# US 11,180,620 B2 · Proton-conducting inorganic particles, method for the preparation thereof, and use thereof to form a fuel cell membrane

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- Number: US 11,180,620 B2
- Document ID: US11180620B2
- Status: Granted
- Kind: B2
- Application number: 16/480,463
- Filed: 2018-01-24
- Published: 2019-11-14
- Granted: 2021-11-23
- Earliest claimed: 2017-01-25
- Assignees: Commissariat A L'energie Atomique Et Aux Energies Alternatives; Specific Polymers
- Applicants: Commissariat à L'éNergie Atomique Et Aux éNergies Alternatives; Specific Polymers
- Inventors: Pierrick Buvat; Janick Bigarré; Julien Cellier; Cédric Loubat; Quentin Crouzet
- Web page: https://patentgrep.com/patent/US11180620B2

## CPC

- B01J 20/103: {comprising silica}
- C08J 5/2237: {containing fluorine}
- B01J 20/02: comprising inorganic material
- B01J 20/264: {derived from different types of monomers, e.g. linear or branched copolymers, block copolymers, graft copolymers}
- B01J 20/28033: {Membrane, sheet, cloth, pad, lamellar or mat}
- B01J 20/3204: {Inorganic carriers, supports or substrates}
- B01J 20/3242: {Layers with a functional group, e.g. an affinity material, a ligand, a reactant or a complexing group}
- B01J 20/3257: {the functional group or the linking, spacer or anchoring group as a whole comprising at least one of the heteroatoms nitrogen, oxygen or sulfur together with at least one silicon atom, these atoms not being part of the carrier as such}
- B01J 20/3276: {Copolymers}
- C08F 12/30: Sulfur
- C08F 214/222: {with fluorinated vinyl ethers}
- C08J 5/2243: {obtained by introduction of active groups capable of ion-exchange into compounds of the type C08J5/2231}
- C08K 3/36: Silica
- H01M 8/1004: characterised by membrane-electrode assemblies [MEA] (H01M8/12 takes precedence)
- H01M 8/1039: halogenated, e.g. sulfonated polyvinylidene fluorides
- H01M 8/1051: Non-ion-conducting additives, e.g. stabilisers, SiO2 or ZrO2
- H01M 8/1069: characterised by the manufacturing processes
- C08J 2325/06: Polystyrene
- C08J 2327/16: Homopolymers or copolymers of vinylidene fluoride
- C08J 2327/18: Homopolymers or copolymers of tetrafluoroethylene
- H01M 2008/1095: {Fuel cells with polymeric electrolytes}
- Y02E 60/50: Fuel cells
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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)
- C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08K: Use of inorganic or non-macromolecular organic substances as compounding ingredients (paints, inks, varnishes, dyes, polishes, adhesives C09)
- 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

## Abstract

The invention relates to inorganic particles which are covalently bonded to first polymer chains made up of at least one polymer carrying proton exchange groups, optionally in the form of salts, and bonded to second polymer chains made up of at least one fluorinated polymer that does not carry any proton exchange groups, the second chains being bonded to the particles via organic spacer groups, or the second chains being bonded to first chains via organic spacer groups, or some of the second chains being bonded to the particles via organic spacer groups while the remaining second chains are bonded to first chains via organic spacer groups.

## Claims

### Claim 1

Proton-conducting membrane for fuel cell formed of inorganic particles bonded, covalently, to first polymer chains constituted of at least one polymer carrying proton-exchanging groups, optionally in the form of salts, said particles also being bonded to second polymer chains constituted of at least one fluorinated polymer not carrying proton-exchanging groups, with the bond between the particles and said second polymer chains corresponding to one of the following alternatives:
said second polymer chains are bonded to the particles via organic spacer groups; or
said second polymer chains are bonded to first polymer chains via organic spacer groups; or
a portion of said second polymer chains is bonded to the particles via organic spacer groups while the other portion of said second polymer chains is bonded to first polymer chains via organic spacer groups.

### Claim 2 (depends on 1)

Membrane according to claim 1, wherein the proton-exchanging groups are groups having formulas —PO3H2, —CO2H, or —SO3H, with these groups optionally able to be in the form of salts.

### Claim 3 (depends on 1)

Membrane according to claim 1, wherein the polymer or polymers carrying proton-exchanging groups, optionally in the form of salts, forming first polymer chains are polymers comprising one or several repetitive units coming from the polymerisation of one or several vinyl monomers, said monomers have at least one proton-exchanging group, optionally in the form of salts.

### Claim 4 (depends on 3)

Membrane according to claim 3, wherein the vinyl monomer or monomers are styrenic monomers comprising at least one proton-exchanging group, optionally in the form of salts.

### Claim 5 (depends on 1)

Membrane according to claim 1, of which the polymer carrying proton-exchanging groups is poly(sodium 4-vinylbenzenesulfonate) or poly(4-vinylbenzenesulfonic acid).

### Claim 6 (depends on 1)

Membrane according to claim 1, wherein all of the second polymer chains are bonded to the particles via organic spacer groups.

### Claim 7 (depends on 1)

Membrane according to claim 1, wherein the fluorinated polymer or polymers not carrying proton-exchanging groups, forming said second polymer chains, are polymers comprising one or several repetitive units, with each one of these repetitive units comprising at least one fluorine atom, with these polymers being chosen from:
the polymers comprising a single repetitive unit coming from a fluorinated monomer, such as polytetrafluoroethylenes (PTFE), polyvinylidene fluorides (known as the abbreviation PVDF);
copolymers comprising two repetitive units coming from two fluorinated monomers, such as copolymers of vinylidene fluoride and of hexafluoropropene (poly(VDF-co-HFP)).

### Claim 8 (depends on 1)

Membrane according to claim 1, wherein the organic spacer group is a non-polymeric hydrocarbon group, having the form of a linear or branched chain, into which can be inserted one or several groups (referred to as linking groups) chosen from —(C═O)—, —(C═O)O—, —SO2, amide groups, amine groups, silanoxy groups.

### Claim 9 (depends on 8)

Membrane according to claim 8, wherein the organic spacer group has the following formula (III):
wherein:
X1 is the group covalently bonded to a particle or to a first polymer chain, with this group being one of the linking groups defined previously;
R1 is an organic group forming a bridge between X1 and X2; and
X2 is the group covalently bonded to at least one second polymer chain, with this group being one of the linking groups defined previously.

### Claim 10 (depends on 9)

Inorganic particici Membrane according to claim 9, wherein the group R1 is an alkylene group.

### Claim 11 (depends on 1)

Inorganic particici Membrane according to claim 1, which are particles of zeolites, particles of zirconium phosphates, particles of zirconium phosphonates, particles of clays, particles of oxides such as silica, alumina, zirconia, titanium oxide.

### Claim 12 (depends on 1)

Inorganic particici Membrane according to claim 1, which are particles of silica.

### Claim 13 (depends on 1)

A fuel cell comprising at least one electrode-membrane-electrode assembly, wherein the membrane is such as defined in claim 1.

### Claim 14 (depends on 1)

Method for the preparation of inorganic particles as defined in claim 1, said method comprising a step of putting into contact of inorganic particles covalently bonded to first polymer chains formed by at least one polymer carrying proton-exchanging groups, optionally in the form of salts, with at least one fluorinated polymer not carrying proton-exchanging groups in the presence of a reagent comprising at least one group able to react with the inorganic particles and/or the first polymer chains in order to form a covalent bond and at least one second group able to react with at least one group of said fluorinated polymer in order to form a covalent bond and a reaction step between the reagent, the particles and the fluorinated polymer which results in inorganic particles covalently bonded, to first polymer chains constituted of at least one polymer carrying proton-exchanging groups, optionally in the form of salts, and being bonded to second polymer chains constituted of at least one fluorinated polymer not carrying proton-exchanging groups, wherein either
said second polymer chains are bonded to the particles via organic spacer groups; or
said second polymer chains are bonded to first polymer chains via organic spacer groups; or
a portion of said second polymer chains being bonded to the particles via organic spacer groups while the other portion of said second polymer chains is bonded to first polymer chains via organic spacer groups.

### Claim 15

Inorganic particles bonded, covalently, to first polymer chains constituted of at least one polymer carrying proton-exchanging groups, optionally in the form of salts, said particles also being bonded to second polymer chains constituted of at least one fluorinated polymer not carrying proton-exchanging groups, with the bond between the particles and said second polymer chains corresponding to one of the following alternatives:
said second polymer chains are bonded to the particles via organic spacer groups; or
said second polymer chains are bonded to first polymer chains via organic spacer groups; or
a portion of said second polymer chains is bonded to the particles via organic spacer groups while the other portion of said second polymer chains is bonded to first polymer chains via organic spacer groups;
wherein the inorganic particles form a membrane in a fuel cell.