polymerizing a monomer selected from the group consisting of: