KR-102962186-B1 - A GAS SEPARATION MEMBRANE COMPRISING METAL-ORGANIC FRAMEWORK AND MANUFACTURING METHOD THEREOF

Abstract

The present invention relates to a gas separation membrane capable of selectively permeating more oxygen by including a metal-organic framework structure, and a method for manufacturing the same. The gas separation membrane may comprise a matrix containing a polymer resin and a metal-organic framework (MOF) dispersed in said matrix. The gas separation membrane can be suitably used in electrochemical devices that require the selective permeation of oxygen, such as lithium-air batteries and fuel cells.

Inventors

• 오광석
• 이지현
• 윤민영

Assignees

• 현대자동차주식회사
• 기아 주식회사
• 가천대학교 산학협력단

Dates

Publication Date

20260507

Application Date

20191114

Claims (20)

1. battery cells, and It includes a case for housing the above-mentioned battery cell, and The above case includes an inlet and an outlet communicating with the outside, and The above-mentioned inlet and outlet sections are equipped with gas separation membranes, and The above gas separation membrane comprises a matrix including a polymer resin; and A lithium-air battery comprising a metal-organic framework (MOF) dispersed in the above matrix.
2. In paragraph 1, A lithium-air battery comprising the above polymer resin selected from the group consisting of polyimide, polysulfone, polydimethylsiloxane (PDMS), polyvinylidene fluoride (PVDF), and combinations thereof.
3. In paragraph 1, A lithium-air battery in which the metal-organic framework structure comprises a metal ion or a cluster of metal ions; and an organic ligand connecting them.
4. In paragraph 3, A lithium-air battery in which the metal ions include ions of a metal selected from the group consisting of Zr, Hf, Cr, Ti, Al, Fe, Cu, Co, Mn, Mg, Ni and combinations thereof.
5. In paragraph 3, A lithium-air battery comprising the above-mentioned organic ligand selected from the group consisting of aromatic dicarboxylic acids, aromatic tricarboxylic acids, imidazole compounds, and combinations thereof.
6. In paragraph 1, A lithium-air battery comprising the metal-organic framework structure selected from the group consisting of UiO-66, UiO-66- NH2 , UiO-67, MIL-101, MIL-125, MIL-53, MIL-100, HKUST-1, Co(fm) 2 , Mn(fm) 2 , Mg(fm) 2 , and combinations thereof.
7. In paragraph 1, A lithium-air battery in which the metal-organic framework structure is a porous crystalline compound and the average diameter of the pores is 1 nm to 10 nm.
8. In paragraph 1, The above metal-organic framework is a lithium-air battery having a specific surface area of 100 m² /g or more.
9. In paragraph 1, A lithium-air battery having a content of 5% to 20% by weight of the metal-organic framework structure.
10. In paragraph 1, A lithium-air battery with a thickness of 100㎛ or more.
11. A step of preparing a composition comprising a monomer of a polymer resin, a solvent, and a metal-organic framework structure; A step of casting the above composition onto a substrate; and The method includes the step of manufacturing a gas separation membrane by polymerizing monomers of a polymer resin, and battery cells, and It includes a case for housing the above-mentioned battery cell, and The above case includes an inlet and an outlet communicating with the outside, and The above inlet and outlet are a method for manufacturing a lithium-air battery equipped with the above gas separation membrane.
12. In Paragraph 11, A method for manufacturing a lithium-air battery in which the monomer of the above polymer resin is a monomer of a polymer resin selected from the group consisting of polyimide, polysulfone, polydimethylsiloxane (PDMS), polyvinylidene fluoride (PVDF), and combinations thereof.
13. In Paragraph 11, A method for manufacturing a lithium-air battery in which the metal-organic framework structure comprises a metal ion or a cluster of metal ions; and an organic ligand connecting them.
14. In Paragraph 13, A method for manufacturing a lithium-air battery in which the metal ions include ions of a metal selected from the group consisting of Zr, Hf, Cr, Ti, Al, Fe, Cu, Co, Mn, Mg, Ni and combinations thereof.
15. In Paragraph 13, A method for manufacturing a lithium-air battery comprising the above-mentioned organic ligand selected from the group consisting of aromatic dicarboxylic acids, aromatic tricarboxylic acids, imidazole compounds, and combinations thereof.
16. In Paragraph 11, A method for manufacturing a lithium-air battery comprising the above metal-organic framework structure selected from the group consisting of UiO-66, UiO-66- NH2 , UiO-67, MIL-101, MIL-125, MIL-53, MIL-100, HKUST-1, Co(fm) 2 , Mn(fm) 2 , Mg(fm) 2 , and combinations thereof.
17. In Paragraph 11, A method for manufacturing a lithium-air battery in which the metal-organic framework structure is a porous crystalline compound and the average diameter of the pores is 1 nm to 10 nm.
18. In Paragraph 11, A method for manufacturing a lithium-air battery in which the above metal-organic framework structure has a specific surface area of 100 m² /g or more.
19. In Paragraph 11, A method for manufacturing a lithium-air battery in which the gas separator comprises 5% to 20% by weight of a metal-organic framework structure.
20. In Paragraph 11, A method for manufacturing a lithium-air battery, wherein a composition cast on a substrate is heat-treated to polymerize the monomers of the polymer resin.

Description

A gas separation membrane comprising a metal-organic framework and a method for manufacturing the same The present invention relates to a gas separation membrane capable of selectively permeating more oxygen by including a metal-organic framework structure, and a method for manufacturing the same. The gas separation membrane can be suitably used in electrochemical devices that require the selective permeation of oxygen, such as lithium-air batteries and fuel cells. Recently, as lithium-air batteries utilizing oxygen gas from the air as the cathode active material have garnered attention as next-generation batteries, research on gas separators that selectively separate only oxygen gas from the air and allow it to permeate into the battery is being actively conducted. However, it is very difficult to increase selectivity for oxygen gas while simultaneously improving its permeability. For example, when a porous gas separation membrane is fabricated to increase the permeability of oxygen gas, the selectivity for oxygen gas decreases. Additionally, the permeability of organic compounds used as electrolytes increases, leading to electrolyte depletion. It has been reported that introducing various functional groups into the polymers forming gas separation membranes can increase oxygen permeability while reducing the permeability of organic compounds and carbon dioxide; however, there is a limitation in that it is difficult to secure market competitiveness due to the price increase resulting from the introduction of functional groups. FIG. 1 is a cross-sectional view schematically illustrating a lithium-air battery according to one embodiment of the present invention. FIG. 2 is a cross-sectional view schematically illustrating a gas separation membrane according to the present invention. FIG. 3a illustrates the overall structure of UiO-66, which can be used as a metal-organic framework structure of the present invention. Figure 3b illustrates the unit cell of the above UiO-66. FIG. 4 is a flowchart illustrating a method for manufacturing the gas separation membrane according to the present invention. Figure 5 shows the results of measuring the oxygen permeability of gas separation membranes according to Examples 1 to 3 and Comparative Examples 1 to 4. Figure 6 shows the results of measuring the carbon dioxide permeation of the gas separation membranes of Examples 1 to 3, Comparative Examples 1 to 3, Comparative Example 5, and Comparative Example 6. Figure 7 shows the results of measuring the dimethyl ether permeation of the gas separation membranes of Example 1, Example 3, Comparative Example 2, and Comparative Example 3. The above objects, other objects, features, and advantages of the present invention will be easily understood through the following preferred embodiments associated with the accompanying drawings. However, the present invention is not limited to the embodiments described herein and may be embodied in other forms. Rather, the embodiments introduced herein are provided to ensure that the disclosed content is thorough and complete and to ensure that the spirit of the invention is sufficiently conveyed to a person skilled in the art. In this specification, terms such as "comprising" or "having" are intended to specify the existence of the features, numbers, steps, actions, components, parts, or combinations thereof described in the specification, and should be understood as not precluding the existence or addition of one or more other features, numbers, steps, actions, components, parts, or combinations thereof. Furthermore, when a part such as a layer, film, region, or plate is described as being "on" another part, this includes not only the case where it is "immediately above" the other part, but also the case where there is another part in between. Conversely, when a part such as a layer, film, region, or plate is described as being "below" another part, this includes not only the case where it is "immediately below" the other part, but also the case where there is another part in between. Unless otherwise specified, all numbers, values, and/or expressions used herein to represent amounts of ingredients, reaction conditions, polymer compositions, and formulations should be understood to be modified by the term “approximately” in all cases, as these numbers are essentially approximations reflecting the various uncertainties of measurement that occur in obtaining these values among other things. Furthermore, where numerical ranges are disclosed herein, such ranges are continuous and, unless otherwise indicated, include all values from the minimum value of such range to the maximum value including said maximum value. Moreover, where such ranges refer to integers, they include all integers from the minimum value to said maximum value including said maximum value, unless otherwise indicated. FIG. 1 is a cross-sectional view schematically illustrating a lithium-air battery according to one embodiment of