Cartridge for membrane humidifier and membrane humidifier for fuel cell including same

Abstract

The present invention relates to a cartridge for a membrane humidifier, the cartridge comprising: an inner case containing a plurality of hollow fiber membranes through which a first fluid flows; an inlet window part into which a second fluid flows and which is disposed at one end of the inner case; and a patterned protective film disposed between the inlet window part and the hollow fiber membranes, wherein the patterned protective film includes an antioxidant.

Description

Cartridge for membrane humidifier and membrane humidifier for fuel cell including same

[0001] The present invention relates to a cartridge and a fuel cell membrane humidifier including the same, and more particularly, to a cartridge configured to prevent deterioration and decomposition of a hollow fiber membrane contained in the cartridge 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] There is a problem in that when the peroxide or hydroxyl radicals generated in this way flow from the fuel cell stack to the membrane humidifier, 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 constituting the humidifying membrane prevents the delivery of sufficiently humidified air to the fuel cell stack, thereby reducing the efficiency of the fuel cell stack and the entire fuel cell.

[0009] Accordingly, various attempts are being made to suppress the decomposition of hollow fiber membranes from peroxide or hydroxyl radicals, but there is still a need in the industry for technology to prevent deterioration of hollow fiber membranes.

[0010] The present invention provides a cartridge configured to prevent a hollow fiber membrane accommodated in the cartridge from being deteriorated and decomposed by peroxide or hydroxyl radicals, and a membrane humidifier for a fuel cell including the cartridge.

[0011] An inner case accommodating a plurality of hollow membranes through which a first fluid flows according to one aspect;

[0012] The second fluid is introduced and the inlet window is arranged at the end of the inner case; and

[0013] a patterned protective film disposed between the inlet window portion and the hollow fiber membrane;

[0014] A cartridge for a membrane humidifier is provided, wherein the patterned protective film includes an antioxidant.

[0015] According to another aspect, a membrane humidifier for a fuel cell is provided, which includes a cartridge for the membrane humidifier.

[0016] According to one aspect, the cartridge has a structure in which a patterned protective film containing an antioxidant is disposed between a hollow fiber membrane accommodated therein and the cartridge. This patterned protective film induces high-temperature and humid air entering the interior through the inlet window of the cartridge to disperse in all directions, thereby reducing stress on the hollow fiber membrane disposed adjacent to the inlet window, thereby reducing local damage. In addition, the antioxidant included in the patterned protective film captures and removes oxidizing substances such as hydrogen peroxide and / or hydroxyl radicals contained in the high-temperature and humid air, thereby effectively suppressing deterioration of the hollow fiber membrane caused by the oxidizing substances.

[0017] Figures 1 to 4 are drawings showing a plan view, a front view, a side view, and a perspective view of a patterned protective film structure according to one embodiment.

[0018] Figures 5 and 6 are drawings showing a plan view of a cartridge according to one embodiment.

[0019] 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.

[0020] 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.

[0021] 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.

[0022] 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.

[0023] 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 polymer resins and polymer macromolecules.

[0024] The term "patterned" as used throughout the specification means having a structure in which a certain shape is repeated.

[0025] The embodiments described below are merely exemplary, and various modifications are possible from these embodiments.

[0026] A cartridge for a membrane humidifier according to one aspect comprises an inner case accommodating a plurality of hollow fiber membranes through which a first fluid flows; an inlet window portion through which a second fluid flows and arranged at one end of the inner case; and a patterned protective film arranged between the inlet window portion and the hollow fiber membranes; wherein the patterned protective film may include an antioxidant.

[0027] A membrane humidifier for a fuel cell comprises one or more membrane humidifier cartridges. The membrane humidifier cartridges include hollow fiber membranes that enable moisture exchange. A first fluid (i.e., outside air) flows into the internal flow passages of the hollow fiber membranes and is transported to a fuel cell stack. However, since the first fluid is not sufficiently wet for use in the fuel cell stack, it must be reformed into a wet state through moisture exchange with a wet second fluid (generated from a reaction in the fuel cell stack). When the fuel cell is operated, a reduction reaction occurs at the cathode, and thereby the high-temperature, wet second fluid is supplied into the cartridge through an inlet window. At this time, since the hollow fiber membranes arranged adjacent to the inlet window are mainly composed of an organic polymer, if exposed to high-temperature, humid air for a long period of time, deformation and deterioration of the hollow fiber membranes occur. In addition, at the cathode of the fuel cell, oxidizing substances such as hydrogen peroxide and / or hydroxyl radicals may be generated by side reactions, and these oxidizing substances enter the cartridge together with the high-temperature and humid second fluid and cause a radical decomposition reaction of the hollow fiber membrane. It was discovered that the radical decomposition reaction causes a radical chain reaction of adjacent polymers, causing a problem of decomposition and deterioration of not only the hollow fiber membrane adjacent to the inlet window inside the cartridge, but also the hollow fiber membrane adjacent to it.

[0028] Accordingly, the inventors of the present invention have discovered that when a patterned protective film is placed between the inlet window through which the second fluid enters the cartridge and the hollow fiber membrane, the local stress load of the hollow fiber membrane is reduced by allowing the second fluid to be radially dispersed by the patterned protective film before reaching the outer surface of the hollow fiber membrane, and by including an antioxidant in the patterned protective film, the exposure of the hollow fiber membrane to high temperatures is minimized and radical decomposition reactions are suppressed by capturing and removing oxidizing substances contained in the second fluid, and from this perspective, the present invention has been completed.

[0029] According to one embodiment, the plurality of hollow fiber membranes may be surrounded by a patterned protective film. For example, the plurality of hollow fiber membranes may be surrounded by a patterned protective film on their entire outer surfaces, including cases where the entire outer surfaces in the longitudinal direction are surrounded or only a portion of the outer surfaces in the longitudinal direction are surrounded.

[0030] When the entire outer surface of the plurality of hollow fiber membranes is surrounded by a patterned protective film, a passage for the second fluid is formed between the outer surface of the hollow fiber membrane and the cartridge, thereby increasing the contact surface area between the second fluid and the hollow fiber membrane, and the second fluid is radially distributed by the patterned protective film, thereby solving the problem of local loss of the hollow fiber membrane due to local stress load on the hollow fiber membrane. In addition, the antioxidant contained in the patterned protective film can contribute to imparting oxidation resistance by suppressing the radical decomposition reaction of the hollow fiber membrane by capturing and removing oxidizing substances.

[0031] According to one embodiment, the plurality of hollow fiber membranes may comprise one or more hollow fiber membrane bundles formed by grouping individual hollow fiber membranes. For example, the plurality of hollow fiber membranes contained within the cartridge may comprise two or more grouped hollow fiber membrane bundles. In this case, the patterned protective film may be disposed on the outer surface of each of the one or more hollow fiber membrane bundles.

[0032] The above patterned protective film is arranged on the outer surface of each of one or more hollow fiber membrane bundles to wrap each hollow fiber membrane bundle, thereby enabling the hollow fiber membrane bundles to be tightly packed. As a result, not only can the flow rate of exchangeable fluid per unit area increase, but physical durability can also be enhanced.

[0033] In addition, the patterned protective film disposed on the outer surface of each of the one or more hollow fiber membrane bundles and surrounding each of the hollow fiber membrane bundles can function as a barrier layer that blocks the radical decomposition reaction initiated in one hollow fiber membrane bundle from leading to a chain reaction in adjacent hollow fiber membrane bundles, thereby preventing chain short circuits.

[0034] According to one embodiment, the patterned protective film may be disposed on the outer surface of each of the plurality of hollow fiber membranes. By surrounding each hollow fiber membrane with the patterned protective film, not only can the radical decomposition reaction of the hollow fiber membrane be effectively suppressed, but also chain-reaction failure due to the radical reaction of the hollow fiber membrane can be prevented.

[0035] According to one embodiment, the patterned protective film may be disposed on the outer surface of each of a plurality of hollow fiber membranes, and the patterned protective film may be disposed on the outer surface of a bundle of hollow fiber membranes formed by grouping one or more hollow fiber membranes having the patterned protective film disposed on the outer surface thereof.

[0036] By this, the oxidation resistance of the hollow fiber membrane is significantly improved, and serial short circuits can be prevented.

[0037] According to one embodiment, the patterned protective film may be positioned to surround the inlet window portion. For example, the patterned protective film may be positioned to cover the inlet window portion on the inner side of the cartridge.

[0038] By arranging the patterned protective film to surround the inlet window, the second fluid can be scattered and dispersed within the cartridge, thereby relieving local stress applied to the adjacent hollow fiber membrane at the inlet window. In addition, the antioxidant dispersed in the patterned protective film can effectively suppress decomposition and deterioration of the hollow fiber membrane accommodated within the cartridge by capturing and removing hydrogen peroxide and hydroxyl radicals contained in the second fluid.

[0039] According to one embodiment, the patterned protective film can be configured with a structure capable of passing and dispersing a second fluid.

[0040] According to one embodiment, the cartridge for the membrane humidifier may further include an outlet window portion arranged at the other end of the inner case so that the second fluid is introduced through the inlet window portion and is discharged to the outside after exchanging moisture with the first fluid, and may further include a patterned protective film arranged between the outlet window portion and the hollow fiber membrane.

[0041] According to one embodiment, the inflow window portion may be composed of a single window or may be composed of two or more windows. In this case, when the inflow window portion is composed of two or more windows, the two or more windows may have the same or different shapes.

[0042] According to one embodiment, the outlet window portion may be composed of a single window or may be composed of two or more windows. In this case, when the outlet window portion is composed of two or more windows, the two or more windows may have the same or different shapes.

[0043] According to one embodiment, the pattern of the patterned protective film may include one or more of a linear repeating structure, a porous structure, a lattice structure, and a mesh structure. For example, the pattern of the patterned protective film may be a mesh structure.

[0044] The pattern of the above patterned protective film can be explained in more detail through FIGS. 1 to 4.

[0045] FIG. 1 schematically illustrates a plan view (A), a front view (B), a side view (C), and a perspective view (D) of an example of a patterned protective film. The patterned protective layer according to the first embodiment has a linear repeating structure. The method for forming the linear repeating structure is not particularly limited, and for example, a method of forming a protective film after masking, a method of coating a mixture containing an antioxidant on the outer surface of a hollow fiber membrane and then removing the linear pattern of the remaining components so that only the antioxidant component remains, etc. may be used, but is not limited to the above-mentioned methods. Alternatively, a method may be used in which a mixture containing an antioxidant is applied to a substrate and then the linear pattern of the remaining components is removed so that only the antioxidant component remains, and then the protective film having the linear pattern is removed from the substrate.

[0046] Figure 2 schematically illustrates a plan view (A), a front view (B), a side view (C), and a perspective view (D) of a structure in which pores are formed in a protective film having a structure in which pores are formed. The patterned protective film is coated so that pores are formed in the direction of the thickness of the thin film, and the size and number of pores are not particularly limited. The method for forming the pattern is not particularly limited, but for example, a method of coating the outer surface of the hollow fiber membrane in the form of a mixture including an antioxidant and then removing the pore pattern composed of a component other than the antioxidant may be used, but is not limited to the above-mentioned method. As described in the linear thin film pattern, it can be manufactured on a separate substrate and then used separately.

[0047] Figure 3 schematically illustrates a plan view (A), a front view (B), and a side view (C) of a protective film having a lattice structure. The patterned protective film can be formed by coating a linear pattern on the outer surface of a hollow fiber membrane, and then laminating a linear pattern coating in a direction orthogonal to the coated linear pattern, and repeating the lamination of linear pattern coating in the orthogonal direction to a target thickness. In order for the patterns of each layer to be stably laminated, it is preferable to laminate a mixture including an antioxidant in which a linear pattern is formed to a target thickness, and then, after the coating is completed, to collectively remove the linear patterns composed of components other than the antioxidant of each layer. As described in the linear repeat pattern, it can be manufactured on a separate substrate and then used separately.

[0048] Figure 4 schematically illustrates a plan view (A), a front view (B), a side view (C), and a perspective view (D) of a patterned protective film having a mesh structure. The patterned protective layer is formed so that pores are observed on the upper surface (A), and a mesh structure is observed on the front surface (B) and the side surface (C). For example, it can be formed by coating a mixture containing an antioxidant on the outer surface of a hollow fiber membrane and then removing a portion of the pattern composed of components other than the antioxidant. As described in the linear repeating pattern, it can be manufactured on a separate substrate and then used separately.

[0049] For example, a patterned protective film can be formed by weaving a mixture containing an antioxidant into a woven form to wrap around the surface of a hollow fiber membrane.

[0050] According to one embodiment, the patterned protective film may include a support and an antioxidant.

[0051] According to one embodiment, the patterned protective film includes a support and an antioxidant layer disposed on a surface of the support, and the antioxidant layer may include an antioxidant.

[0052] For example, the patterned protective film can be modified by coating an antioxidant on a support by spin coating or spray coating, etc.

[0053] By disposing an antioxidant layer on the surface of a patterned protective film, there is an advantage in that an antioxidant can be introduced without reducing the strength of the patterned protective film, and some of the antioxidant can flow out from the coating layer and be contained in the second fluid, thereby removing oxidized substances that have passed through the patterned protective film, thereby preventing decomposition and deterioration of the hollow fiber membrane. In addition, some of the antioxidant can flow into the fuel cell stack, thereby having an advantage in that oxidized substances generated by side reactions during fuel cell operation can be removed at an early stage.

[0054] According to one embodiment, the patterned protective film may include an anti-oxidation layer disposed over the entire surface thereof or disposed only on a portion thereof.

[0055] For example, from the perspective of efficiently capturing and / or removing oxidizing substances contained in the second fluid, the patterned protective film may include, but is not limited to, an anti-oxidizing layer disposed on a surface facing the direction in which the first fluid flows.

[0056] According to one embodiment, the antioxidant may be dispersed within the patterned protective film. For example, the patterned protective film may include an antioxidant uniformly dispersed within a support.

[0057] According to one embodiment, the patterned protective film may include an antioxidant having a concentration gradient in the support thickness direction.

[0058] For example, the concentration of the antioxidant may have a concentration gradient that decreases from the area where the patterned protective film and the second fluid first contact each other toward the interior of the cartridge.

[0059] For example, the concentration of the antioxidant may have a concentration gradient that increases from the area where the patterned protective film and the second fluid first contact each other toward the interior of the cartridge.

[0060] Since the patterned protective film has an antioxidant concentration gradient, the oxidizing material can be effectively removed from the second fluid without deteriorating the physical properties of the patterned protective film.

[0061] According to one embodiment, the support of the patterned protective film may include an organic material, an inorganic material, or a combination thereof.

[0062] For example, the organic material may include polypropylene (PP), polyethylene terephthalate (PET), polyamide (PA), acrylonitrile butadiene styrene (ABS), polycarbonate (PC), polyethylene (PE), polymethyl methacrylate (PMMA), or any combination thereof.

[0063] For example, the inorganic material may include a metal material such as stainless steel, aluminum, silver, copper, nickel, tungsten, molybdenum, chromium, or an alloy thereof.

[0064] According to one embodiment, the antioxidant may include one or more antioxidants selected from a phenol antioxidant, an amine antioxidant, a phosphorus antioxidant, a sulfur antioxidant, a metal antioxidant, and an organo-metallic antioxidant.

[0065] 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.

[0066] For example, the amine antioxidant may include phenyl-α-naphthylamine, phenyl-β-naphthylamine, N,N'-diphenyl-p-phenylenediamine, N,N'-di-naphthyl-p-phenylenediamine, a HALS compound, or a combination thereof.

[0067] 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.

[0068] For example, the metal-based antioxidant may include cerium, nickel, tungsten, ruthenium, palladium, silver, platinum, rhodium, cesium, zirconium, cobalt, chromium, yttrium, manganese, iron, molybdenum, lead, vanadium, titanium, niobium, neodymium, lanthanum, ions thereof, oxides thereof, nitrides thereof, halides thereof, sulfides thereof, phosphides thereof, or any mixture thereof.

[0069] For example, the organo-metallic antioxidant may include a Ce-crown complex, a Ce-phosphoric acid complex, a Ce-Bypyridine, or any mixture thereof.

[0070] 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.

[0071] According to one embodiment, the antioxidant may be included in an amount of 0.001 to 5 parts by weight per 100 parts by weight of the patterned protective film.

[0072] According to one embodiment, the patterned protective film may have a thickness of 0.01 mm to 1 mm.

[0073] When the thickness of the patterned protective film satisfies the above range, sufficient rigidity of the support is obtained, and a sufficient amount of antioxidant can be dispersed within the support.

[0074] According to one embodiment, the hollow fiber membrane may include a polymer. For example, the polymer may include 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 foregoing polymers.

[0075] According to one embodiment, the hollow fiber membrane may include a polystyrene-based polymer.

[0076] According to one embodiment, the thickness of the hollow fiber membrane may be 0.5 nm to 1 mm. The thickness of the hollow fiber membrane should be considered in terms of moisture exchange, and sufficient moisture exchange can be achieved when the thickness satisfies the above range.

[0077] According to one embodiment, the average pore size of the hollow fiber membrane may be from 0.1 nm to 100,000 nm, and the porosity may be from 50% to 90%. The pore size and porosity of the hollow fiber membrane should be considered in terms of moisture exchange, and sufficient moisture exchange can be achieved when the above ranges are satisfied.

[0078] According to one embodiment, the hollow fiber membrane may further include additives such as surfactants, hydrophilic organic compounds, or hydrophilic polymers. These additives may be selected and added in an appropriate amount within a range that does not impair the inherent physical 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 may also be used.

[0079] 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.

[0080] 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:

[0081] 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:

[0082] Below, the structure of a cartridge according to one aspect is briefly described with reference to the plan views of the cartridge in FIGS. 5 and 6. FIG. 5 is a plan view of a cartridge accommodating a plurality of hollow fiber membranes therein.

[0083] Referring to Fig. 5, the cartridge (50) may be formed of an exterior material with excellent dimensional stability, resin flowability, and heat resistance. Examples of materials forming the exterior of the cartridge include acrylonitrile-butadiene-styrene resin, nylon, etc.

[0084] The cartridge (50) includes an inner case (not shown) that accommodates a plurality of hollow fiber membranes therein. It includes an inlet window section (W1) through which a high-temperature, humid second fluid from a fuel cell stack flows in to exchange moisture with a first fluid flowing inside the hollow fiber membrane, and an outlet window section (W2) through which the humidified second fluid after moisture exchange is discharged outside the cartridge.

[0085] Although the above inlet window portion (W1) and the outlet window portion (W2) are illustrated as having a rectangular shape, they are not limited to this shape, and a person skilled in the art can recognize that they can be transformed into window portions of various shapes such as triangles, squares, pentagons, polygons, and circles.

[0086] In addition, the area of ​​the inlet window portion (W1) and the outlet window portion (W2) can be appropriately adjusted by a person skilled in the art according to the inlet and outlet flow rates of the second fluid.

[0087] In the past, there were efforts to modify the structure of the inlet window portion (W1) itself in order to prevent the flow of the second fluid entering the inlet window portion (W1) from being locally stagnant. However, there still remained a problem that the stress on the portion of the hollow fiber membrane exposed to the inlet window portion (W1) due to the inflow pressure of the second fluid was still higher than that on other portions, resulting in the occurrence of short circuits. Short circuits in the hollow fiber membrane not only lead to a decrease in the moisture exchange capacity, but also serve as initiators of radical reactions in adjacent hollow fiber membranes, which can cause chain-repeated short circuit problems.

[0088] According to one embodiment of the present invention, a cartridge has a patterned protective film (51) containing an antioxidant disposed on an inlet window portion (W1) and an outlet window portion (W2), so that when a second fluid flows into the cartridge and is dispersed, oxidizing substances such as hydrogen peroxide and hydroxyl radicals can be captured by the antioxidant. In addition, by configuring a certain amount of the antioxidant to flow into the cartridge from the protective film (51) containing the antioxidant, oxidizing substances contained in the second fluid and entering the cartridge can be captured and removed before they come into contact with the hollow fiber membrane, thereby preventing deterioration of the hollow fiber membrane.

[0089] The patterned protective film containing an antioxidant effectively captures hydrogen peroxide and hydroxyl radicals contained in the second fluid due to the large surface area of ​​the mesh pattern, thereby preventing the ingress of these oxidizing substances into the cartridge. Furthermore, when used in conjunction with the aforementioned fluid dispersing member, the mesh pattern can provide high dispersibility of the second fluid within the cartridge.

[0090] Inside the cartridge, the second fluid exchanges moisture with the first fluid flowing within the hollow fiber membrane. The humidified first fluid, having undergone moisture exchange, passes through the outlet window (W2) and is transported into the fuel cell stack.

[0091] At this time, the patterned protective film (52) placed on the above-mentioned outlet window portion (W2) is arranged in the path along which the humidified first fluid moves into the stack, so that a portion of the antioxidant is eluted and moves into the stack.

[0092] The patterned protective film (52) may be arranged to cover the inlet window portion (W1) and / or the outlet window portion (W2), or the patterned protective film (52) may be arranged to cover the outer surface of each of a plurality of hollow fiber membranes, the outer surface of each of a bundle of hollow fiber membranes formed by grouping one or more hollow fiber membranes, the outer surface of all of a plurality of hollow fiber membranes accommodated inside the cartridge, or any combination thereof.

[0093] According to one embodiment, the patterned protective film disposed on the outflow window portion (W2) can be configured to provide an antioxidant of 1 ug / 1000 hr or more into the fuel cell stack.

[0094] Referring to FIG. 6, instead of being formed as a single window as shown in FIG. 5, the inlet window portion (W1) and the outlet window portion (W2) are formed as a plurality of window sections (W11, W22).

[0095] A patterned protective film may be provided at the bottom of the plurality of window compartments.

[0096] The cartridge of FIG. 6 is identical to the cartridge of FIG. 5 except that the window portion is composed of multiple window compartments, and therefore, for the remaining cartridge structure, refer to the contents of FIG. 5. In addition, in the drawing of FIG. 6, the configurations indicated by numbers similar to those in FIG. 5 mean the same configurations as the corresponding configurations in FIG. 5.

[0097]

[0098] A membrane humidifier for a fuel cell according to one aspect may include one or more cartridges for the membrane humidifier described above.

[0099] For example, the membrane humidifier may include one cartridge inside the membrane humidifier.

[0100] Hereinafter, an 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.

[0101] [Example]

[0102]

[0103] Example 1

[0104] A bundle was made of hollow fiber membrane, and the outer surface of the hollow fiber membrane bundle was wrapped with a patterned protective film having a mesh shape and containing 1 part by weight of irganox 1010, a phenolic antioxidant, and placed in the inner space of the inner case. The cartridge of Example 1 was manufactured so that each of the inlet window section and the outlet window section of the cartridge was composed of a plurality of window sections.

[0105] The above patterned protective film was obtained by spinning a spinning solution obtained by mixing 1 part by weight of polypropylene (PET) polymer and an antioxidant (Irganox 1010) with a known solvent into a yarn, and the process of obtaining the yarn was performed by a method generally known in the art. The spun yarn was woven into a plain weave, and the mesh number of the woven mesh was made to be 1. In other words, the yarn was woven so that the gap between the meshes was 1 inch.

[0106] Example 2

[0107] A cartridge was manufactured in the same manner as Example 1, except that each of the inlet window and outlet window of the cartridge was manufactured to consist of a single window without a window compartment.

[0108] Example 3

[0109] A cartridge was manufactured in the same manner as in Example 2, except that 1 part by weight of Tinuvin 770 was used instead of irganox1010 as an antioxidant.

[0110] Example 4

[0111] A cartridge was manufactured in the same manner as in Example 2, except that 1 part by weight of Salsalate was used instead of irganox1010 as an antioxidant.

[0112] Example 5

[0113] A cartridge was manufactured in the same manner as in Example 2, except that 3 parts by weight of Salsalate was used instead of irganox1010 as an antioxidant.

[0114] Example 6

[0115] A cartridge was manufactured in the same manner as in Example 2, except that 5 parts by weight of Salsalate was used instead of irganox1010 as an antioxidant.

[0116] Comparative Example 1

[0117] A cartridge was manufactured in the same manner as in Example 1, except that no patterned protective film was provided on the outer surface of the hollow fiber bundle.

[0118] Comparative Example 2

[0119] A cartridge was prepared in the same manner as in Example 2, except that a patterned protective film containing no antioxidant was used.

[0120] Evaluation Example 1 - Evaluation of Antioxidant Effect

[0121] An H10N humidifier manufactured and sold by our company was manufactured and sold to accommodate one cartridge manufactured in Example 1 and Comparative Example 1. The manufactured humidifier was operated under conditions that allowed for acceleration of approximately 100 times the operating conditions, thereby accelerating the wear of the hollow fiber membrane for 30 hours. After the test, the breakage rate of the hollow fiber membrane contained within the cartridge was confirmed.

[0122] As a result, the single-strand breakage rate of the hollow fiber membrane in the cartridge of Example 1 was found to be at the level of 0.3 to 0.6%, and the single-strand breakage rate of the hollow fiber membrane in the cartridge of Comparative Example 1 was found to be at the level of 6 to 8%. That is, it was confirmed that when the outer surface of the hollow fiber membrane bundle is covered with a patterned protective film containing an antioxidant, the single-strand breakage durability is improved by more than 10 times.

[0123] Evaluation Example 2 - Evaluation of Antioxidant Effect

[0124] An H10N humidifier manufactured and sold by our company that accommodates the cartridges of Examples 2 to 6 and Comparative Example 2 was manufactured. Thereafter, a solution used in the Fenton test (3% H2O2, 2 ppm FeSO4) was injected into the humid air (RH95%, 1000 SLPM, 80°C) entering the shell side of the humidifier at a rate of 10 cc / min, and a test was conducted for 72 hours. The results are shown in Table 1 below. Here, the internal leak value was confirmed by measuring the flow rate of gas flowing out toward the shell when 0.5 bar of gas was pressurized toward the hollow fiber membrane tube.

[0125] Molecular weight reduction rate after 72 hoursInternal leak value (slpm) after 72 hoursComparative example 220 %43.3 slpmExample 216 %32.5 slpmExample 313 %30.3 slpmExample 411 %25.6 slpmExample 58 %18.5 slpmExample 65 %12.5 slpm

[0126]

[0127] As shown in Table 1 above, when a patterned protective film including an antioxidant was applied, the rate of increase in the internal leak value in the Fenton reaction was confirmed to be reduced, suggesting that the durability of the humidifier was improved. In addition, the rate of decrease in the molecular weight of the hollow fiber membrane within the membrane humidifier was confirmed to be reduced, suggesting that an antioxidant effect was achieved that suppresses the decomposition of the hollow fiber membrane by oxidizing substances.

Claims

1. An inner case containing a plurality of hollow fiber membranes through which a first fluid flows; An inlet window portion into which a second fluid is introduced and which is positioned at one end of the inner case; and a patterned protective film disposed between the inlet window portion and the hollow fiber membrane; A cartridge for a membrane humidifier, wherein the patterned protective film contains an antioxidant.

2. In paragraph 1, A cartridge for a membrane humidifier, wherein the plurality of hollow fiber membranes are surrounded by a patterned protective film.

3. In paragraph 1, The above plurality of hollow fiber membranes include one or more hollow fiber membrane bundles formed by grouping individual hollow fiber membranes, A cartridge for a membrane humidifier, wherein the above patterned protective film is disposed on the outer surface of each of one or more hollow fiber membrane bundles.

4. In paragraph 1, A cartridge for a membrane humidifier, wherein the above patterned protective film is arranged on the outer surface of each of the plurality of hollow fiber membranes.

5. In paragraph 1, A cartridge for a membrane humidifier, wherein the pattern of the above patterned protective film includes at least one of a linear repeating structure, a porous structure, a lattice structure, and a mesh structure.

6. In paragraph 1, A cartridge for a membrane humidifier, wherein the pattern of the above patterned protective film is a mesh structure.

7. In paragraph 1, A cartridge for a membrane humidifier, wherein the patterned protective film further comprises an organic material, an inorganic material, or a combination thereof.

8. In the 7th paragraph, A cartridge for a membrane humidifier, wherein the organic material comprises polypropylene (PP), polyethylene terephthalate (PET), polyamide (PA), acrylonitrile butadiene styrene (ABS), polycarbonate (PC), polyethylene (PE), polymethyl methacrylate (PMMA), or any combination thereof.

9. In the 7th paragraph, A cartridge for a membrane humidifier, wherein the above inorganic material comprises stainless steel, aluminum, silver, copper, nickel, tungsten, molybdenum, chromium or a combination thereof.

10. In paragraph 1, A cartridge for a membrane humidifier, wherein the thickness of the patterned protective film is 0.01 mm to 1 mm.

11. In paragraph 1, A cartridge for a membrane humidifier, wherein the above antioxidant is dispersed and present in the patterned protective film.

12. In paragraph 1, A cartridge for a membrane humidifier, wherein the antioxidant comprises at least one antioxidant selected from among a phenol-based antioxidant, an amine-based antioxidant, a phosphorus-based antioxidant, a sulfur-based antioxidant, a metal-based antioxidant, and an organo-metallic antioxidant.

13. In paragraph 1, A cartridge for a membrane humidifier, wherein the above inlet window portion is composed of a single window or two or more windows, and the two or more windows have the same or different shapes.

14. In paragraph 1, It further includes an outlet window portion arranged at the other end of the inner case so that the second fluid is introduced through the inlet window portion and is discharged to the outside after exchanging moisture with the first fluid. A cartridge for a membrane humidifier, further comprising a patterned protective film disposed between the above-mentioned leakage window portion and the hollow fiber membrane.

15. A membrane humidifier for a fuel cell comprising a membrane humidifier cartridge according to any one of claims 1 to 14.

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