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

Patent metadata

Field	Value
Publication number	US-10439245-B2
Application number	US-201415022120-A
Country	US
Kind code	B2
Filing date	Oct 17, 2014
Priority date	Oct 18, 2013
Publication date	Oct 8, 2019
Grant date	Oct 8, 2019

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 sulfonate group-containing partially fluorine-based polymer, 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 the copolymer:

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,
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 R, and * represents a portion which is linked to a main chain, and
R is an element of Group 1 in the periodic table, 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,
wherein an area occupied by the inorganic particles per square micrometer area is 2% to 30% based on a two-dimensional cross-section obtained by forming the ion transport material as a membrane and capturing one surface of the membrane using a device selected from the group consisting of an atomic force microscope (AFM), an optical profiler, and a scanning electron microscope (SEM).

2. The ion transport material of claim 1 , wherein L is a direct bond, an alkylene group, an alkenylene group, an alkynylene group, —[(CRR′)rO(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′)pQ″ 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 the electrolyte membrane of claim 9 , the method comprising:
preparing solution A containing a copolymer comprising a unit of the following Formula 1A 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;
preparing solution B comprising a precursor of inorganic particles and an acid catalyst;
mixing solutions A and B; and
forming a membrane by using the mixture solution:

in Formula 1A, Z is a trivalent aromatic cyclic group or a trivalent heterocyclic group,
L is a direct bond, or a divalent linking group,
X 4 to X 6 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 M, and * represents a portion which is linked to a main chain, and
M is an alkali metal element, 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,
wherein an area occupied by the inorganic particles per square micrometer area is 2% to 30% based on a two-dimensional cross-section obtained by forming the ion transport material as a membrane and capturing one surface of the membrane using a device selected from the group consisting of an atomic force microscope (AFM), an optical profiler, and a scanning electron microscope (SEM).

14. The method of claim 13 , wherein L is a direct bond, an alkylene group, an alkenylene group, an alkynylene group, —[(CRR′)rO(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′)pQ″ 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-aminopropyltrimethoxysilane, 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 , further comprising:
substituting the alkali metal with hydrogen after the forming of the membrane.

19. The method of claim 13 , wherein solution B comprises a precursor of inorganic particles, an acid catalyst, and a solvent.

20. The ion transport material of claim 1 , wherein the copolymer includes at least one unit of the following Formula 5, Formula 6, Formula 7, Formula 8, Formula 9 or Formula 10:

wherin, R is an element of Group 1 in the periodic table, and
a and b represent a mole fraction relative to the entire copolymer, and
a+b≤1, 0.1≤a≤0.9, and 0.1≤b≤0.9.

Assignees

• Lg Chemical Ltd

Inventors

• Choi Hyungsam
• Han Joong Jin
• Kim Youngjea
• Kang Esder
• Shin Chong Kyu
• Noh Tae Geun
• Moon Sikwon

Classifications

• H01M8/1069

  characterised by the manufacturing processes · CPC title

• H01M8/188

  by recharging of redox couples containing fluids; Redox flow type batteries · CPC title

• H01M8/1051 Primary

  Non-ion-conducting additives, e.g. stabilisers, SiO2 or ZrO2 · CPC title

• H01M8/02

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