Carrier-nanoparticle composite, catalyst comprising same, and method for producing same

Patent metadata

Field	Value
Publication number	US-11245119-B2
Application number	US-201716097606-A
Country	US
Kind code	B2
Filing date	Apr 28, 2017
Priority date	May 2, 2016
Publication date	Feb 8, 2022
Grant date	Feb 8, 2022

Abstract

A carrier-nanoparticle complex including a carbon carrier, a polymer layer provided on the surface of the carbon carrier and having an amine group and a hydrogen ion exchange group, and metal nanoparticles provided on the polymer layer, a catalyst including the same, an electrochemical battery or a fuel cell including the catalyst, and a method for preparing the same.

First claim

The invention claimed is:

1. A carrier-nanoparticle complex comprising:
a carbon carrier;
a polymer layer provided on a surface of the carbon carrier, the polymer layer comprising:
a polyalkyleneimine having an amine group, and comprising:
at least one repeating unit of Chemical Formula 1:

and
at least one repeating unit of Chemical Formula 2:

wherein in Chemical Formulae 1 and 2:
E1 and E2 are each independently a straight or branched alkylene group having 2 to 10 carbon atoms,
R is a substituent of any one of the following Chemical Formulae 3 to 5, and
o and p are each an integer from 1 to 1,000,

wherein in Chemical Formulae 3 to 5,
A1 to A3 are each independently a straight or branched alkylene group having 2 to 10 carbon atoms, and
R1 to R3 are each independently a substituent of one of Chemical Formulae 6 to 8,

wherein in Chemical Formulae 6 to 8:
A4 to A6 are each independently a straight or branched alkylene group having 2 to 10 carbon atoms, and
R4 to R6 are each independently a substituent of Chemical Formula 9,

wherein in Chemical Formula 9,
A7 is a straight or branched alkylene group having 2 to 10 carbon atoms; and
a hydrogen ion exchange polymer having a hydrogen ion exchange group of Chemical Formula 12:
—SO 3 − X  [Chemical Formula 12]

wherein X is a monovalent cation group; and

metal nanoparticles provided on the polymer layer,
wherein the polymer layer includes a polymer in which a hydrogen ion exchange group of the hydrogen ion exchange polymer and the amine group of the polyalkyleneimine are crosslinked to each other to form a sulfonamide bonding structure.

2. A carrier-nanoparticle complex, comprising:
a carbon carrier;
a polymer layer provided on a surface of the carbon carrier, the polymer layer comprising:
a polyalkyleneimine comprising a compound of Chemical Formula 11 below, and a hydrogen ion exchange polymer having a hydrogen ion exchange group of Chemical Formula 12 below; and
metal nanoparticles provided on the polymer layer,
wherein the polymer layer includes a polymer in which a hydrogen ion exchange group of the hydrogen ion exchange polymer and the amine group of the polyalkyleneimine are crosslinked to each other to form a sulfonamide bonding structure:

wherein in Chemical Formulae 11:
Y1, Y2, and Y3 are each independently an alkylene group having 2 to 10 carbon atoms,
R is a substituent of one of Chemical Formulae 3 to 5,
n and m are each an integer from 1 to 5,
1 is an integer from 1 to 200,

wherein in Chemical Formulae 3 to 5:
A1 to A3 are each independently an alkylene group having 2 to 10 carbon atoms,
R1 to R3 are each independently a substituent of any one of Chemical Formulae 6 to 8,

wherein in Chemical Formulae 6 to 8:
A4 to A6 are each independently an alkylene group having 2 to 10 carbon atoms, and
R4 to R6 are each independently a substituent of Chemical Formula 9:

wherein in Chemical Formula 9:
A7 is an alkylene group having 2 to 10 carbon atoms;
—SO 3 − X  [Chemical Formula 12]

wherein in Chemical Formula 12, X is a monovalent cation group.

3. The carrier-nanoparticle complex of claim 1 , wherein the metal nanoparticles are bonded to the amine group of the polymer layer.

4. The carrier-nanoparticle complex of claim 1 , wherein based on the total elements on a surface of the polymer layer, the content of the nitrogen element of the amine group is greater than or equal to 0.01% by weight and less than or equal to 5% by weight, and the content of the sulfur element of the hydrogen ion exchange group of Chemical Formula 12 is greater than or equal to 0.01% by weight and less than or equal to 1% by weight.

5. The carrier-nanoparticle complex of claim 1 , wherein a weight ratio of the polyalkyleneimine to the hydrogen ion exchange polymer is 15 or more and 100 or less.

6. A catalyst comprising the carrier-nanoparticle complex of claim 1 .

7. An electrochemical battery comprising the catalyst of claim 6 .

8. A membrane electrode assembly comprising:
an anode catalyst layer;
a cathode catalyst layer; and
a polymer electrolyte membrane provided between the anode catalyst layer and the cathode catalyst layer,
wherein the anode catalyst layer or the cathode catalyst layer comprises the carrier-nanoparticle complex according to claim 1 .

9. The membrane electrode assembly of claim 8 , wherein the anode catalyst layer and the cathode catalyst layer each comprises an ionomer.

10. A method for preparing a carrier-nanoparticle complex, the method comprising:
forming on a surface of a carbon carrier a polymer layer comprising:
a polyalkyleneimine having an amine group and comprising:
at least one repeating unit of Chemical Formula 1:

and
at least one repeating unit of Chemical Formula 2:

wherein in Chemical Formulae 1 and 2:
E1 and E2 are each independently a straight or branched alkylene group having 2 to 10 carbon atoms,
R is a substituent of any one of the following Chemical Formulae 3 to 5, and
and p are each an integer from 1 to 1,000,

wherein in Chemical Formulae 3 to 5,
A1 to A3 are each independently a straight or branched alkylene group having 2 to 10 carbon atoms, and
R1 to R3 are each independently a substituent of one of Chemical Formulae 6 to 8,

wherein in Chemical Formulae 6 to 8:
A4 to A6 are each independently a straight or branched alkylene group having 2 to 10 carbon atoms, and
R4 to R6 are each independently a substituent of Chemical Formula 9,

wherein in Chemical Formula 9,

A7 is a straight or branched alkylene group having

Assignees

• Lg Chemical Ltd

Inventors

• Cho Jun Yeon
• Kim Kwanghyun
• Hwang Gyo Hyun
• Kim Sang Hoon
• Choi Ran
• Lee Wonkyun

Classifications

• B01J35/45

  Nanoparticles · CPC title

• H01M8/1004 Primary

  characterised by membrane-electrode assemblies [MEA] (H01M8/12 takes precedence) · CPC title

• H01M2008/1095

  Fuel cells with polymeric electrolytes · CPC title

• Y02E60/50

  Fuel cells · CPC title

• C08J5/2256

  based on macromolecular compounds obtained by reactions other than those involving carbon-to-carbon bonds, e.g. obtained by polycondensation · CPC title