# US 10,374,244 B2 · Fluorine-based nanocomposite membrane comprising polyhedral oligomeric silsesquioxanes having proton donor and proton acceptor, and method for manufacturing same

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- Number: US 10,374,244 B2
- Document ID: US10374244B2
- Status: Granted
- Kind: B2
- Application number: 15/742,010
- Filed: 2016-03-15
- Published: 2018-07-12
- Granted: 2019-08-06
- Earliest claimed: 2016-03-15
- Assignees: Sogang University Research Foundation
- Applicants: Sogang University Research Foundation
- Inventors: Heewoo Rhee; Sangwoo Kim; Taeyung Youn
- Web page: https://patentgrep.com/patent/US10374244B2

## CPC

- H01M 8/1004: characterised by membrane-electrode assemblies [MEA] (H01M8/12 takes precedence)
- B82Y 40/00: Manufacture or treatment of nanostructures
- C08G 77/24: halogen-containing groups
- C08G 77/26: nitrogen-containing groups
- C08G 77/28: sulfur-containing groups
- C08G 77/30: phosphorus-containing groups
- C08J 5/2237: {containing fluorine}
- C08L 27/22: modified by chemical after-treatment
- C08L 83/06: containing silicon bound to oxygen-containing groups (C08L83/12 takes precedence)
- C08L 83/08: containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
- H01M 8/1011: Direct alcohol fuel cells [DAFC], e.g. direct methanol fuel cells [DMFC]
- H01M 8/1041: Polymer electrolyte composites, mixtures or blends
- B82Y 30/00: Nanotechnology for materials or surface science, e.g. nanocomposites
- C08G 77/385: containing halogens
- C08G 77/392: containing sulfur
- C08J 2327/12: containing fluorine atoms
- C08J 2327/18: Homopolymers or copolymers of tetrafluoroethylene
- C08J 2483/06: containing silicon bound to oxygen-containing groups (C08J2483/12 takes precedence)
- C08L 2203/20: use in electrical or conductive gadgets
- H01M 2300/0082: Organic polymers
- H01M 2300/0088: Composites
- 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
- B82Y: SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- 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)
- C08L: COMPOSITIONS OF MACROMOLECULAR COMPOUNDS (compositions based on polymerisable monomers C08F, C08G; artificial filaments or fibres D01F; textile treating compositions D06)
- 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

The present invention relates to a proton conductive nanocomposite membrane comprising a fluorinated proton conductive polymer substance introduced with polyhedral oligomeric silsesquioxane (POSS) having a proton donor and polyhedral oligomeric silsesquioxane (POSS) having a proton acceptor, and a method for preparing the same, in which the addition of the very small size POSS having proton donors and POSS having proton acceptors to the nanocomposite membrane increases ion conductivity due to easy hopping of generated protons (cations) within ion channels, thereby realizing excellent proton conductivity while the nanocomposite membrane shows excellent mechanical strength even though the degree of sulfonation of the membrane is increased.

## Claims

### Claim 1

A proton conductive nanocomposite membrane comprising a fluorinated proton conductive polymer substance introduced with polyhedral oligomeric silsesquioxane (POSS) having a proton donor and polyhedral oligomeric silsesquioxane (POSS) having a proton acceptor.

### Claim 2 (depends on 1)

The nanocomposite membrane of claim 1, wherein the fluorinated proton conductive polymer substance comprises at a terminal thereof a functional group selected from the group consisting of sulfonic acid group, a phosphoric acid group and a carboxylic acid group.

### Claim 3 (depends on 1)

The nanocomposite membrane of claim 1, wherein the nanocomposite membrane comprises from 1 wt % to 20 wt % of the polyhedral oligomeric silsesquioxane (POSS) having a proton donor and the polyhedral oligomeric silsesquioxane (POSS) having a proton acceptor.

### Claim 4 (depends on 3)

The nanocomposite membrane of claim 3, wherein a weight ratio of the polyhedral oligomeric silsesquioxane (POSS) having a proton donor and the polyhedral oligomeric silse squioxane (POSS) having a proton acceptor is 1:0.05-1.

### Claim 5 (depends on 1)

The nanocomposite membrane of claim 1, wherein the polyhedral oligomeric silsesquioxane (POSS) has a particle size of from 1 nm to 3 nm.

### Claim 6 (depends on 1)

The nanocomposite membrane of claim 1, wherein the polyhedral oligomeric silsesquioxane (POSS) having a proton donor has the following formula 1:
where R is a proton donor, and
R is a compound having a functional group selected from the group consisting of acetic acid, nitric acid, phosphoric acid, sulfonic acid, perchloric acid, chloric acid, carbonic acid, a salt thereof, and a mixture thereof.

### Claim 7 (depends on 6)

The nanocomposite membrane of claim 6, wherein R is —R1-R2,
where R1 is (CH2)n (n is an integer of 1-6) or phenylene, and
R2 is acetic acid, nitric acid, phosphoric acid, sulfonic acid, perchloric acid, chloric acid,
carbonic acid, a salt thereof, or a mixture thereof.

### Claim 8 (depends on 6)

The nanocomposite membrane of claim 6, wherein the polyhedral oligomeric silsesquioxane (POSS) having a proton donor has the following formula 2:
where at least one R of the formula 2 is —SO3H and is functionalized with up to 16 functional groups.

### Claim 9 (depends on 1)

The nanocomposite membrane of claim 1, wherein the polyhedral oligomeric silsesquioxane (POSS) having a proton acceptor has the following formula 3:
where A of the formula 3 is a compound selected from the group consisting of nitrogen, oxygen, phosphorene, sulfur, fluorine, chlorine atoms having lone pair electrons.

### Claim 10 (depends on 9)

The nanocomposite membrane of claim 9, wherein A is -A1A2,
where A1 is (CH2)n (n is an integer of 1-6) or phenylene, and A2 is NH2, NO3−, NH3, PH3, NH2−, Cl−, O2−, S2−, F−, a salt thereof, or a mixture thereof.

### Claim 11 (depends on 9)

The nanocomposite membrane of claim 9, wherein the polyhedral of igomeric silsesquioxane (POSS) having a proton acceptor has the following formula 4:
where at least one A is NH2 and is functionalized with up to 16 functional groups.

### Claim 12 (depends on 1)

A method of preparing the proton conductive nanocomposite membrane of claim 1 comprising the steps of:
mixing polyhedral oligomeric silsesquioxane (POSS) having a proton donor and polyhedral oligomeric silsesquioxane (POSS) having a proton acceptor with a fluorinated proton conductive polymer solution; and
casting the mixed solution, followed by removing a solvent.

### Claim 13 (depends on 12)

The method of claim 12, wherein the nanocomposite membrane comprises from 1 wt % to 20 wt % of the polyhedral oligomeric silsesquioxane (POSS) having a proton donor and the polyhedral oligomeric silsesquioxane (POSS) having a proton acceptor, and wherein a weight ratio of the polyhedral oligomeric silsesquioxane (POSS) having a proton donor and the polyhedral oligomeric silsesquioxane (POSS) having a proton acceptor is 1:0.05-1.