Hollow fiber membrane and fuel cell membrane humidifier comprising same

Abstract

The present invention relates to a hollow fiber membrane for a fuel cell membrane humidifier, a method for manufacturing same, and a fuel cell membrane humidifier comprising the hollow fiber membrane, the hollow fiber membrane comprising a polymer support and an amine-based antioxidant having a molecular weight of 1000 or less, wherein the amine-based antioxidant is included in the polymer support in a non-crosslinked form.

Description

Hollow fiber membrane and fuel cell membrane humidifier containing the same

[0001] The present invention relates to a hollow fiber membrane and a fuel cell membrane humidifier including the same, and more particularly, to a hollow fiber membrane that prevents deterioration and decomposition of the hollow fiber membrane and a fuel cell membrane humidifier including the same.

[0002] Fuel cells are power-generating cells that convert the chemical energy of hydrogen and oxygen into electrical energy through an electrochemical reaction. Unlike conventional chemical cells like batteries or accumulators, fuel cells can continuously produce electricity as long as hydrogen and oxygen are supplied. They also have the advantage of no heat loss, making them more than twice as efficient as internal combustion engines.

[0003] Furthermore, fuel cells are environmentally friendly energy generators that generate no pollutants, as they use hydrogen and oxygen as raw materials and produce water as a product. Therefore, fuel cells are not only environmentally friendly but also offer the advantage of reducing concerns about resource depletion due to increased energy consumption.

[0004] Fuel cells can be classified into polymer electrolyte membrane fuel cells (PEMFC), phosphoric acid fuel cells (PAFC), molten carbonate fuel cells (MCFC), solid oxide fuel cells (SOFC), and alkaline fuel cells (AFC).

[0005] Among these, polymer electrolyte fuel cells are known to be suitable for use in transportation systems because they can operate at lower temperatures and have a higher power density than other fuel cells.

[0006] Meanwhile, polymer electrolyte fuel cells generally form water by reacting 2 moles of hydrogen and 1 mole of oxygen in the fuel cell stack during operation. However, if the reaction is incomplete, peroxide or hydroxyl radicals may be formed as byproducts.

[0007] When the peroxide or hydroxyl radicals generated in this way flow from the fuel cell stack to the membrane humidifier, there is a problem in that they cause oxidation of the organic hollow fiber membrane within the membrane humidifier, resulting in decomposition and deterioration of the hollow fiber membrane.

[0008] Decomposition and deterioration of the hollow fiber membrane impede the delivery of sufficiently moist air to the fuel cell stack, thereby reducing the efficiency of the fuel cell stack and the entire fuel cell.

[0009] Accordingly, there is an industrial demand for hollow fiber membranes that are resistant to decomposition by peroxide or hydroxyl radicals.

[0010] The present invention provides a hollow fiber membrane with improved durability that is prevented from deterioration and decomposition by peroxide or hydroxyl radicals.

[0011] According to one aspect, a hollow fiber membrane for a membrane humidifier is provided, which comprises a polymer support and an amine-based antioxidant having a molecular weight of 1000 or less, wherein the amine-based antioxidant is included in the polymer support in a non-crosslinked form.

[0012] According to another aspect, a step of preparing a radiation source solution comprising a polymer and an amine-based antioxidant having a molecular weight of 1000 or less;

[0013] A step of radiating the above-mentioned radiation source into a coagulation tank through a nozzle;

[0014] A method for manufacturing a hollow fiber membrane for a fuel cell membrane humidifier is provided, including a step of solidifying a radiation source in the above-mentioned coagulation tank.

[0015] According to another aspect, a membrane humidifier for a fuel cell including the above hollow fiber membrane is provided.

[0016] According to one aspect, the hollow fiber membrane comprises a non-crosslinked amine-based antioxidant having a molecular weight of 1000 or less in a polymer support, so that hydroxyl radicals or peroxides generated in a fuel cell stack and introduced into a membrane humidifier preferentially react with the amine-based antioxidants, thereby suppressing deterioration and decomposition of the hollow fiber membrane, thereby improving the durability of the membrane humidifier. In addition, the outside air introduced into the membrane humidifier is humidified and supplied to the fuel cell stack. At this time, a trace amount of the amine-based antioxidants included in the hollow fiber membrane are included in the humidified air and transferred to the fuel cell stack, thereby preventing decomposition of the polymer electrolyte membrane by peroxides or hydroxyl radicals generated within the fuel cell stack. In addition, the hollow fiber membrane can improve durability or oxidation resistance against hydroxyl radicals or peroxides without significantly reducing the moisture exchange capacity of the hollow fiber membrane by including a certain amount of the amine-based antioxidant. Therefore, the hollow fiber membrane according to one aspect contributes to improving the durability of not only the humidifier but also the fuel cell stack while maintaining the existing humidifying capacity.

[0017] Figures 1 and 2 are exploded perspective views of a fuel cell humidifier according to one embodiment.

[0018] The present inventive concept described below is capable of various modifications and embodiments. Specific embodiments are illustrated in the drawings and described in detail in the detailed description. However, this is not intended to limit the present inventive concept to specific embodiments, but should be understood to encompass all modifications, equivalents, or alternatives within the technical scope of the present inventive concept.

[0019] The terminology used below is only used to describe specific embodiments and is not intended to limit the present invention. Singular expressions include plural expressions unless the context clearly indicates otherwise. Hereinafter, it should be understood that terms such as "comprises" or "has" indicate the presence of a feature, number, step, operation, component, part, ingredient, material, or combination thereof described in the specification, but do not exclude in advance the possibility of the presence or addition of one or more other features, numbers, steps, operations, components, parts, ingredients, materials, or combinations thereof.

[0020] When a component is referred to as being "connected, coupled" to another component, it should be understood that while the component may be directly connected or coupled to the other component, there may also be a new component between the component and the other component. Conversely, when a component is referred to as being "directly connected" or "directly coupled" to another component, it should be understood that no new component exists between the component and the other component.

[0021] Throughout the specification, when an element, such as a layer, film, region, or plate, is referred to as being "on" or "above" another element, this includes not only instances where the element is directly above the other element, but also instances where there are other elements intervening between them. Terms such as first, second, etc. may be used throughout the specification to describe various components, but the components themselves should not be limited by these terms. These terms are used solely to distinguish one element from another.

[0022] The term "polymer" as used throughout the specification means a polymer formed by polymerization of one or more monomer units, and has a meaning encompassing a polymer matrix, a polymer backbone, and a polymer structure.

[0023] The term "molecular weight" as used throughout the specification has units of g / mol and, in relation to polymers or macromolecules, should be understood as weight average molecular weight (Mw).

[0024] The embodiments described below are merely exemplary, and various modifications are possible from these embodiments.

[0025] A hollow fiber membrane for a fuel cell membrane humidifier according to one aspect comprises a polymer support and an amine-based antioxidant having a molecular weight of 1000 or less, wherein the amine-based antioxidant may be included in the polymer support in a non-crosslinked form. The hollow fiber membrane may be a moisture-selective membrane that selectively permeates moisture.

[0026] According to one embodiment, the antioxidant may be present in a dispersed state by being impregnated in the polymer support constituting the hollow fiber membrane, in the form of a coating layer on the outer surface of the hollow fiber membrane composed of the polymer, or in a mixed form thereof.

[0027] In the past, cross-linking agents were added to fix antioxidants to hollow fiber membranes for the purpose of improving the oxidation resistance of hollow fiber membranes. However, the addition of cross-linking agents has a limitation in that it adversely affects the membrane formation of hollow fiber membranes and reduces humidifying performance. Therefore, the commercial applicability of hollow fiber membranes cross-linked with antioxidants is still insufficient. According to one embodiment of the present invention, a hollow fiber membrane is achieved by including an antioxidant in a non-cross-linked form in a polymer support, thereby maintaining the humidifying ability of the hollow fiber membrane while improving the oxidation resistance. Here, "including in a non-cross-linked form" means that the antioxidant is not fixed in the polymer support by chemical cross-linking, but is dispersed so as to be fluid within the polymer support, or is held on the surface by physical force rather than chemical bonding.

[0028] According to one embodiment, the hollow fiber membrane can prevent degradation of the hollow fiber membrane including the polymer by hydrogen peroxide or hydroxyl radicals flowing in from the fuel cell stack by including an amine-based antioxidant having a molecular weight of 1000 or less, and a portion of the amine-based antioxidant included in the hollow fiber membrane can be contained in humidified air and transferred to the fuel cell stack, thereby preventing oxidation of the fuel cell stack. In addition, by removing hydrogen peroxide and hydroxyl radicals generated within the fuel cell stack during the operation of the fuel cell in advance, the content of hydrogen peroxide and hydroxyl radicals in high-temperature, humid air transferred from the fuel cell stack to the membrane humidifier can be reduced.

[0029] The amine-based antioxidant included in the hollow fiber membrane has the effect of inhibiting the decomposition of the organic polymer by preventing the initiation of a radical reaction between the organic polymer constituting the hollow fiber membrane and the hydrogen peroxide or hydroxyl radical by having the unshared electron pair of the amine capture the hydrogen peroxide or hydroxyl radical.

[0030] In particular, the amine-based antioxidant having a molecular weight of 1000 or less used in one embodiment of the present invention has a higher number of antioxidant functional groups relative to its molecular weight than the amine-based antioxidant having a molecular weight exceeding 1000, and can move more easily than the high-molecular-weight antioxidant within the polymer matrix constituting the hollow fiber membrane, thereby effectively capturing oxidants generated in the initial stage of fuel cell operation, thereby contributing to improving initial oxidation resistance.

[0031] According to one embodiment, the hollow fiber membrane selectively permeates moisture and has a three-dimensional membrane shape with a cavity in the center. For example, the three-dimensional membrane may have a shape of a cylinder with a circular cross-section, a square column with a square cross-section, a triangular column with a triangular cross-section, a hexagonal column with a hexagonal cross-section, or a polygonal column with a polygonal cross-section.

[0032] According to one embodiment, the hollow fiber membrane has an inner surface and an outer surface, and the amine-based antioxidant may be included in an antioxidant layer disposed on the inner surface, the outer surface, or the inner and outer surfaces.

[0033] For example, the anti-oxidation layer may be a continuous coating layer or a discontinuous coating layer in the shape of an island.

[0034] According to one embodiment, the polymer support may be porous. For example, the polymer support may have an average pore size of 0.05 nm to 90,000 nm. If the pore size of the hollow fiber membrane is excessively large, durability may be compromised, and if the pore size is excessively small, moisture exchange may be difficult, making it difficult to sufficiently humidify the external air passing through the humidifier.

[0035] The above average pore size was measured using CFP (Capillary flow porometry), and the pore size refers to the straight-line distance connecting the two furthest points on the pore cross-section circumference.

[0036] Additionally, the porosity of the porous polymer forming the hollow fiber membrane may be 45% to 85%. The porosity can be calculated by the ratio of the air volume to the total volume of the hollow porous polymer, as shown in the following mathematical equation 1.

[0037] [Mathematical Formula 1]

[0038] Porosity (%) = (air volume / total volume) X 100

[0039] The average pore size of the hollow fiber membrane not including the antioxidant is 0.1 nm to 100,000 nm, and the porosity is 50% to 90%. Even when the antioxidant is applied to the hollow fiber membrane, the difference in the average pore size and porosity is not large, so that the moisture exchange capacity of the hollow fiber membrane is maintained, while deterioration of the hollow fiber membrane by hydroxyl radicals and peroxides is effectively prevented, thereby improving durability.

[0040] According to one embodiment, the antioxidant may be dispersed within a polymer support. For example, the polymer support may form the skeleton of the hollow fiber membrane, the polymer support may include a plurality of pores, and at least a portion of the antioxidant may be present within the pores.

[0041] For example, some of the antioxidants may be physically attached to the surface of the pores of the polymer support or may be present embedded in the surface of the pores.

[0042] According to one embodiment, the antioxidant can be embedded within the skeleton of the polymer support to form an integral part with the porous polymer.

[0043] For example, some of the antioxidant may be present on the pore surface of the polymer support, and the remaining part may be embedded within the skeleton of the polymer support to form one body with the polymer support.

[0044] Since the above antioxidant does not form a chemical bond with the polymer support, the antioxidant can be released and delivered to the fuel cell stack along with the humidified air as ambient air passes through the hollow portion of the hollow fiber membrane. As a result, oxidants generated in the stack during fuel cell operation can be removed before being delivered to the humidifier.

[0045] According to one embodiment, the antioxidant may be incorporated into the hollow fiber membrane by the manufacturing process described below. For example, the antioxidant may be incorporated into the hollow fiber membrane by mixing it into a dope solution and then being incorporated into the hollow fiber membrane during the membrane-forming process, or the antioxidant may be incorporated into the hollow fiber membrane by discharging a complex antioxidant into the core solution and then being incorporated into the hollow fiber membrane during the phase inversion process, or the antioxidant solution may be injected into the hollow portion after the hollow fiber membrane is manufactured to form an antioxidant coating layer on the inner surface of the hollow fiber membrane.

[0046] For example, the antioxidant may be mixed into the dope solution, and the other may be included in the core solution or included in the hollow fiber membrane coating layer forming solution.

[0047] In one embodiment, some of the antioxidants may be present and exposed on the surface of the polymer support.

[0048] According to one embodiment, the antioxidant may be dispersed on at least one of the inner and outer surfaces of the hollow fiber or may be in the form of a coating layer. For example, the antioxidant may be attached in the form of particles to at least one of the inner and outer surfaces of the hollow fiber or a plurality of particles may form a coating layer.

[0049] For example, the antioxidant particles can be uniformly distributed over the entire surface so as not to block the pores of the hollow fiber.

[0050] According to one embodiment, the antioxidant may form an antioxidant coating layer disposed on at least one surface among the inner and outer surfaces of the hollow fiber. At this time, the antioxidant coating layer may be configured so that a certain amount of the antioxidant can flow out when in contact with the outside air. In order for the composite antioxidant to be configured so that a certain amount can flow out, there must be no chemical bonding between the antioxidant and the porous polymer, and it is advantageous for it to be located on the inner surface of the membrane. Therefore, when forming a humidifying membrane, a crosslinking agent or additive that can cause crosslinking between the antioxidant and the main polymer must not be used.

[0051] According to one embodiment, the hollow fiber membrane may include a concentration gradient region in which the concentration of the antioxidant varies within the hollow fiber membrane. For example, the concentration of the antioxidant may increase from the inner surface of the hollow fiber membrane toward the outer surface.

[0052] By configuring the outer surface of the hollow fiber membrane to have more antioxidants, it is possible to effectively capture and decompose hydrogen peroxide or hydroxyl radicals flowing into the humidifier together with high-humidity air from the fuel cell stack.

[0053] According to one embodiment, the amine-based antioxidant can be used without limitation as long as it has a molecular weight of 1000 or less, contains at least one amine group in the molecule, and is a material that scavenges hydrogen peroxide and hydroxyl radicals.

[0054] For example, the amine antioxidant may include phenyl-α-naphthylamine, phenyl-β-naphthylamine, N,N'-diphenyl-p-phenylenediamine, N,N'-di-naphthyl-p-phenylenediamine, 2,4,4-trimethylpent-1-ene, a HALS compound having a molecular weight of 1000 or less, or a combination thereof. For example, examples of the above HALS compounds include bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, a mixture of bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate and 1-(methyl)-8-(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate, and bis(2,2,6,6-tetramethyl-1-(octyloxy)-4-piperidinyl)ester. (2,2,6,6-tetramethyl-1-(octyloxy)-4-piperidinyl) ester) etc.

[0055] According to one embodiment, the amine-based antioxidant may be included in an amount of more than 0 and less than 5 parts by weight, or 0.001 to 5 parts by weight, 0.01 to 5 parts by weight, 0.05 to 5 parts by weight, or 0.1 to 5 parts by weight, based on 100 parts by weight of the polymer forming the skeleton of the hollow fiber membrane.

[0056] If an antioxidant is not included in the hollow fiber membrane, the hollow fiber membrane may be easily deteriorated by peroxide or hydroxyl radicals generated during fuel cell operation, and if it exceeds 5 parts by weight, the hollow fiber membrane may not be formed smoothly, and the pores of the hollow fiber membrane may be closed, which may lower the moisture exchange performance and deteriorate the membrane humidifier function.

[0057] In addition, since the antioxidant is included within the above-described range in the hollow fiber membrane, an antioxidant of 1 ug / 1000 hr or more can be provided from the humidifying membrane into the fuel cell stack.

[0058] According to one embodiment, the hollow fiber membrane may further include a phenol-based antioxidant, a phosphorus-based antioxidant, a metal-based antioxidant, an organo-metallic antioxidant, or a sulfur-based antioxidant in addition to an amine-based antioxidant.

[0059] For example, the phenolic antioxidants include Irganox 1010 (Irganox 1010: pentaerythritol tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, manufactured by BASF), Irganox 1076 (Irganox 1076: octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, manufactured by BASF), Irganox 1330 (Irganox 1330: 3,3',3",5,5',5"-hexa-t-butyl-a,a',a"-(mesitylene-2,4,6-triyl)tri-p-cresol, manufactured by BASF), and Irganox 3114 (Irganox 3114: 1,3,5-Tris(3,5-di-t-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, manufactured by BASF Corporation), Irganox 3790 (Irganox 3790: 1,3,5-Tris((4-t-butyl-3-hydroxy-2,6-xylyl)methyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, manufactured by BASF Corporation), Irganox 1035 (Irganox 1035: thiodiethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], manufactured by BASF Corporation), Irganox 1135 (Irganox 1135: Benzenepropanoic acid, 3,5-bis(1,1-dimethylethyl)-4-hydroxy-C7-C9 branched alkyl ester, manufactured by BASF Corporation), Irganox 1520L (Irganox 1520L: 4,6-bis(octylthiomethyl)-o-cresol, manufactured by BASF Corporation), Irganox 3125 (Irganox 3125, manufactured by BASF Corporation), Irganox 565 (Irganox 565: 2,4-bis(n-octylthio)-6-(4-hydroxy-3',5'-di-t-butylanilino)-1,3,5-triazine, manufactured by BASF Corporation), Adekastab (registered trademark) AO-80 (Adekastab AO-80: 3,9-bis(2-(3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy)-1,1-dimethylethyl)-2,4,8,10-tetraoxaspiro(5,5)undecane, (manufactured by ADEKA Co., Ltd.), Smilizer (registered trademark) BHT, Dong GA-80, Dong GS (above,It may include Cyanox 1790 (manufactured by Sumitomo Chemical Co., Ltd.), Cyanox (registered trademark) 1790 (manufactured by Cytech Co., Ltd.), and Vitamin E (manufactured by Eisai Co., Ltd.), or any combination thereof.

[0060] For example, phosphorus antioxidants include tris(2,4-di-t-butylphenyl)phosphite (Irgafos 168), tris[2-[[2,4,8,10-tetra-t-butyldibenzo[d,f][1,3,2]dioxaphosphepin-6-yl]oxy]ethyl]amine (Irgafos 12), bis(2,4-bis(1,1-dimethylethyl)-6-methylphenyl)ethyl esterphosphite (Irgafos 38), Adecastab 329K, Adecastab PEP36, Adecastab PEP-8, Sandstab P-EPQ, Weston 618, Weston 619G, Ultranox 626, (6-[3-(3-t-butyl-4-hydroxy-5-methylphenyl)propoxy]-2,4,8,10-tetra-t-butyldibenzo[d,f][1,3,2]dioxaphosphepin) (Smilizer GP), or a combination thereof.

[0061] For example, the metal-based antioxidant may include cerium, nickel, tungsten, ruthenium, palladium, silver, rhodium, cesium, zirconium, cobalt, chromium, yttrium, manganese, iron, molybdenum, lead, vanadium, titanium, niobium, lanthanum, ions thereof, oxides thereof, salts thereof, or any mixture thereof.

[0062] For example, the organo-metallic antioxidant may include a Ce-crown complex, a Ce-phosphoric acid complex, a Ce-Bypyridine, or any mixture thereof.

[0063] For example, the sulfur-based antioxidant may include dilaurylthiodipropionate (DLTDP), distearylthiodipropionate (DSTDP), ditridecylthiodipropionate (DMTDP), bis 2-methyl-4(3-alkylthio)-propionyloxy)-5-tert-butylphenol sulfide, tetrakis methylene-3-(laurylthio)propionate methane, or combinations thereof.

[0064] According to one embodiment, the polymer may be selected from known polymers suitable for forming a hollow fiber membrane, and may include, for example, a polyvinylidene fluoride (PVDF) polymer, a polysulfone polymer, a sulfonated polysulfone, cellulose acetate, cellulose triacetate, polymethyl methacrylate, Nafion, a polystyrene (PS) polymer, a polytetrafluoroethylene (PTFE) polymer, a perfluorosulfonic acid (PFSA) polymer, a polyphenylsulfone polymer, a polyethersulfone (PES) polymer, a polyacrylonitrile (PAN) polymer, a polyetherimide (PEI) polymer, a polyimide (PI) polymer, or any combination of the above-mentioned polymers.

[0065] For example, the polymer may include a polyethersulfone polymer.

[0066] According to one embodiment, the polymer may be included in an amount of 90 parts by weight or more and less than 100 parts by weight, or 95 parts by weight to 99.999 parts by weight, based on 100 parts by weight of the hollow fiber membrane.

[0067] According to one embodiment, the thickness of the hollow fiber membrane may be 0.5 nm to 1 mm.

[0068] According to one embodiment, the hollow fiber membrane does not show a significant difference in porosity even when it includes an amine-based antioxidant.

[0069] For example, the average pore size of the hollow fiber membrane not including an amine-based antioxidant may be 0.1 nm to 100,000 nm, and the porosity may be 50% to 90%, and the average pore size of the hollow fiber membrane according to one embodiment of the present invention including an amine-based antioxidant may be 0.05 nm to 90,000 nm, and the porosity may be 45% to 85%.

[0070] Even when an amine-based antioxidant is applied to a hollow fiber membrane, since the difference in the above-mentioned average pore size and porosity is not large, the moisture exchange capacity of the hollow fiber membrane is maintained, while deterioration of the hollow fiber membrane due to hydroxyl radicals and peroxides is effectively prevented, thereby improving durability.

[0071] According to one embodiment, the hollow fiber membrane may further include additives such as a surfactant, a hydrophilic organic compound, a hydrophilic polymer, or a crosslinking agent.

[0072] For example, the additive may include at least one of polyethylene glycol, glycerin, diethyl glycol, triethylene glycol, ethanol, polyvinylpyrrolidone, water, zinc chloride, and lithium chloride.

[0073] These additives can be selected and added in appropriate amounts, as long as they do not impair the inherent properties of the hollow fiber membrane. It will be apparent to those skilled in the art that any known materials used in the manufacture of hollow fiber membranes can also be used.

[0074] According to one embodiment, the hollow fiber membrane has a water vapor permeability of 0.1 g / s / m measured under conditions of 1 bar pressure and 80 ℃ temperature. 2 It could be strange.

[0075] According to one implementation example, the hollow fiber membrane has a nitrogen permeability of 100 cc / min / cm under a pressure condition of 0.7 bar. 2 It could be as follows:

[0076] According to one embodiment, the hollow fiber membrane has an oxygen permeability of 100 cc / min / cm under a pressure condition of 0.7 bar. 2 It could be as follows:

[0077] The above hollow fiber membrane has the aforementioned water vapor permeability, nitrogen permeability and oxygen permeability, and is suitable for use in a humidifier of a fuel cell with improved durability by having sufficient moisture exchange and gas permeability even when an antioxidant is introduced to improve durability.

[0078]

[0079] A method for manufacturing a hollow fiber membrane according to one aspect may include the steps of: mixing a spinning material including a polymer and an amine-based antioxidant having a molecular weight of 1000 or less in an organic solvent, wherein the amine-based antioxidant is mixed in an amount of more than 0 and less than 5 parts by weight relative to 100 parts by weight of the polymer to obtain a spinning solution; spinning the spinning solution into a coagulation tank through a nozzle; and solidifying the spinning solution in the coagulation tank.

[0080] For the overlapping components of the manufacturing method of the above hollow fiber membrane with the above-described ones, refer to the above.

[0081] According to one embodiment, the step of obtaining the above-mentioned radiation source may include a step of mixing a radiation source material comprising the amine-based antioxidant and the polymer in a solvent. The radiation source may be formed by dissolving the polymer and the amine-based antioxidant in a solvent. In this case, the radiation source material may further include the aforementioned additives.

[0082] The solvent may include at least one of a first solvent, a second solvent, and a third solvent. For example, the solvent may be a mixed solvent including two types of solvents among the first solvent, the second solvent, and the third solvent.

[0083] The first solvent is a solvent that cannot dissolve the polymer at room temperature (e.g., 23 to 25°C) but can dissolve the polymer at high temperatures (e.g., 80°C or higher), and may include butanol, isobutanol, octanol, pentanol, isopentanol, dimethyl phthalate, diethyl phthalate, dibutyl phthalate, dioctyl phthalate, polyoxylethylene octylphenyl ether, or a combination thereof.

[0084] The second solvent is a solvent that cannot dissolve the polymer, and may include water, methanol, ethanol, isopropanol, acetone, hexane, pentane, benzene, toluene, carbon tetrachloride, o-dichlorobenzene, polyethylene glycol, or a combination thereof.

[0085] The third solvent is a solvent that can dissolve the polymer even at room temperature, and may include N-methyl-2-pyrrolidone, dimethyl sulfoxide, dimethyl acetamide, dimethyl formamide, methyl ethyl ketone, tetrahydrofuran, tetramethyl urea, or trimethyl phosphate.

[0086] A person skilled in the art can use one or a mixture of two or more of the first solvent, the second solvent, and the third solvent, taking into consideration the characteristics of the polymer raw material and the production of a hollow fiber membrane having desired properties.

[0087] According to one embodiment, when the solvent is a mixed solvent of two types of solvents, the mixing ratio of the solvents may be 1:9 to 9:1 by weight, but is not limited thereto, and a person skilled in the art may select an appropriate range by considering the content of the polymer and the antioxidant, the viscosity of the spinning solution, the porosity of the hollow fiber membrane, and the physical properties of the final hollow fiber membrane.

[0088] According to one embodiment, the spinning solution comprises a polymer forming the skeleton of a hollow fiber membrane, an antioxidant, a solvent, and, if necessary, additional additives. The solvent is removed during the spinning solution forming into a hollow fiber membrane, so that the final product has a structure in which the antioxidant is incorporated into the polymer skeleton.

[0089] According to one embodiment, the content of the polymer contained in the spinning solution may be 15 to 25 parts by weight based on 100 parts by weight of the total spinning solution. For example, the content of the polymer contained in the spinning solution may be 16 to 24 parts by weight, 17 to 23 parts by weight, 18 to 22 parts by weight, or 19 to 21 parts by weight.

[0090] According to one embodiment, the content of the antioxidant included in the above-described radiation source may be more than 0 and less than 5 parts by weight, or 0.001 to 5 parts by weight, or 0.1 to 5 parts by weight, relative to 100 parts by weight of the polymer forming the skeleton of the hollow fiber membrane.

[0091] According to one embodiment, the temperature at which the polymer, antioxidant, and optionally additives are mixed in the solvent in the step of obtaining the above-described radiation source may be appropriately selected at room temperature or high temperature in consideration of the polymer, antioxidant, additive, and solvent used.

[0092] According to one embodiment, the mixing time of the above-described radiation source may be performed for a time sufficient for the polymer, antioxidant, and any additives to be sufficiently dissolved and / or dispersed in the solvent.

[0093] According to one embodiment, the viscosity of the spinning solution may be 5,000 to 50,000 cps at 35°C. When the viscosity of the spinning solution satisfies the above range, the spinning solution can be smoothly discharged through the nozzle without clogging.

[0094] In order to maintain the viscosity of the above-mentioned spinning solution within the aforementioned range, the temperature of the spinning nozzle may be adjusted to a temperature above a certain temperature. Alternatively, the spinning solution may further include a viscosity modifier to control the viscosity, if necessary.

[0095] According to one embodiment, the spinning solution may further include an additive in consideration of the membrane forming properties and porosity of the hollow fiber membrane, the dispersibility of the antioxidant, and the viscosity of the spinning solution.

[0096] For example, the additive may include at least one of polyethylene glycol, glycerin, diethyl glycol, triethylene glycol, ethanol, polyvinylpyrrolidone, water, zinc chloride, and lithium chloride.

[0097] According to one embodiment, the step of irradiating the above-mentioned radiation source into the coagulation tank may include a step of irradiating the discharge liquid using a tubular radiation device, for example, a double-tubular radiation device or a triple-tubular radiation device, but is not limited to such a tubular type, and any discharge method capable of forming a hollow shape may be used without limitation.

[0098] According to one embodiment, when the spin-off solution is discharged into the coagulation tank through a double-tube type spin-off device, the composition of the spin-off solution discharged from each tube of the double-tube type may be the same or different. For example, when the spin-off solution is discharged using a triple-tube type spin-off device, the composition of the spin-off solution passing through each tube may be the same or different. For example, when a triple-tube type spin-off device is used, the composition of the spin-off solution passing through the tubes arranged on the inner and outer sides of the tube may be the same, and only the composition of the spin-off solution passing through the intermediate tube between the inner and outer sides may be different.

[0099] According to one embodiment, in the step of irradiating the above-mentioned radiation source into the coagulation tank, the radiation temperature may be set to a temperature equal to or higher than the radiation source mixing temperature. In this case, when using a multi-tubular nozzle, the temperature of each nozzle may be set differently, enabling the optimal radiation source to be discharged at an appropriate temperature.

[0100] According to one embodiment, in the step of radiating the above-mentioned radiation source into the coagulation tank, the discharge speed may be 5 to 100 g / min.

[0101] According to one embodiment, the radiation emitted from the radiation device can contact the coagulation liquid in the coagulation tank through the air gap.

[0102] The above air gap is the region where the radiant comes into contact with air, and artificial cooling air can be introduced therein, taking into account the physical properties of the radiant. For example, the length of the air gap can be set to 0.1 to 50 cm. The air gap is the region where the first phase transition occurs, where the phase transition is achieved by exchanging moisture in the atmosphere with the organic solvent in the radiant solution. When the length of the air gap satisfies the above range, sufficient phase transition occurs, and a hollow fiber membrane having a desired pore structure can be obtained.

[0103] The above radiation passes through the air gap and comes into contact with the coagulation liquid contained in the coagulation tank, thereby solidifying and forming a porous hollow fiber membrane.

[0104] According to one embodiment, the coagulation tank may be configured as a single tank, but is not limited thereto, and may be configured such that two or more coagulation tanks are arranged in series. When there are two or more coagulation tanks, the coagulant used in each coagulation tank may be the same or different.

[0105] According to one embodiment, the coagulant contained in the coagulation tank serves to coagulate the discharged liquid through the detention into the form of a hollow fiber membrane, and the coagulant used at this time can be appropriately selected and used by a person skilled in the art from among known coagulants by considering the porosity of the hollow fiber membrane, the pore structure of the hollow fiber membrane, etc.

[0106] For example, a second solvent such as an acidic solution or water, or a mixed solvent of a second solvent and a third solvent may be used as the coagulant.

[0107] According to one embodiment, the hollow fiber membrane obtained through the above coagulation tank may undergo a post-processing step.

[0108] According to one embodiment, the post-treatment step may include performing a chemical treatment and / or a physical treatment.

[0109] For example, the chemical treatment in the above post-treatment step is performed to remove and dry the coagulant contained in the pores after the hollow fiber membrane is formed, and may include water washing, washing, hot water treatment, etc., and if necessary, the solution used for water washing, washing, hot water treatment, etc. may further include an antioxidant.

[0110] For example, the physical treatment in the above post-processing step may further include a stretching or shrinking process to control the size and shape of the pores inside the hollow fiber membrane to improve the strength and durability of the hollow fiber membrane.

[0111]

[0112] A humidifier according to one aspect may include the hollow fiber membrane described above.

[0113] For the hollow fiber desert, please refer to the above, and below, the humidifier will be described with reference to FIGS. 1 and 2.

[0114] Figures 1 and 2 are perspective views of a fuel cell humidifier (100) according to one embodiment of the present invention.

[0115] As shown in FIGS. 1 and 2, the fuel cell humidifier (100) of the present invention includes a middle case (110), a cap case (120), a fixing part (130), and a hollow fiber membrane bundle (200).

[0116] The middle case (110) is combined with the cap case (120) to form the outer shape of the membrane humidifier (100). The middle case (110) and the cap case (120) may be made of a hard plastic such as polycarbonate or a metal. The middle case (110) and the cap case (120) may have a circular cross-sectional shape in the width direction, as shown in FIG. 1, or a polygonal cross-sectional shape in the width direction, as shown in FIG. 2. The polygon may be a rectangle, a square, a trapezoid, a parallelogram, a pentagon, a hexagon, etc., and the polygon may have rounded corners. In addition, the circle may be an oval.

[0117] In the middle case (110), a second fluid inlet (112) through which the second fluid is supplied and a second fluid outlet (113) through which the second fluid is discharged are formed, respectively.

[0118] In FIGS. 1 and 2, a plurality of hollow fiber membranes (210) are arranged in the middle case (110) in the form of a single hollow fiber membrane bundle (200), but the hollow fiber membranes (210) may also be arranged in the middle case (110) in a state of being divided and accommodated in two or more cartridges.

[0119] A fluid inlet (121) is formed in the cap case (120). The fluid inlet (121) formed in one of the cap cases (120) respectively connected to both ends of the middle case (110) becomes a first fluid inlet, and the fluid inlet (121) formed in the other one becomes a first fluid outlet. The first fluid introduced through the fluid inlet (121) functioning as the first fluid inlet passes through the internal conduits (i.e., lumens) of the hollow fiber membranes (210) accommodated inside the middle case (110) and then exits through the fluid inlet (121) functioning as the first fluid outlet.

[0120] The ends of the hollow fiber membranes (210) are potted in the fixing member (130). The fixing member (130) binds the hollow fiber membranes (210) and fills the gap between the hollow fiber membranes (210) and the gap between the hollow fiber membranes (210) and the middle case (110). As a result, each of the two ends of the middle case (110) is blocked by the fixing member (130), and a flow path through which a second fluid passes is formed therein. The material of the fixing member (130) is known in the art, and a detailed description thereof is omitted herein.

[0121]

[0122] Hereinafter, one embodiment of the present invention will be described through examples and comparative examples, and the scope of the present invention is not intended to be limited to the examples.

[0123]

[0124] Example 1

[0125] A spinning solution was prepared by including 1 part by weight of an amine-based antioxidant (product name: Tinuvin 765, molecular weight: 508 g / mol) per 100 parts by weight of polyethersulfone in the hollow fiber membrane polymer composition, and then the spinning solution was spun into a coagulation tank through a tubular spinneret. At this time, the spinning solution was stretched to a length of about 10 cm and passed through the air, and after being solidified in the coagulation tank, it was washed and dried to produce a humidifying membrane. Here, the hollow fiber membrane polymer composition includes 20% by weight of polyethersulfone (PES), 77% by weight of N-methyl-2-pyrrolidone (NMP), and 3% by weight of polyvinylpyrrolidone (PVP) as other additives, and the coagulation tank includes a 60°C coagulation solution in which water and NMP are mixed in a mass ratio of 7:3.

[0126]

[0127] Example 2

[0128] A humidifying film was manufactured in the same manner as in Example 1, except that the spinning solution was prepared to contain 1 wt% of an amine-based antioxidant (product name: Tinuvin PA 123, molecular weight: 737.20 g / mol) based on the polymer content.

[0129]

[0130] Comparative Example 1

[0131] A humidifying film was manufactured in the same manner as in Example 1, except that the spinning solution was prepared so as not to contain an antioxidant.

[0132]

[0133] Comparative Example 2

[0134] A humidifying film was manufactured in the same manner as in Example 1, except that the spinning solution was prepared to contain 1 wt% of an amine-based antioxidant (product name: UV40, molecular weight: 2600-3400 g / mol) based on the polymer content.

[0135]

[0136] Comparative Example 3

[0137] A humidifying film was manufactured in the same manner as in Example 1, except that the spinning solution was prepared to contain 1 wt% of an amine-based antioxidant (product name: UV94, molecular weight: 2000-3100 g / mol) based on the polymer content.

[0138]

[0139] Comparative Example 4

[0140] A humidifying film was manufactured in the same manner as in Example 1, except that the spinning solution was prepared to contain 1 wt% of an amine-based antioxidant (product name: UV119, molecular weight: 2285.75 g / mol) based on the polymer content.

[0141]

[0142] Comparative Example 5

[0143] A humidifying film was manufactured in the same manner as in Example 1, except that the spinning solution was prepared to contain 1 wt% of a phenol-based antioxidant (product name: Irganox 1010, molecular weight: 1177.6 g / mol) based on the polymer content.

[0144]

[0145] Comparative Example 6

[0146] A humidifying film was manufactured in the same manner as in Example 1, except that the spinning solution was prepared to contain 1 wt% of a phenol-based antioxidant (product name: Irganox 1076, molecular weight: 530.9 g / mol) based on the polymer content.

[0147]

[0148] Comparative Example 7

[0149] A humidifying film was manufactured in the same manner as in Example 1, except that the spinning solution was prepared to contain 1 wt% of the metallic antioxidant CeO2 based on the polymer content.

[0150]

[0151] Comparative Example 8

[0152] A humidifying film was manufactured in the same manner as in Example 1, except that the spinning solution was prepared to contain 1 wt% of the metal-based antioxidant Co3O4 based on the polymer content.

[0153]

[0154] Evaluation Example 1 - Evaluation of Antioxidant Effect

[0155] The humidifying films manufactured in Examples 1 to 2 and Comparative Examples 1 to 8 were immersed in an 8% H2O2 (containing 8 ppm FeSO4) solution at 80°C for 12, 24, and 36 hours, and then the molecular weight reduction ratio was confirmed. After a certain period of time, the ratio of the reduced weight to the initial oxide film weight was confirmed, and the results are shown in Table 1 below.

[0156]

[0157] 12hr (%)24hr (%)36hr (%)Example 1969287Example 2959086Comparative Example 1684221Comparative Example 2898479Comparative Example 3878278Comparative Example 4837260Comparative Example 5785837Comparative Example 6785838Comparative Example 7917040Comparative Example 8906838

[0158] As shown in Table 1 above, Examples 1 and 2 using amine-based antioxidants having a molecular weight of 1000 or less showed superior oxidation resistance compared to Comparative Examples 2 and 3 using amine-based antioxidants having a molecular weight of more than 1000, and showed significantly improved oxidation resistance compared to phenol-based antioxidants and metal-based antioxidants regardless of molecular weight. In the case of metal-based antioxidants, oxidation resistance similar to that of the present invention was initially shown, but it was confirmed that the oxidation resistance rapidly decreased over time. This is thought to be because the phenol-based antioxidants and metal-based antioxidants leak out and disappear from the hollow fiber membrane over time.

[0159] Example 3

[0160] A spinning solution was prepared by including 5 parts by weight of a hindered amine compound (Tinuvin 770; Mw: 480.7 g / mol) as an amine antioxidant per 100 parts by weight of polyethersulfone in the hollow fiber membrane polymer composition, and then the spinning solution was spun into a coagulation tank through a tubular spinneret. At this time, the spinning solution was stretched to a length of about 10 cm and passed through the air, and after being solidified in the coagulation tank, it was washed and dried to produce a humidifying membrane. Here, the hollow fiber membrane polymer composition includes 20% by weight of polyethersulfone (PES), 77% by weight of N-methyl-2-pyrrolidone (NMP), and 3% by weight of polyvinylpyrrolidone (PVP) as other additives, and the coagulation tank includes a 60°C coagulation solution in which water and NMP are mixed in a mass ratio of 7:3.

[0161]

[0162] Example 4

[0163] A humidifying film was manufactured in the same manner as in Example 3, except that 3 parts by weight of an amine-based antioxidant was used.

[0164]

[0165] Example 5

[0166] A humidifying film was manufactured in the same manner as in Example 3, except that 1 part by weight of an amine-based antioxidant was used.

[0167]

[0168] Example 6

[0169] A humidifying film was manufactured in the same manner as in Example 3, except that 0.1 part by weight of an amine-based antioxidant was used.

[0170]

[0171] Comparative Example 9

[0172] A humidifying film was manufactured in the same manner as in Example 3, except that the amine-based antioxidant was not included in the radiation solution.

[0173]

[0174] Comparative Example 10

[0175] A humidifying film was manufactured in the same manner as in Example 5, except that a post-treatment was performed to crosslink the amine-based antioxidant to the polyethersulfone by flowing dry air of approximately 130°C to 140°C for 3 hours inside the tube of the dry humidifying film.

[0176]

[0177] Evaluation Example 1 - Evaluation of Antioxidant Effect

[0178] The humidifying films manufactured in Examples 3 to 6 and Comparative Examples 9 and 10 were immersed in a 3% H2O2 (containing 2 ppm FeSO4) solution at 80°C for 24 hours, and the molecular weight reduction ratio was confirmed. After immersion for 48 hours, the ratio of the reduced weight to the initial oxide film weight was confirmed, and the results are shown in Table 2 below.

[0179]

[0180] Evaluation Example 2 - Humidification Performance Evaluation

[0181] Humidifying membranes manufactured in Examples 3 to 6 and Comparative Examples 9 and 10 were manufactured as H10N products and their humidifying performance was evaluated. The performance was evaluated by having wet air (2000 slpm, 70°C, RH 100%) and dry air (2000 slpm, 70°C) meet in counter flow, and the performance was confirmed by dew point, and the results are shown in Table 3.

[0182] Molecular weight reduction ratio after 24 hoursWeight reduction ratio after 24 hoursMolecular weight reduction ratio after 48 hoursWeight reduction ratio after 48 hoursExample 34%5%6%9%Example 44%5%7%9%Example 55%7%14%19%Example 68%11%20%23%Comparative example 912%15%25%30%Comparative example 106%8%15%19%

[0183]

[0184] Humidification performance (dew point) Example 345 Example 449 Example 549 Example 650 Comparative Example 950 Comparative Example 1040

[0185] As shown in Tables 2 and 3 above, the humidifying films of Examples 3 to 6 containing an amine-based antioxidant having a molecular weight of 1000 or less showed a significantly lower rate of molecular weight decrease after 24 hours compared to the humidifying film of Comparative Example 9 not containing an amine-based antioxidant, and maintained a humidifying performance similar to that of Comparative Example 9 not containing an antioxidant. In light of these data, it was confirmed that the humidifying film containing an amine-based antioxidant sufficiently prevented deterioration of the humidifying film while maintaining the moisture exchange ability, which is the original performance of the humidifying film. On the other hand, in the case of Comparative Example 10, in which the antioxidant was crosslinked inside the hollow fiber membrane by a crosslinking agent, the humidifying performance was rapidly reduced, suggesting that not using a crosslinking agent is preferable in terms of maintaining the humidifying performance.

[0186] In addition, it was confirmed that the humidifying performance decreased as the content of the amine-based antioxidant increased from 0.1 parts by weight to 5 parts by weight, and it was shown that the humidifying performance decreased rapidly to a dew point value of 45 at 5 parts by weight. Therefore, it can be seen that application may be difficult when the content of the amine-based antioxidant exceeds 5 parts by weight due to deterioration in humidifying performance.

Claims

1. A hollow fiber membrane for a fuel cell membrane humidifier, comprising a polymer support and an amine-based antioxidant having a molecular weight of 1000 or less, wherein the amine-based antioxidant is contained in the polymer support in a non-crosslinked form.

2. In paragraph 1, A hollow fiber membrane for a fuel cell membrane humidifier, wherein the above-mentioned amine-based antioxidant is contained in an amount of more than 0 and less than 5 parts by weight based on 100 parts by weight of the hollow fiber membrane.

3. In paragraph 2, A hollow fiber membrane for a fuel cell membrane humidifier, wherein the above amine-based antioxidant is included in an amount of 0.1 to 5 parts by weight.

4. In paragraph 1, A hollow fiber membrane for a fuel cell membrane humidifier, wherein the above amine-based antioxidant comprises a compound having at least one amine functional group in the molecule.

5. In paragraph 4, The above amine antioxidants are phenyl-α-naphthylamine, phenyl-β-naphthylamine, N,N'-diphenyl-p-phenylenediamine, N,N'-di-naphthyl-p-phenylenediamine, 2,4,4,-trimethylpent-1-ene, bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, a mixture of bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate and 1-(methyl)-8-(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate. A hollow fiber membrane for a fuel cell membrane humidifier, comprising 1-(methyl)-8-(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate), bis(2,2,6,6,-tetramethyl-1-(octyloxy)-4-piperidinyl) ester, or a combination thereof.

6. In paragraph 1, A hollow fiber membrane for a fuel cell membrane humidifier, wherein the above amine-based antioxidant is impregnated into a polymer.

7. In paragraph 1, A hollow fiber membrane for a fuel cell membrane humidifier, wherein the hollow fiber membrane includes a concentration gradient region in which the concentration of the amine-based antioxidant increases from the inner surface to the outer surface of the hollow fiber membrane.

8. In paragraph 1, A hollow fiber membrane for a fuel cell membrane humidifier, wherein the hollow fiber membrane further comprises a phenol-based antioxidant, a phosphorus-based antioxidant, a metal-based antioxidant, an organo-metallic antioxidant, a sulfur-based antioxidant, or a combination thereof.

9. In paragraph 1, A hollow fiber membrane for a fuel cell membrane humidifier, wherein the polymer comprises a polyvinylidene fluoride (PVDF) polymer, a polysulfone polymer, a sulfonated polysulfone, cellulose acetate, cellulose triacetate, polymethyl methacrylate, Nafion, a polystyrene (PS) polymer, a polytetrafluoroethylene (PTFE) polymer, a perfluorosulfonic acid (PFSA) polymer, a polyphenylsulfone polymer, a polyethersulfone (PES) polymer, a polyacrylonitrile (PAN) polymer, a polyetherimide (PEI) polymer, a polyimide (PI) polymer, or a combination thereof.

10. In paragraph 1, A hollow fiber membrane for a fuel cell membrane humidifier, wherein the polymer is contained in an amount of 90 parts by weight or more and less than 100 parts by weight per 100 parts by weight of the hollow fiber membrane.

11. In paragraph 1, The hollow fiber membrane above has a thickness of 0.5 nm to 1 mm, and is a hollow fiber membrane for a fuel cell membrane humidifier.

12. In paragraph 1, The hollow fiber membrane for a fuel cell membrane humidifier has a weight loss ratio of less than 25% after being immersed in a 3% H2O2 solution at a temperature of 80°C for 48 hours.

13. A fuel cell membrane humidifier comprising a hollow fiber membrane according to any one of claims 1 to 12.

14. A step of preparing a radiation source solution containing a polymer and an amine-based antioxidant having a molecular weight of 1000 or less; A step of radiating the above-mentioned radiation source into a coagulation tank through a nozzle; A method for manufacturing a hollow fiber membrane for a fuel cell membrane humidifier, comprising the step of solidifying a radiation source in the above-mentioned coagulation tank.

15. In paragraph 14, A method for manufacturing a hollow fiber membrane for a fuel cell membrane humidifier, wherein the above-mentioned amine-based antioxidant is contained in an amount of more than 0 and less than 5 parts by weight based on 100 parts by weight of the above-mentioned polymer.

16. In paragraph 14, The above amine antioxidants are phenyl-α-naphthylamine, phenyl-β-naphthylamine, N,N'-diphenyl-p-phenylenediamine, N,N'-di-naphthyl-p-phenylenediamine, 2,4,4,-trimethylpent-1-ene, bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, a mixture of bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate and 1-(methyl)-8-(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate. A method for producing a hollow fiber membrane for a fuel cell membrane humidifier, comprising 1-(methyl)-8-(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate), bis(2,2,6,6,-tetramethyl-1-(octyloxy)-4-piperidinyl) ester, or a combination thereof.

17. In paragraph 14, The step of obtaining the above-mentioned radiation source includes a step of mixing the above-mentioned antioxidant and the above-mentioned polymer in a solvent, A method for manufacturing a hollow fiber membrane for a fuel cell membrane humidifier, wherein the solvent comprises at least two kinds of solvents among a first solvent, a second solvent, and a third solvent.

18. In paragraph 17, The first solvent comprises butanol, isobutanol, octanol, pentanol, isopentanol, dimethyl phthalate, diethyl phthalate, dibutyl phthalate, dioctyl phthalate, polyoxyethylene octylphenyl ether, or a combination thereof, The second solvent comprises water, methanol, ethanol, isopropanol, acetone, hexane, pentane, benzene, toluene, carbon tetrachloride, o-dichlorobenzene, polyethylene glycol, or a combination thereof, A method for producing a hollow fiber membrane for a fuel cell membrane humidifier, wherein the third solvent comprises N-methyl-2-pyrrolidone, dimethyl sulfoxide, dimethyl acetamide, dimethyl formamide, methyl ethyl ketone, tetrahydrofuran, tetramethyl urea, or trimethyl phosphate.

19. In paragraph 14, A method for manufacturing a hollow fiber membrane for a fuel cell membrane humidifier, further comprising a post-treatment step after the step of coagulating the above-mentioned radiation source.

20. In paragraph 19, A method for manufacturing a hollow fiber membrane for a fuel cell membrane humidifier, wherein the above post-treatment step includes chemical treatment and / or physical treatment.

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