KR102466227B1 - Method for manufacturing catalyst layer, Catalyst layer, Bipolar-membrane - Google Patents

Abstract

The present invention relates to a catalyst layer formed by mixing a catalyst material in a particulate state and a fluid material in a liquid state and spraying, and then remaining the catalyst material through a drying process, and also to a bipolar membrane using the catalyst layer. Specifically, a first preparation step (S100) of preparing a catalyst material 100 of a homogeneous size; A second preparation step (S200) of preparing a fluid material 200 formed of a fluid; After the second preparation step, a mixing step (S300) of mixing the catalytic material to form a mixture 300; After the mixing step, a coating step (S400) of forming a coating layer 400 with the mixture; After the coating step, a drying step (S500) of removing fluid materials;

Description

Method for manufacturing catalyst layer, Catalyst layer, Bipolar-membrane}

The present invention relates to a catalyst layer formed by mixing a catalyst material in a particulate state and a fluid material in a liquid state and spraying, and then remaining the catalyst material through a drying process, and also to a bipolar membrane using the catalyst layer.

Patent Invention 001 is an invention for a method for producing a slurry for forming a catalyst layer of a hydrogen ion exchange membrane (PEM) fuel cell. Specifically, the method for producing a slurry for forming a catalyst layer for a PEM fuel cell is Converting PFSI in the solution to M+ form by adding Li, Na, K) as alkali metals, b) adding a polar organic solvent having a higher boiling point than the residual alcohol in the PFSI solution to the mixed solution of a), and then Obtaining a pretreated PFSI solution by heating at a boiling point of from +20 ° C to remove residual alcohol, and c) mixing the pretreated PFSI solution and Pt / carbon powder to form a slurry for forming a catalyst layer of a PEM fuel cell Steps to do; are presented.

Patent Invention 002 is an invention for a method of forming a catalyst layer on a hydrogen ion exchange membrane of a membrane electrode assembly for a fuel cell, specifically, a polymer electrolyte membrane fuel cell (PEMFC), a direct methanol fuel cell (DMFC) A technique for forming a uniform catalyst layer with highly dispersed catalyst particles is proposed, which is completely different from the method of forming a catalyst layer by the spray method or brush method, which is mainly used in the manufacture of membrane electrode assemblies (MEAs) such as Fuel Cell). .

Patent Invention 003 is an invention for a bipolar ion exchange sheet and a method for manufacturing the same, specifically, a bipolar ion exchange sheet in which a cation adsorption sheet, a cation exchange coating layer, an anion exchange coating layer, and an anion adsorption sheet are sequentially arranged, the cation adsorption sheet and providing a bipolar ion exchange sheet in which at least one of the anion adsorption sheets has a plurality of through holes, forming a plurality of through holes in one of the cation adsorption sheet and the anion adsorption sheet; Forming a first ion exchange coating layer by coating a first ion exchange coating liquid containing a polymer having an ion exchange group of the same polarity on one surface of an ion adsorption sheet having no through holes and drying the same, on the first ion exchange coating layer coating a second ion exchange coating liquid containing a polymer having an ion exchange group of a different polarity; and before the second ion exchange coating liquid is dried, the ion adsorbing sheet having the plurality of through holes is coated with the second ion exchange coating liquid. A method for manufacturing a bipolar ion exchange sheet is provided, which includes forming a second ion exchange coating layer by laminating on an exchange coating solution and drying the same, and bonding the ion exchange sheet having the through holes formed thereon.

Patent Invention 004 is an invention for a bipolar ion exchange membrane having an asymmetric structure and a method for manufacturing the same. a first polar ion exchange membrane including a homogeneous first polar ion exchange resin layer made of a polymer having a polar ion exchange group; and a heterogeneous second polar ion exchange membrane in which powder of a second polar ion exchange resin having an ion exchange group of a second polarity on a surface of the first polar ion exchange resin layer is dispersed in a matrix resin, wherein the ion exchange membrane of the first polarity A bipolar ion exchange membrane in which an ion exchange membrane of polarity and a second polarity face each other in an asymmetric layer structure is proposed.

KR 10-0446607 (registered on August 23, 2004) KR 10-0705553 (registered on April 3, 2007) KR 10-2017-0035718 (published on March 31, 2017) KR 10-2018-0109586 (published on October 08, 2018)

The present invention relates to a catalyst layer formed by mixing a catalyst material in a particulate state and a fluid material in a liquid state and spraying, and then remaining the catalyst material through a drying process, and also to a bipolar membrane using the catalyst layer.

The present invention relates to a method for preparing a catalyst layer, and specifically, a first preparation step (S100) of preparing a catalyst material 100 of a homogeneous size; A second preparation step (S200) of preparing a fluid material 200 formed of a fluid; After the second preparation step, a mixing step (S300) of mixing the fluid material and the catalyst material to form a mixture 300; After the mixing step, a coating step (S400) of forming a coating layer 400 with the mixture; After the coating step, a drying step (S500) of removing fluid materials;

The present invention relates to a method for manufacturing a catalyst layer, and in the above-described invention, among the mixing step or the second preparation step, an addition step (S310) of adding a solvent 500; additionally further includes.

The present invention relates to a method for manufacturing a catalyst layer, and in the above-described invention, the first preparation step further includes a hydrophilization step (S130) of hydrophilizing the catalyst material.

The present invention relates to a method for preparing a catalyst layer, and in the above-described invention, before or simultaneously with the hydrophilization step, a nanofluid preparation step (S140) of preparing a nanofluid is included.

The present invention is an invention for a catalyst layer, and includes a catalyst layer prepared by the manufacturing method presented above.

The present invention relates to a bipolar membrane, and includes a first membrane layer 10 in the form of a thin plate; a catalyst layer 20 attached to one surface of the first membrane layer and manufactured by the manufacturing method of claim 1; It consists of a configuration including; a second membrane layer 30 attached to one surface of the catalyst layer.

The catalyst layer of the present invention is formed as a thin layer, and a high water splitting effect can be obtained by using low power by reducing the water splitting voltage.

Since the present invention uses a catalyst material of 100 nanometers or less and a fluid material having fluidity, the water decomposition voltage can be reduced with only a small amount of catalyst, so the amount of catalyst used can be greatly reduced.

Since the present invention uses a small amount of catalyst, there is little interference between the anion membrane and the cation membrane, and thus the adhesion of the membranes can be improved.

Since the present invention adds a solvent during the mixing process, it is possible to uniformly disperse the catalyst during the spraying and drying processes.

In the present invention, hydrophilization and dispersion stability can be improved on the surface of the catalyst material by the surfactant, so that the catalyst powder can be homogeneously dispersed.

1 is a flow chart of a catalyst layer production step according to the present invention.
Figure 2 is a flow chart of the bipolar membrane production steps including the catalyst layer of the present invention.
Figure 3 is a conceptual diagram of the bipolar membrane production step including the catalyst layer and the catalyst layer of the present invention.

Hereinafter, the most preferred embodiment of the present invention will be described in detail in order to explain the present invention in detail to the extent that those skilled in the art can easily practice the present invention.

Numbers cited in the examples below are not limited to the referenced subject and can be applied to all examples. An object that exhibits the same purpose and effect as the configuration presented in the embodiment corresponds to an equivalent replacement object. High-level concepts presented in the examples include sub-concept objects that are not described.

[Example 1-1] The present invention relates to a method for preparing a catalyst layer, and specifically, a first preparation step (S100) of preparing a catalyst material 100 of a homogeneous size; A second preparation step (S200) of preparing a fluid material 200 formed of a fluid; After the second preparation step, a mixing step (S300) of mixing the fluid material and the catalyst material to form a mixture 300; After the mixing step, a coating step (S400) of forming a coating layer 400 with the mixture; After the coating step, a drying step (S500) of removing fluid materials;

The present invention (see Example 1-1, Figure 1) relates to a method for forming a catalyst layer. The bipolar membrane brings the cation membrane and the anion membrane into contact with each other, and forms a catalyst layer on the contact surface. That is, the catalyst layer of the present invention is formed as a thin layer, and a high water splitting effect can be obtained by using low power by reducing the water splitting voltage.

As a step to realize this, a catalytic material having a size of 100 nm or less is prepared in a mixed state with a fluid material, and the mixed material is applied to one surface of the ion exchange membrane. It is characterized in that the fluid material is dried after being coated so that the powdery catalytic material is placed on the surface of the ion exchange membrane.

[Example 1-2] The present invention relates to a method for preparing a catalyst layer, and in Example 1-1, the fluid material is formed of water (210); includes.

[Example 1-3] The present invention relates to a method for preparing a catalyst layer, and in Example 1-1, the fluid material is formed of water 210 and alcohol 220; includes.

[Example 1-4] The present invention relates to a catalyst layer manufacturing method, and in Examples 1-3, the alcohol is isopropyl alcohol (210a), ethanol (210b), methyl alcohol (210c), methanol (210d) ), fusel alcohol (210e), glycerol (210f), glycerin (210g) selected from any one or formed of two or more; includes.

The present invention (Example 1-2 to Example 1-4, see Figure 1) is an invention for a fluid substance. The fluid material mixed with the catalyst material of the present invention includes water. However, since water has surface tension (the surface tension of water is 72 Ns/m2), it is difficult to widely and uniformly distribute the catalyst layer on the surface of the ion exchange membrane.

To solve this, mix alcohol with water. The surface tension of the fluid is lowered by alcohol (the surface tension of isopropyl alcohol is 21.7 Ns/m2, the surface tension of ethanol is 22.75 Ns/m2), and it enables a wide, thin and homogeneous distribution of the fluid on the surface of the ion exchange membrane. .

The alcohol may be selected from among isopropyl alcohol, ethanol, methyl alcohol, methanol, fusel alcohol, glycerol, and glycerin.

[Example 1-5] The present invention relates to a method for preparing a catalyst layer, and in Example 1-1, the catalyst material is formed of a metal oxide.

[Example 1-6] The present invention relates to a method for manufacturing a catalyst layer, and in Examples 1-5, the catalyst material is a metal oxide, a metal hydroxide, a metal hydrochloride ( metal hydrochloride) is formed of any one or a combination of two or more selected from; includes.

[Example 1-7] The present invention relates to a method for preparing a catalyst layer, and in Example 1-1, the mixing step includes mixing the catalyst material in an amount of 0.01 to 30% by weight with respect to the fluid material. .

[Example 1-8] The present invention relates to a method for preparing a catalyst layer, and in Example 1-1, the catalyst material has a particle size of 1 nm to 100 nm.

The present invention (Examples 1-5 and 1-6, see Figure 1) relates to a catalyst material. The catalyst material of the present invention is preferably formed of a metal oxide, and specifically, it is preferably formed of a metal oxide, metal hydroxide, or metal hydrochloride. The metal oxide includes Fe2O3 and Fe3O4, the metal hydroxide includes Fe(OH)3 and FeOOH, and the metal hydrochloride includes tin chloride hydroxide [Sn(OH)xCL2; x(0<x<2)].

The catalyst material is preferably selected in the range of 0.01% by weight to 30% by weight based on the fluid material. In the above numerical value, in the case of 0.01% by weight or less, it is difficult to apply the required amount to the surface of the ion exchange membrane, and in the case of 30% by weight or more, it is difficult to uniformly apply the required amount to the surface of the ion exchange membrane.

[Example 1-9] The present invention relates to a method for manufacturing a catalyst layer, and in Example 1-1, the drying step includes an infrared drying step (S510) of irradiating and drying infrared rays by an infrared lamp 510; includes

[Example 1-10] The present invention relates to a catalyst layer manufacturing method, and in Example 1-1, the drying step is a hot air drying step (S520) of drying by sending hot air by a hot air blower 520; include

[Example 1-11] The present invention relates to a catalyst layer manufacturing method, and in Example 1-1, the coating step includes a spray spraying step (S410) of spraying by a spray nozzle 410.

[Example 1-12] The present invention relates to a catalyst layer manufacturing method, and in Example 1-1, after the first preparation step, a first quantitative input step (S120) of measuring the input amount of the catalyst material; include

[Example 1-13] The present invention relates to a catalyst layer manufacturing method, and in Example 1-1, after the second preparation step, the second quantitative input step (S220) of measuring the input amount of the fluid material; include

The present invention (Examples 1-9 to 1-13) presents additional catalyst layer manufacturing method steps. The catalyst layer is prepared in a state composed of the catalyst material included in the fluid material, and should be applied to the surface of the anion membrane in a uniform thickness. To this end, it is applied by spraying, and may include a method equivalent to this.

The fluid material forming the catalyst layer is removed by drying, and only the catalyst material should remain. To this end, the drying process removes the fluid substance formed of the alcohol component and water by infrared drying or hot air drying. Equivalent targets for drying moisture other than the infrared rays or hot air are also included.

The first preparation step is a step of preparing a catalyst material, and a fixed amount of the catalyst material is introduced by the first quantitative input step. In addition, the catalytic material must be introduced into the fluid material prepared in advance, and the fluid material is also prepared in advance by the second quantitative input step.

[Example 2-1] The present invention relates to a method for preparing a catalyst layer, and in Example 1-1, an addition step (S310) of adding a solvent 500 among the mixing step or the second preparation step; It consists of time-series steps that include

[Example 2-2] The present invention relates to a method for preparing a catalyst layer, and in Example 2-1, the additives are NMP (n-methylpyrollidone), DMAc (dimethylacetamide), GBL (gamma-butyrolactone), DMF ( Dimethylformamide), one selected from DMSO (Dimethylformamide), or formed by a combination of two or more; includes.

The present invention (Examples 2-1 and 2-2, see Figure 1) relates to the addition step. A solvent is added to the inside of the fluid, and the solvent may be any one selected from NMP, DMAc, GBL, DMF, and DMSO, or a mixture of two or more solvents.

Solvents have dissolving properties. Therefore, a fluid material is applied to the surface of the anion membrane, and the surface of the anion membrane is melted by the solvent so that the catalyst powder adheres completely. Therefore, it is possible to secure the effect of improving the binding force of the catalytic material by the addition step.

[Example 3-1] The present invention relates to a method for preparing a catalyst layer, and in Example 1-1, the first preparation step further includes a hydrophilization step of hydrophilizing the catalyst material (S130).

[Example 3-2] The present invention relates to a method for manufacturing a catalyst layer, and in Example 3-1, the hydrophilization step is performed using metal oxides, metal hydroxides, and metal hydroxides. hydrochloride) nanoparticles are mixed with a surfactant to form a hydrophilic step.

[Example 3-3] The present invention relates to a method for preparing a catalyst layer, and in Example 3-2, the surfactant is an anionic, cationic, nonionic, amphoteric surfactant and fatty acid, PEG (polyethylene glycol) and TMAOH (tetramethyl ammonium hydroxide).

[Example 4-1] The present invention relates to a method for preparing a catalyst layer, and in Example 3-1, before or simultaneously with the hydrophilization step, a nanofluid preparation step (S140) of preparing a nanofluid is included.

The hydrophilization step of the present invention (see Examples 3-1 to 4-1, Figure 1) is to synthesize nano-sized hydrophilization catalyst materials, such as FeCl3, FeCl2, and FeOOH, such as metal oxides, metal hydroxides, and metal hydroxide chlorides. Nanoparticles such as iron oxide (magnetite or magnetite) particles with a size of less than 30 nm are synthesized by mixing and stirring a surfactant such as TMAOH (tetramethyl ammonium hydroxide) in an aqueous solution of the precursor of A nanofluid can be realized.

The catalyst material is in powder form, and the fluid material is in liquid form. The synthesized nano-sized catalytic material must be present in a homogeneously dispersed state in the fluid material. However, nano-sized catalytic materials cause aggregation due to their surface energy.

Therefore, homogenized dispersion conditions cannot be formed. In order to solve this problem, a surfactant is included in the fluid material, which is attached to the surface of the catalyst material and can prevent the nanoparticles from aggregating with each other.

[Example 5-1] The present invention relates to a catalyst layer, and includes a catalyst layer prepared by the catalyst layer manufacturing method of the above-described embodiment.

The present invention (see Example 5-1, Figure 3) relates to the catalyst layer of the present invention, and to a catalyst layer formed by the above-described manufacturing method. The catalyst layer of the present invention has a specificity obtained by the manufacturing method, and the product is affected by the manufacturing method.

[Example 6-1] The present invention relates to a bipolar membrane, and specifically, the first membrane layer 10 in the form of a thin plate; a catalyst layer 20 attached to one surface of the first membrane layer and manufactured by the manufacturing method of Example 1-1; It consists of a configuration including; a second membrane layer 30 attached to one surface of the catalyst layer.

[Example 6-2] The present invention relates to a bipolar membrane, and in Example 6-1, the first membrane layer is an anion membrane layer and the second membrane layer is formed of a cationic membrane layer; includes

[Example 6-3] The present invention relates to a bipolar membrane, and in Example 6-1, the first membrane layer is a cationic membrane layer and the second membrane layer is formed of an anionic membrane layer; includes

[Example 6-4] The present invention relates to a bipolar membrane, and in Example 6-2, the present invention relates to a bipolar membrane, and in Example 6-3, the cation membrane layer and the anion membrane The layer is formed of a hydrocarbon-based; includes.

[Example 6-5] The present invention relates to a bipolar membrane, and in Example 6-4, the anion membrane layer is formed of APPO (anion polyphenylene oxide).

[Example 6-6] The present invention relates to a bipolar membrane, and in Example 6-4, the cation membrane layer is formed of CPPO (cation polyphenylene oxide); includes.

The present invention (see Examples 6-1 to 6-6 and FIG. 2) relates to a bipolar membrane, wherein a first membrane is formed on one side of the catalyst layer presented above, and a second membrane is formed on the other side. Preferably, the first and second membranes are formed of cationic membranes or anionic membranes. The cation or anion membrane is characterized in that a cation or anion exchanger is introduced into a high molecular weight polymer formed of a hydrocarbon system. For example, polymers obtained by polymerizing monomers such as vinyl, styrene, and acrylic, or polysulfone, polyphenylene sulfide, polyether ketone, polyether ether ketone, polyetherimide, polyphenylene oxide, polyether sulfone, It is not limited to those having a structure in which an ion exchanger, specifically a cation exchanger or anion exchanger, that expresses ion exchange ability is introduced into a hydrocarbon-based resin such as a polymer containing an aromatic ring in the main chain such as polybenzimidazole, but is not limited thereto. Any possible membrane is possible, and it is characterized in that it is formed of APPO and CPPO.

That is, it is possible to form a membrane including a bipolar polarity in one form. The cation membrane and the anion membrane must ensure intact binding properties. To this end, it is necessary to artificially form a certain roughness on the surface of the membrane, which can improve the contact area by forming micro-sized scratches or forming bends with sandpaper.

In addition, the anion membrane and the cationic membrane may have the same or different thicknesses.

[Example 6-7] The present invention relates to a bipolar membrane, and in Example 6-1, the first membrane layer and/or the second membrane layer include ion exchange resin powder (11, 31), polymer solute (12, 32), solvents (13, 33) and ion exchange solutions (14, 34) formed by mixing;

[Example 6-8] The present invention relates to a bipolar membrane, and in Examples 6-7, additives 15 and 35 are further included.

[Example 6-9] The present invention relates to a bipolar membrane, and in Examples 6-8, the additive is formed of a silane compound.

[Example 6-10] The present invention relates to a bipolar membrane, and in Examples 6-7, the solvent is formed of an amphoteric solvent.

[Example 6-11] The present invention relates to a bipolar membrane, and in Examples 6-7, the ion exchange resin powder (11, 31) is formed of a cation resin powder or an anion resin powder; including do.

[Example 6-12] The present invention relates to a bipolar membrane, and in Examples 6-7, the polymer solute is formed of any one selected from PP, PE, PS, ABC, PA, PVC, PET, and PVDF. It includes; includes.

The present invention (Examples 6-7 to 6-11, see FIG. 2) is to form a heterogeneous ion exchange bipolar membrane. The cation membrane layer and the anion membrane layer are formed by casting a compound in a slurry state. The compound in the slurry state is formed by combining ion exchange resin powder, polymer solute, solvent, ion exchange solution and additives. In particular, the additive is preferably formed of a sarlan compound, and the solvent is preferably formed of an amphoteric solvent. The purpose of the ion exchange resin powder is to impart ion selectivity. A polymer solute may also be included.

[Example 6-13] The present invention relates to a bipolar membrane, and in Example 6-1, a first ion exchange layer forming step (S10) of forming an anion exchange layer in a thin film form; a catalyst layer forming step (S20) of forming a catalyst layer on one surface after the first ion exchange layer forming step; After the catalyst layer forming step, a second ion exchange layer forming step (S30) of forming a cation exchange layer on one surface; a manufacturing step including is additionally included.

[Example 6-14] The present invention relates to a bipolar membrane, and in Examples 6-8, the first ion exchange layer and the second ion exchange layer are cast to form an ion exchange material in a slurry state in a thin film form. step; includes.

The present invention (Examples 6-12 and 6-13, see Fig. 2) adds a step of manufacturing a bipolar membrane. First, an anion exchange layer is formed on the base layer by a casting technique, and a first ion exchange layer is formed through a drying process. After the first ion exchange layer is completed, a catalyst layer is formed by spraying, and a catalyst material is placed on one side of the anion exchange layer by a drying process. In addition, after the step of forming the catalyst layer, a step of forming a second ion exchange layer by casting and drying a cation exchange layer on one surface of the catalyst layer is performed. The procedure presented above affects the finished product, and in particular, in forming a plurality of layers formed of thin films, it affects the production efficiency and product quality improvement, so there is an influence on the specification of the product by methodological description. do.

10: first membrane layer 20: catalyst layer
30: second membrane layer
100: catalyst material 200: fluid material
210: water 220: alcohol
300: mixture 400: coating layer
410: injection nozzle
500: solvent 510: infrared lamp
520: hot air blower

Claims (6)

In the catalyst layer manufacturing method,
A first preparation step (S100) of preparing a catalyst material 100 of a homogeneous size;
A second preparation step (S200) of preparing a fluid material 200 formed of a fluid;
After the second preparation step (S200), a mixing step (S300) of mixing the fluid material and the catalyst material to form a mixture 300;
After the mixing step (S300), a coating step (S400) of forming a coating layer (400) with the mixture;
After the application step (S400), a drying step (S500) of removing the fluid material; includes,
Among the second preparation step (S200) or mixing step (S300), an addition step (S310) of adding a solvent 500; includes,
The fluid material is formed by mixing water 210 and alcohol 220; includes,
The catalytic material is formed of a metal oxide, wherein the metal oxide is formed of any one or a combination of two or more selected from among metal oxide, metal hydroxide, and metal hydrochloride; including,
The additive in the addition step (S310) is formed as a solvent, and the solvent is any one selected from NMP (n-methylpyrollidone), DMAc (dimethylacetamide), GBL (gamma-butyrolactone), DMF (dimethylformamide), and DMSO (dimethylformamide). Or formed in a combination of two or more; Catalyst layer manufacturing method comprising a.
delete The method of claim 1,
The first preparation step is a catalyst layer manufacturing method comprising a; hydrophilization step (S130) of making the catalyst material hydrophilic.
The method of claim 3,
Prior to or simultaneously with the hydrophilization step, a nanofluid manufacturing step (S140) of manufacturing a nanofluid
Catalyst layer manufacturing method comprising a.
In the catalyst layer,
Catalyst layer 20 manufactured by any one manufacturing method selected from claims 1, 3 and 4.
In the bipolar membrane,
a first membrane layer 10 in the form of a thin plate;
a catalyst layer 20 attached to one surface of the first membrane layer and manufactured by the manufacturing method of claim 1;
a second membrane layer 30 attached to one surface of the catalyst layer;
A bipolar membrane comprising a.

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