Ion transport material, electrolyte membrane comprising same, and method for producing same

Patent metadata

Field	Value
Publication number	US-9923225-B2
Application number	US-201415022454-A
Country	US
Kind code	B2
Filing date	Oct 17, 2014
Priority date	Oct 18, 2013
Publication date	Mar 20, 2018
Grant date	Mar 20, 2018

Abstract

The present application relates to an ion transport material, an electrolyte membrane including the same, and a method for manufacturing the same, and more specifically, provides an ion transport material in which inorganic particles are dispersed in a peripheral portion of a sulfonic acid group of a partially fluorinated polymer containing sulfonic acid, an electrolyte membrane including the same, and a method for manufacturing the same.

First claim

The invention claimed is:

1. An ion transport material comprising:
a copolymer comprising a unit of the following Formula 1 and at least one unit of a unit of the following Formula 2, a unit of the following Formula 3, or a unit of the following Formula 4; and
inorganic particles dispersed in a peripheral portion of a sulfonic acid group of the copolymer, wherein a ratio of a weight of inorganic particles dispersed in a portion including the unit of Formula 1 to a weight of inorganic particles dispersed in a portion including at least one unit of the units of Formulae 2 to 4 in the copolymer is 70%:30% to 100%:0% based on a total weight of the inorganic particles:

in Formula 1,
Z is a trivalent aromatic cyclic group or a trivalent heterocyclic group,
L is a direct bond, or a divalent linking group, and
X 1 to X 3 are the same as or different from each other, and are each independently a direct bond, oxygen (O), a carbonyl group (—CO—), a sulfone group (SO 2 —), an arylene group, a heteroarylene group, or *—Z-L-SO 3 H, and * represents a portion which is linked to a main chain, and
in Formulae 2 to 4,
Y 1 to Y 22 are the same as or different from each other, and are each independently hydrogen (H), fluorine (F), or a substituted or unsubstituted alkyl group, and
the units of Formulae 2 to 4 each have at least one fluorine substituent.

2. The ion transport material of claim 1 , wherein L is a direct bond, an alkylene group, an alkenylene group, an alkynylene group, —[(CRR′) r O(CR″R′″) s ] t —, or —CO—Ar—, R, R′, R″, and R′″ are the same as or different from each other, and are each independently hydrogen, an alkyl group, or a halogen group, r and s are 0 to 3, t is 1 to 5, and Ar is an arylene group or a heteroarylene group.

3. The ion transport material of claim 1 , wherein L is —(CH 2 ) m [(CF 2 ) 2 O(CF 2 ) 2 ) n ]—, and m and n are an integer of 0 to 5.

4. The ion transport material of claim 1 , wherein the substituted or unsubstituted alkyl group is —(CQQ′) p Q″ as an alkyl group having 1 to 10 carbon atoms, Q, Q′, and Q″ are hydrogen (—H) or fluorine (—F), and p is 1 to 10.

5. The ion transport material of claim 1 , wherein the inorganic particle is silica.

6. The ion transport material of claim 1 , wherein a content of the inorganic particles is 2 to 30 parts by weight based on 100 parts by weight of a solid content of the ion transport material.

7. The ion transport material of claim 1 , wherein the inorganic particles have a diameter of 5 to 200 nm.

8. The ion transport material of claim 1 , wherein the copolymer has a weight average molecular weight of 10,000 to 1,000,000.

9. An electrolyte membrane comprising the ion transport material of claim 1 .

10. The electrolyte membrane of claim 9 , wherein the electrolyte membrane has a thickness of 5 to 200 μm.

11. A fuel cell comprising the electrolyte membrane of claim 9 .

12. A redox flow battery comprising the electrolyte membrane of claim 9 .

13. A method for manufacturing an electrolyte membrane, the method comprising:
mixing solutions A and B; and
forming a membrane by using the mixture solution,
wherein solution A contains a copolymer comprising a unit of the following Formula 1 and at least one unit of a unit of the following Formula 2, a unit of the following Formula 3, or a unit of the following Formula 4,
wherein solution B contains a precursor of inorganic particles, and
wherein the membrane having an ion transport material comprising the copolymer and the inorganic particles, wherein a ratio of a weight of inorganic particles dispersed in a portion including the unit of Formula 1 to a weight of inorganic particles dispersed in a portion including at least one unit of the units of Formulae 2 to 4 in the copolymer is 70%:30% to 100%:0% based on a total weight of the inorganic particles:

in Formula 1,
Z is a trivalent aromatic cyclic group or a trivalent heterocyclic group,
L is a direct bond, or a divalent linking group, and
X 1 to X 3 are the same as or different from each other, and are each independently a direct bond, oxygen (O), a carbonyl group (—CO—), a sulfone group (—SO 2 —), an arylene group, a heteroarylene group, or *—Z-L-SO 3 H, and * represents a portion which is linked to a main chain, and
in Formulae 2 to 4,
Y 1 to Y 22 are the same as or different from each other, and are each independently hydrogen (H), fluorine (F), or an alkyl group unsubstituted or substituted with fluorine, and
the units of Formulae 2 to 4 each have at least one fluorine substituent.

14. The method of claim 13 , wherein L is a direct bond, an alkylene group, an alkenylene group, an alkynylene group, —[(CRR′) r O(CR″R′″) s ] t —, or —CO—Ar—, R, R′, R″, and R′″ are the same as or different from each other, and are each independently hydrogen, an alkyl group, or a halogen group, r and s are 0 to 3, t is 1 to 5, and Ar is an arylene group or a heteroarylene group.

15. The method of claim 13 , wherein L is —((CH 2 ) m [(CF 2 ) 2 O(CF 2 ) 2 )] n —, and m and n are an integer of 0 to 5.

16. The method of claim 13 , wherein the substituted or unsubstituted alkyl group is —(CQQ′) p Q″ as an alkyl group having 1 to 10 carbon atoms, Q, Q′, and Q″ are hydrogen (—H) or fluorine (—F), and p is 1 to 10.

17. The method of claim 13 , wherein the precursor of inorganic particles is at least one selected from tetraethyl orthosilicate (TEOS), tetramethyl orthosilicate (TMOS), 3-glycidyloxypropyltrimethoxysilane (GOTMS), monophenyl triethoxysilane (MPh), polyethoxysilane (PEOS),3-glycidoxypropyltrimethoxysilane, vinyltriethoxysilane, 3-aminopropyltr imethoxysilane, 3-aminopropyltriethoxysilane, N-2-aminoethyl-3-aminopropyltrimethoxysilane, N-(beta-aminoethyl)gamma-aminopropyltrimethoxysilane, N-(beta-aminoethyl)gamma-aminopropylmethyldimethoxysilane, gamma-ureidopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, and 3-isocyanatopropyltrimethoxysilane.

18. The method of claim 13 , wherein the forming of the membrane by using the mixture solution comprises applying a membrane on a substrate, and heating the membrane.

19. The method of claim 13 , wherein the solution of the precursor of inorganic particles comprises a precursor of inorganic particles and a solvent.

Assignees

• Lg Chemical Ltd

Inventors

• Choi Hyungsam
• Han Joong Jin
• Shin Chong Kyu
• Jeong Seungpyo
• Kim Youngjea

Classifications

• H01M8/1039

  halogenated, e.g. sulfonated polyvinylidene fluorides · CPC title

• H01M8/1081

  starting from solutions, dispersions or slurries exclusively of polymers · CPC title

• H01M8/02

  Details (electrodes H01M4/86 - H01M4/98) · CPC title

• H01M8/102

  characterised by the chemical structure of the main chain of the ion-conducting polymer · CPC title

• H01M8/103 Primary

  having nitrogen, e.g. sulfonated polybenzimidazoles [S-PBI], polybenzimidazoles with phosphoric acid, sulfonated polyamides [S-PA] or sulfonated polyphosphazenes [S-PPh] · CPC title