KR-20260066928-A - Composition and manufacturing method of multi-component pore-filling composite ion exchange membrane

KR20260066928AKR 20260066928 AKR20260066928 AKR 20260066928AKR-20260066928-A

Abstract

The present invention relates to a multi-component pore-filled composite ion exchange membrane and a method for manufacturing the same, and more specifically, to a multi-component pore-filled composite ion exchange membrane comprising two or more nano-sized inorganic materials manufactured by simple impregnation of an inorganic dispersion and a method for manufacturing the same. In addition, the present invention relates to a multi-component pore-filled composite ion exchange membrane containing two types of nano-sized inorganic materials simultaneously by carrying out the step of impregnating in an inorganic particle dispersion solution in two stages, and a method for manufacturing the same.

Inventors

양승철
정연길
김영서
박정근
김민규
이정현

Assignees

국립창원대학교 산학협력단

Dates

Publication Date: 20260512
Application Date: 20241105

Claims (20)

A porous support containing nano-sized inorganic materials within the pores; A monomer selected from the group consisting of sulfonate anionic monomers containing olefins and ammonium cationic monomers, comprising one or more monomers; a crosslinking agent; and an initiator; comprising, A multi-component pore-filled composite ion exchange membrane in which the above-mentioned nano-sized inorganic material comprises a first-type inorganic material and a second-type inorganic material.
In Article 1, The above porous support is, A multi-component pore-filled composite ion exchange membrane characterized by having a pore size of 1 to 200 nm, a porosity of 20 to 90%, and a thickness of 1 to 100 μm.
In Article 1, The above porous support is, A multi-component pore-filled composite ion exchange membrane characterized by being one or more selected from the group consisting of polyethylene, polyolefin, polyester, polysulfone, polyimide, polyetherimide, polyamide, polytetrafluoroethylene, and rayon.
In Article 1, The above Type 1 inorganic material is, Non-carbon inorganic materials composed of SiO₂ , ZrO₂ , MgO, MnO₂ , TiO₂ , ITO, and ZrP; and A multi-component pore-filled composite ion exchange membrane characterized by being one or more selected from the group consisting of carbon-based inorganic materials comprising carbon nanotubes, graphene, graphene oxide, activated carbon, and graphite.
In Article 1, The above Type 2 inorganic material is, Non-carbon inorganic materials composed of SiO₂ , ZrO₂ , MgO, MnO₂ , TiO₂ , ITO, and ZrP; and A multi-component pore-filled composite ion exchange membrane characterized by being one or more selected from the group consisting of carbon-based inorganic materials comprising carbon nanotubes, graphene, graphene oxide, activated carbon, and graphite.
In Article 1, The sulfonate anionic monomer containing the above olefin is, A multi-component pore-filled composite ion exchange membrane characterized by being a sulfonate anionic monomer comprising one or more olefins selected from the group consisting of acrylamide, acrylate, vinyl, aryl, and styrene.
In Article 1, The ammonium-based cation monomer containing the above olefin is, A multi-component pore-filled composite ion exchange membrane characterized by being an ammonium-based cationic monomer comprising one or more olefins selected from the group consisting of acrylamide, acrylate, vinyl, aryl, and styrene.
In Article 1, The above-mentioned crosslinking agent is, A multi-component pore-filled composite ion exchange membrane characterized by comprising two or more olefins selected from the group consisting of acrylamide, acrylate, vinyl, aryl, and styrene.
In Article 1, The above initiator is, A multi-component pore-filled composite ion exchange membrane characterized by being one or more selected from the group consisting of alpha-hydroxyalkylphenones and acylphosphine oxides.
In Article 1, The above-mentioned multi-component pore-filled composite ion exchange membrane is, A multi-component pore-filled composite ion exchange membrane characterized by being prepared by impregnating and drying the porous support in a solvent in which the nano-sized inorganic material is dispersed, then impregnating the porous support in a mixture comprising one or more monomers selected from the group consisting of sulfonate-based anionic monomers containing olefins and ammonium-based cationic monomers; a crosslinking agent; and an initiator, followed by photopolymerization.
A step of primary impregnating and drying a porous support having nano-sized pores in a solution in which a nano-sized Type 1 inorganic material is dispersed; A step of secondarily impregnating and drying the porous support, which was first impregnated, in a solution in which a nano-sized second type inorganic material is dispersed; A step of tertiarily impregnating the porous support, which comprises two types of nano-sized inorganic materials within the pores after the above secondary impregnation, into a mixture comprising one or more monomers selected from the group consisting of sulfonate-based anionic monomers containing olefins and ammonium-based cationic monomers; a crosslinking agent; and an initiator; and A method for manufacturing a multi-component pore-filled composite ion exchange membrane, comprising the step of photopolymerizing the above-mentioned tertiary porous support to manufacture a multi-component pore-filled composite ion exchange membrane.
In Paragraph 11, The above porous support is, A method for manufacturing a multi-component pore-filled composite ion exchange membrane characterized by having a pore size of 1 to 200 nm, a porosity of 20 to 90%, and a thickness of 1 to 100 μm.
In Paragraph 11, The above porous support is, A method for manufacturing a multi-component pore-filled composite ion exchange membrane, characterized by being one or more selected from the group consisting of polyethylene, polyolefin, polyester, polysulfone, polyimide, polyetherimide, polyamide, polytetrafluoroethylene, and rayon.
In Paragraph 11, The above first impregnation step is, A method for manufacturing a multi-component pore-filled composite ion exchange membrane, characterized by further including the step of pre-treating the porous support by adding it to a solvent to which a surfactant has been added.
In Paragraph 11, The above Type 1 inorganic material is, Non-carbon inorganic materials composed of SiO₂ , ZrO₂ , MgO, MnO₂ , TiO₂ , ITO, and ZrP; and A method for manufacturing a multi-component pore-filled composite ion exchange membrane, characterized by being one or more selected from the group consisting of carbon-based inorganic materials composed of carbon nanotubes, graphene, graphene oxide, activated carbon, and graphite.
In Paragraph 11, The above Type 2 inorganic material is, Non-carbon inorganic materials composed of SiO₂ , ZrO₂ , MgO, MnO₂ , TiO₂ , ITO, and ZrP; and A method for manufacturing a multi-component pore-filled composite ion exchange membrane, characterized by being one or more selected from the group consisting of carbon-based inorganic materials composed of carbon nanotubes, graphene, graphene oxide, activated carbon, and graphite.
In Paragraph 11, The above-mentioned nano-sized solution in which the first type of inorganic material is dispersed is, A method for manufacturing a multi-component pore-filled composite ion exchange membrane, characterized by comprising 5 to 70 weight% of the first type of inorganic material relative to 100 weight% of the above solution.
In Paragraph 11, The above-mentioned solution in which the nano-sized Type 2 inorganic material is dispersed is, A method for manufacturing a multi-component pore-filled composite ion exchange membrane, characterized by comprising 5 to 70 weight percent of the second type of inorganic material relative to 100 weight percent of the above solution.
In Paragraph 11, The above second impregnation step is, A method for manufacturing a multi-component pore-filled composite ion exchange membrane, characterized by further including the step of secondary pretreatment by adding a porous support containing two types of nano-sized inorganic materials within the pores, which has been secondarily impregnated as described above, to a solution in which a surfactant is dissolved.
In Paragraph 11, The sulfonate anionic monomer containing the above olefin is, A method for manufacturing a multi-component pore-filled composite ion exchange membrane, characterized by being a sulfonate anionic monomer comprising one or more olefins selected from the group consisting of acrylamide, acrylate, vinyl, aryl, and styrene.

Description

Composition and manufacturing method of multi-component pore-filling composite ion exchange membrane The present invention relates to a multi-component pore-filled composite ion exchange membrane and a method for manufacturing the same, and more specifically, to a multi-component pore-filled composite ion exchange membrane comprising two or more nano-sized inorganic materials manufactured by simple impregnation of an inorganic dispersion and a method for manufacturing the same. Ion exchange membranes are actively used in various systems such as water treatment, energy production, and energy storage. To improve system performance, ion exchange membranes must possess high ion exchange capacity, low resistance, high selectivity, high dimensional stability, and excellent mechanical and chemical properties; however, since it is difficult to satisfy all of these characteristics simultaneously, ion exchange membranes with properties suitable for specific applications are being developed. Composite ion exchange membranes are being studied to improve trade-offs between membrane properties by integrating two constituent materials through the chemical and physical modification of polymer ion exchange membranes. Composite ion exchange membranes can be classified into four types: polymer-mixed ion exchange membranes, pore-filled ion exchange membranes, surface-modified ion exchange membranes, and nanocomposite ion exchange membranes. Among them, nano-composite ion exchange membranes are attracting attention for their ability to improve ion transport and mechanical properties by adding various nanomaterials to electrolyte polymers, and for their ability to improve ion transport characteristics by inducing deformation of the ion conduction channels of the ion exchange membrane. The manufacturing methods of nano-composite ion exchange membranes can be classified into four types: solution blending, in situ polymerization, melt mixing, and sol-gel reaction. The four methods described above require the uniform dispersion of nanomaterials within the material, but dispersing nanomaterials within materials composed of various organic materials is difficult. Furthermore, since dispersing two or more nanomaterials within a material is even more difficult, there is a limitation in that it is challenging to manufacture nanocomposite ion exchange membranes containing two or more nanomaterials. To overcome the limitations mentioned above, there is a need to develop nanocomposite ion exchange membranes containing two or more nanomaterials. FIG. 1 is a drawing showing a multi-component pore-filled composite ion exchange membrane according to the present invention. FIG. 2 is a diagram showing a method for manufacturing a multi-component pore-filled composite ion exchange membrane according to the present invention. FIG. 3 is a diagram showing the XPS analysis results of (a) a cation exchange membrane and (b) anion exchange membrane of an example and a comparative example according to the present invention. FIG. 4 is a diagram showing the cross-sectional TEM analysis results of (a) the cation exchange membrane and (b) the anion exchange membrane of the example and comparative example according to the present invention, and the top (or bottom) and middle portions. FIG. 5 is a diagram showing the TGA analysis results of (a) a cation exchange membrane and (b) anion exchange membrane of an example and a comparative example according to the present invention. Figure 6 is a diagram showing the measurement results of the ion exchange capacity (IEC) of the ion exchange membranes of the embodiments and comparative examples according to the present invention. Figure 7 is a diagram showing the measurement results of the permeability selectivity of the ion exchange membranes of the embodiments and comparative examples according to the present invention. FIG. 8 is a diagram showing the electrical resistance measurement results of the ion exchange membranes of the embodiments and comparative examples according to the present invention. The terms used in this specification have been selected based on currently widely used general terms whenever possible, taking into account their functions in the present invention; however, these terms may vary depending on the intent of those skilled in the art, case law, the emergence of new technologies, etc. Additionally, in specific cases, terms have been arbitrarily selected by the applicant, and in such cases, their meanings will be described in detail in the corresponding description of the invention. Therefore, the terms used in this invention should be defined not merely by their names, but based on their meanings and the overall content of the invention. Unless otherwise defined, all terms used herein, including technical or scientific terms, have the same meaning as generally understood by those skilled in the art to which the present invention pertains. Terms such as those defined in commonly used dictionar