Hollow fiber membrane capsule, humidifier for fuel cell, and fuel cell including humidifier

Abstract

The present invention relates to a hollow fiber membrane capsule, a humidifier for a fuel cell, and a fuel cell including the humidifier. According to the present invention, the hollow fiber capsule has excellent heat resistance and hydrolysis resistance, and has a heat distortion temperature of 120 DEG C or more and a moisture absorption rate of 1% or less, and thus a reduction in mechanical properties and a dimensional change that may occur during use of a fuel cell can be minimized, thereby improving durability of a product.

Description

Technical Field

[0001] The present disclosure relates to a hollow fiber membrane cartridge having heat resistance and hydrolysis resistance to a high-temperature and high-humidity humidification fluid, a humidifier for a fuel cell, and a fuel cell including the humidifier. Background Art

[0002] A fuel cell is a power generation cell that combines hydrogen and oxygen to generate electricity. The advantage of a fuel cell is that, unlike conventional chemical cells such as dry cells or storage batteries, electricity can be generated continuously as long as hydrogen and oxygen are supplied, and there is no heat loss, so the efficiency of a fuel cell is higher than that of an internal combustion engine.

[0003] In addition, fuel cells convert chemical energy generated by combining hydrogen and oxygen directly into electrical energy, thereby emitting less pollutants. Therefore, fuel cells are advantageous in that they are environmentally friendly and can reduce the problem of resource depletion due to increased energy consumption.

[0004] Among different types of fuel cells, polymer electrolyte membrane fuel cells (PEMFCs) are known to be advantageous for transportation systems and small stationary power generation equipment because they operate at low temperatures and have a high output density, so they can be miniaturized.

[0005] An important factor in improving the performance of a polymer electrolyte membrane fuel cell (PEMFC) is to provide more than a predetermined amount of water to the polymer electrolyte membrane or proton exchange membrane (PEM) of a membrane electrode assembly (MEA) to maintain the moisture content. To maintain the moisture content, humidification is required.

[0006] A hollow fiber membrane having a large permeation area per unit volume can be used as a selective permeation membrane for humidification. When a humidifier is manufactured using a hollow fiber membrane, a high degree of integration of the hollow fiber membrane having a large contact surface area can be achieved, thereby enabling sufficient humidification of a fuel cell even at a small capacity, enabling the use of low-cost materials, and enabling the recovery of moisture and heat included in exhaust gas discharged from a fuel cell at a high temperature, and reuse of the recovered moisture and heat by the humidifier.

[0007] In the humidification process of the humidifier using the hollow fiber membrane, the humidifier is used while being exposed to the high temperature and high humidity humidification fluid, so the material constituting the humidifier needs to have heat resistance and hydrolysis resistance. Therefore, it is necessary to develop a material for the humidifier having excellent heat resistance and hydrolysis resistance. Summary of the invention

[0008] Technical issues

[0009] Embodiments of the present disclosure made in view of the above provide a hollow fiber membrane cassette having excellent heat resistance.

[0010] Another embodiment of the present disclosure provides a hollow fiber membrane cassette having excellent hydrolysis resistance.

[0011] Another embodiment of the present disclosure provides a hollow fiber membrane cassette having excellent mechanical properties and dimensional stability.

[0012] Another embodiment of the present disclosure is directed to providing a humidifier for a fuel cell including a hollow fiber membrane cartridge.

[0013] Yet another embodiment of the present disclosure provides a fuel cell including a humidifier for the fuel cell.

[0014] Technical Solution

[0015] In order to achieve the above-mentioned objectives, embodiments of the present disclosure may include the following structures.

[0016] The hollow fiber membrane box according to an embodiment of the present disclosure may include: an inner shell having an inner space; a plurality of hollow fiber membranes disposed in the inner space of the inner shell; a first potting part disposed on one side of the inner shell, the first potting part being configured to fix one side of each of the plurality of hollow fiber membranes; and a second potting part disposed on the other side of the inner shell, the second potting part being configured to fix the other side of each of the plurality of hollow fiber membranes. The heat deformation temperature of the inner shell may be above 120°C and the moisture absorption rate may be below 1%.

[0017] The moisture absorption rate of the inner shell may be 0.5% or less.

[0018] The inner housing may include a polymer resin.

[0019] The polymer resin may include at least one selected from the group consisting of polyphenylene ether (PPE), polyphenylene sulfone (PPSU), polysulfone (PSU), polyetheretherketone (PEEK), and polyarylate (PAR).

[0020] The polyphenylene ether (PPE) may be polyphenylene ether (m-PPE) modified by polystyrene-butadiene copolymer (HIPS).

[0021] The m-PPE may include 90 wt % to 99 wt % of polyphenylene ether (PPE) and 1 wt % to 10 wt % of polystyrene-butadiene copolymer (HIPS), based on the total weight of the m-PPE.

[0022] The weight reduction rate of the inner case after the high temperature and high humidity treatment may be 10% or less.

[0023] Here, the high temperature and high humidity treatment means that the inner case is placed in an autoclave containing water, the temperature of the autoclave is set to 120° C.±3° C., and the high temperature and high humidity treatment is performed for 200 hours.

[0024] The coefficient of thermal expansion (CTE) of the inner shell can be 100×10 -6 mm / mm / ℃ or less.

[0025] The specific gravity of the inner shell can be 1.5g / cm 3 the following.

[0026] According to another embodiment of the present disclosure, a humidifier for a fuel cell may include: an intermediate shell having an internal space, an exhaust gas inlet and an exhaust gas outlet; a hollow fiber membrane box arranged in the internal space of the intermediate shell; a first cover combined with one end of the intermediate shell; and a second cover combined with the other end of the intermediate shell.

[0027] A fuel cell according to still another embodiment of the present disclosure may include a battery cell stack and a humidifier connected to the battery cell stack.

[0028] Beneficial Effects

[0029] The hollow fiber membrane cassette according to an embodiment of the present disclosure may have excellent heat resistance, and may have excellent hydrolysis resistance.

[0030] In addition, the hollow fiber membrane cassette according to an embodiment of the present disclosure may have excellent mechanical properties and dimensional stability.

[0031] A humidifier for a fuel cell including a hollow fiber membrane cartridge according to another embodiment of the present disclosure may have excellent heat resistance, hydrolysis resistance, mechanical properties, and dimensional stability.

[0032] A fuel cell including a humidifier for a fuel cell according to another embodiment of the present disclosure can have excellent heat resistance, hydrolysis resistance, mechanical properties and dimensional stability. A fuel cell according to another embodiment of the present disclosure can have excellent durability and long life characteristics, and can prevent or stop problems such as cracking or failure. BRIEF DESCRIPTION OF THE DRAWINGS

[0033] Figure 1 is a schematic perspective view of a hollow fiber membrane cassette according to an embodiment of the present disclosure.

[0034] Figure 2 is a perspective view of a hollow fiber membrane according to an embodiment of the present disclosure.

[0035] Figure 3 is a schematic exploded perspective view of a humidifier for a fuel cell according to another embodiment of the present disclosure. DETAILED DESCRIPTION

[0036] The present disclosure may be variously modified and may have various embodiments, of which specific embodiments will be described in detail hereinafter with reference to the accompanying drawings.

[0037] When "having" or "including" mentioned in this specification is used, other parts may be added unless "only" is used. When a component is expressed in the singular, the component includes the plural unless otherwise explicitly stated. In addition, when describing a component, the component is interpreted as including a tolerance range even if it is not explicitly described.

[0038] Although the terms “first,” “second,” etc. may be used herein to describe various components, these components are not limited by the terms, and the terms are only used to distinguish one component from another.

[0039] Figure 1 is a schematic perspective view of a hollow fiber membrane cassette 100 according to an embodiment of the present disclosure.

[0040] Reference Figure 1 The hollow fiber membrane cassette 100 according to an embodiment of the present disclosure may include an inner housing 110 , a plurality of hollow fiber membranes 120 , a first potting part 131 , and a second potting part 132 .

[0041] The inner case 110 may have an inner space. The inner case 110 may be box-shaped with open ends. One open end of the inner case 110 may be referred to as one side, and the other open end may be referred to as the other side.

[0042] A plurality of hollow fiber membranes 120 may be disposed in the inner space of the inner case 110 .

[0043] Figure 2 is a perspective view of a hollow fiber membrane 120 according to an embodiment of the present disclosure.

[0044] Reference Figure 2 The hollow fiber membrane 120 according to an embodiment of the present disclosure may have a hollow portion 121. For example, the hollow fiber membrane 120 may have a tubular shape including a hollow center. Any commercially available hollow fiber membrane may be used as the hollow fiber membrane 120.

[0045] According to an embodiment of the present disclosure, one end portion of the tubular hollow fiber membrane 120 is referred to as one side, and the other end portion is referred to as the other side.

[0046] The first potting part 131 may be combined with one side of the inner case 110 to fix one side of each of the plurality of hollow fiber membranes 120. The second potting part 132 may be combined with the other side of the inner case 110 to fix the other side of each of the plurality of hollow fiber membranes 120.

[0047] The opposite ends of the hollow fiber membrane cassette 100 are potted by the first potting part 131 and the second potting part 132. In this case, the first potting part 131 and the second potting part 132 may be formed so as not to block the hollow parts of the plurality of hollow fiber membranes 120. The first potting part 131 and the second potting part 132 are generally formed by hardening a liquid polymer such as a liquid polyurethane (PU) resin using a casting method.

[0048] The thermal deformation temperature of the inner case 110 according to the embodiment of the present disclosure may be 120° C. or more.

[0049] The heat deformation temperature may be measured using a sample of the inner case 110. For example, the sample of the inner case 110 is a sample made of a material for the inner case. Hereinafter, the sample of the inner case 110 is also referred to as a "sample".

[0050] According to an embodiment of the present disclosure, the heat deformation temperature can be measured according to ASTM D 648. In order to measure the heat deformation temperature, an unannealed sample having a thickness of 4 mm is prepared. When a pressure of 1.8 MPa is applied to the sample and the temperature is increased from room temperature (25° C.) at a rate of 2° C. / min, the temperature at which the sample bends 0.25 mm is referred to as the heat deformation temperature.

[0051] If the thermal deformation temperature of the inner case 110 is less than 120° C., the size or shape of the inner case may be changed by the hot humidification fluid, which may cause delamination of the bonding interface between the first potting part 131 and the inner case 110 or the bonding interface between the second potting part 132 and the inner case 110 .

[0052] The thermal deformation temperature of the inner housing 110 according to the embodiment of the present disclosure may be, for example, 140° C. or more.

[0053] More specifically, the thermal deformation temperature of the inner case 110 according to the embodiment of the present disclosure may be 150° C. or more or 160° C. or more.

[0054] The moisture absorption rate of the inner case 110 according to the embodiment of the present disclosure may be 1% or less.

[0055] For example, the moisture absorption rate may be obtained by immersing a sample of the inner case 110 in water at 23° C. for 24 hours and then measuring the moisture absorption amount of the sample according to ASTM D570.

[0056] The moisture absorption rate can be measured by Formula 1 below.

[0057] [Formula 1]

[0058]

[0059] If the moisture absorption rate is greater than 1%, continuous supply of high-temperature and high-humidity humidification fluid to the inner case 110 may increase the possibility of hydrolysis of the inner case 110 and may reduce mechanical properties, resulting in rupture and failure of the inner case 110 .

[0060] For example, the moisture absorption rate of the inner case 110 according to the embodiment of the present disclosure may be 0.5% or less or 0.3% or less.

[0061] The inner case 110 according to the embodiment of the present invention may include polymer resin.

[0062] The polymer resin may include at least one selected from the group consisting of polyphenylene ether (PPE), polyphenylene sulfone (PPSU), polysulfone (PSU), polyetheretherketone (PEEK), and polyarylate (PAR).

[0063] The polyphenylene ether (PPE) may be, for example, polyphenylene ether (m-PPE) modified by polystyrene-butadiene copolymer (HIPS). According to an embodiment of the present disclosure, m-PPE refers to polyphenylene ether (PPE) modified by polystyrene-butadiene copolymer (HIPS).

[0064] According to an embodiment of the present disclosure, the m-PPE may include 90 wt % to 99 wt % of polyphenylene ether (PPE) and 1 wt % to 10 wt % of polystyrene-butadiene copolymer (HIPS), based on the total weight of the m-PPE.

[0065] If the content of polyphenylene ether (PPE) is less than 90 wt % based on the total weight of m-PPE, it may cause problems with heat resistance or mechanical strength, and if the content of polyphenylene ether (PPE) is greater than 99 wt %, it is difficult to exhibit the performance of HIPS due to the excessively large proportion of PPE, and it may cause problems with moldability.

[0066] According to an embodiment of the present disclosure, the m-PPE may have a Mw molecular weight (weight average molecular weight) of 70,000 to 100,000.

[0067] According to an embodiment of the present disclosure, the inner case 110 may have excellent hydrolysis resistance.

[0068] If the inner shell 110 does not have hydrolysis resistance, the polymer constituting the inner shell 110 may be hydrolyzed by the high-temperature and high-humidity humidification fluid. In addition, this may cause the mechanical properties of the inner shell 110 to be rapidly degraded. Therefore, delamination may occur between the inner shell 110 and the potting parts 131 and 132 of the hollow fiber membrane cassette 100.

[0069] According to an embodiment of the present disclosure, the hydrolysis resistance of the inner case 110 may be evaluated by a weight reduction rate of the inner case 110 .

[0070] The inner case 110 according to the embodiment of the present disclosure has excellent hydrolysis resistance, and can produce a small or very small weight reduction even after high temperature and high humidity treatment.

[0071] The weight reduction rate (WR) of the inner case 110 according to the embodiment of the present disclosure may be 10% or less.

[0072] The weight reduction rate (WR) may be measured according to Formula 2 below.

[0073] [Formula 2]

[0074]

[0075] In Formula 2, W1 is the weight of the sample of the inner case before the high temperature and high humidity treatment, and W2 is the weight of the sample of the inner case 110 after the high temperature and high humidity treatment.

[0076] As the high temperature and high humidity treatment conditions for measuring the weight reduction rate (WR) according to an embodiment of the present disclosure, a sample of the inner case 110 is placed in an autoclave containing water, the temperature of the autoclave is set to 120° C.±3° C., and the high temperature and high humidity treatment is performed for 200 hours. For example, a product from JAOTECH can be used as the autoclave.

[0077] According to an embodiment of the present disclosure, the inner case 110 may have excellent hydrolysis resistance, whereby shape deformation or chemical changes of the inner case may not occur or may occur less even after high temperature and high humidity treatment.

[0078] As one method of evaluating the degree of deformation or chemical change of the inner case 110 , delamination characteristics between the inner case 110 and the potting parts 131 and 132 may be evaluated.

[0079] To evaluate delamination characteristics, according to an embodiment of the present disclosure, the hollow fiber membrane cassette 100 may be subjected to high temperature and high humidity treatment and delamination between the inner case 110 and the potting parts 131 and 132 may be checked. An autoclave may be used to subject the hollow fiber membrane cassette 100 to high temperature and high humidity treatment.

[0080] As high temperature and high humidity treatment conditions for evaluating delamination characteristics according to an embodiment of the present disclosure, the hollow fiber membrane cassette 100 was placed in an autoclave containing water, the temperature of the autoclave was set to 120° C.±3° C., and high temperature and high humidity treatment was performed for 200 hours.

[0081] According to an embodiment of the present disclosure, the inner case 110 and the potting parts 131 and 132 are evaluated as delamination occurring between the inner case 110 and the potting parts 131 and 132 when the inner case 110 and the potting parts 131 and 132 are spaced apart from each other or separated from each other.

[0082] According to an embodiment of the present disclosure, delamination between the inner case 110 and the potting parts 131 and 132 may not occur in the hollow fiber membrane cassette 100 even after high temperature and high humidity treatment.

[0083] According to an embodiment of the present disclosure, delamination between the inner case 110 and the potting parts 131 and 132 does not occur, and thus malfunction or damage of a humidifier or a fuel cell including the inner case 110 may be prevented.

[0084] The coefficient of thermal expansion (CTE) of the inner housing 110 according to an embodiment of the present disclosure may be 100×10 -6 mm / mm / ℃ or less.

[0085] For example, the thermal expansion coefficient can be measured using a thermomechanical analyzer (TMA) according to the TMA method and ASTM E 696. For example, Q400 from TA Instrument can be used as a thermomechanical analyzer (TMA).

[0086] If the coefficient of thermal expansion is greater than 100×10 -6 If the dimensional change is increased by 20 mm / mm / °C due to repeated temperature changes during use, the resulting stress accumulation may cause delamination of the bonding interface between the inner shell 110 and the potting parts 131 and 132 or failure of the humidifier or fuel cell including the inner shell 110 due to cracking.

[0087] The specific gravity of the inner housing 110 according to the embodiment of the present disclosure may be 1.5 g / cm 3 the following.

[0088] For example, the specific gravity of the inner case 110 may be measured according to ASTM D 792. The inner case 110 according to an embodiment of the present disclosure may have a low specific gravity while having excellent mechanical properties, which may contribute to lightweight product design.

[0089] Figure 3 is a schematic exploded perspective view of a humidifier 200 for a fuel cell according to another embodiment of the present disclosure.

[0090] Reference Figure 3 A humidifier 200 for a fuel cell according to another embodiment of the present disclosure may include an intermediate housing 210 , a first cover 221 , and a second cover 222 .

[0091] The intermediate housing 210 may have an inner space, and at least one hollow fiber membrane cassette 100 may be disposed in the inner space of the intermediate housing 210 .

[0092] The intermediate housing 210 may be box-shaped with open ends. One open end of the intermediate housing 210 may be referred to as one end, and the other open end may be referred to as the other end.

[0093] The first cover 221 may be combined with one end portion of the intermediate case 210. The second cover 222 may be combined with the other end portion of the intermediate case 210.

[0094] A resin layer 213 may be provided between the intermediate housing 210 and the hollow fiber membrane cassette 100 to fix the hollow fiber membrane cassette 100 to the intermediate housing 210. For example, the resin layer 213 may be provided at one end and the other end of the intermediate housing 210.

[0095] One space may be formed by the first cover 221 and the resin layer 213, and another space may be formed by the second cover 222 and the resin layer 213. An additional space may be formed by the resin layer 213 disposed at one end of the intermediate case 210 and the resin layer 213 disposed at the other end of the intermediate case 210.

[0096] For example, the resin layer 213 may be disposed in the inner space of the middle case 210 using a casting method. The resin layer 213 may be formed by hardening a liquid polymer such as a liquid polyurethane (PU) resin.

[0097] The intermediate housing 210 may include an exhaust gas inlet 211 and an exhaust gas outlet 212. Exhaust gas introduced into the intermediate housing 210 through the exhaust gas inlet 211 may contact the outer surface of the plurality of hollow fiber membranes 120, and may be discharged from the intermediate housing 210 through the exhaust gas outlet 212. When the exhaust gas contacts the outer surface of the plurality of hollow fiber membranes 120, moisture contained in the exhaust gas may permeate the plurality of hollow fiber membranes 120, thereby humidifying air flowing along the plurality of hollow fiber membranes 120.

[0098] Yet another embodiment of the present disclosure provides a fuel cell including a battery cell stack (not shown) and a humidifier 200 for the fuel cell connected to the battery cell stack.

[0099] Hereinafter, the present disclosure will be described with reference to more specific examples and comparative examples. However, the following examples are provided only for easy understanding of the present disclosure and do not limit the scope of the present disclosure.

[0100] <Example 1>

[0101] (1) Manufacturing of Inner Housing 110

[0102] M-PPE (Mw molecular weight: 85000) including polyphenylene ether (PPE) and polystyrene-butadiene copolymer (HIPS) was melt-molded as a polymer resin, and the inner case 110 having an internal space was manufactured.

[0103] (2) Manufacturing of Hollow Fiber Membrane Box 100

[0104] A bundle of hollow fiber membranes 120 is placed in the inner space of the inner housing 110 .

[0105] Polyurethane (PU) is prepared to form the first potting part 131 and the second potting part 132 .

[0106] The first potting part 131 is formed at one side of the inner case 110 , and the second potting part 132 is formed at the other side of the inner case 110 , thereby fixing the hollow fiber membrane 120 to the inner case 110 using a casting method.

[0107] Thus, the hollow fiber membrane cassette 100 according to Example 1 was manufactured.

[0108] <Example 2>

[0109] (1) Manufacturing of Inner Housing 110

[0110] The inner case 110 was manufactured in the same manner as (1) of Example 1, except that polyphenylsulfone (PPSU) was used instead of m-PPE.

[0111] (2) Manufacturing of Hollow Fiber Membrane Box 100

[0112] The hollow fiber membrane cassette 100 was manufactured in the same manner as (2) of Example 1, except that the inner case 110 made of polyphenylsulfone (PPSU) was used.

[0113] <Example 3>

[0114] (1) Manufacturing of Inner Housing 110

[0115] The inner case 110 was manufactured in the same manner as (1) of Example 1, except that polysulfone (PSU) was used instead of m-PPE.

[0116] (2) Manufacturing of Hollow Fiber Membrane Box 100

[0117] The hollow fiber membrane cassette 100 was manufactured in the same manner as (2) of Example 1, except that the inner case 110 made of polysulfone (PSU) was used.

[0118] <Example 4>

[0119] (1) Manufacturing of Inner Housing 110

[0120] The inner housing 110 was prepared in the same manner as (1) of Example 1, except that polyetheretherketone (PEEK) was used instead of m-PPE.

[0121] (2) Manufacturing of Hollow Fiber Membrane Box 100

[0122] The hollow fiber membrane cassette 100 was manufactured in the same manner as (2) of Example 1, except that the inner housing 110 made of polyetheretherketone (PEEK) was used.

[0123] <Example 5>

[0124] (1) Manufacturing of Inner Housing 110

[0125] The inner case 110 was manufactured in the same manner as (1) of Example 1, except that polyarylate (PAR) was used instead of m-PPE.

[0126] (2) Manufacturing of Hollow Fiber Membrane Box 100

[0127] The hollow fiber membrane cassette 100 was manufactured in the same manner as (2) of Example 1, except that the inner case 110 made of polyarylate (PAR) was used.

[0128] <Comparative Example>

[0129] (1) Manufacturing of Inner Housing 110

[0130] The inner case 110 was manufactured in the same manner as (1) of Example 1, except that polycarbonate (PC) was used instead of m-PPE.

[0131] (2) Manufacturing of Hollow Fiber Membrane Box 100

[0132] The hollow fiber membrane cassette 100 was manufactured in the same manner as (2) of Example 1, except that the inner case 110 made of polycarbonate (PC) was used.

[0133] Physical properties of the inner housing 110 and the hollow fiber membrane cassette 100 manufactured according to Examples 1 to 5 and the Comparative Example were measured. The following measuring method was used.

[0134] <Measurement of Heat Deformation Temperature (HDT)>

[0135] 1) The heat deformation temperature of the inner shell 110 manufactured according to Examples 1 to 5 and the comparative example is obtained by supporting the opposite ends of the sample in a heating bath and raising the temperature of the heating medium from room temperature (25°C) at a rate of 2°C / min while applying a predetermined bending stress with a rod in contact with the center of the sample, and measuring the temperature of the heating medium when the bending of the sample reaches a predetermined value.

[0136] 2) More specifically, the heat deformation temperature of the inner housing 110 manufactured according to Examples 1 to 5 and the comparative example was measured according to ASTM D 648. In order to measure the heat deformation temperature, the samples manufactured according to Examples 1 to 5 and the comparative example in an unannealed state with a thickness of 4 mm were prepared and placed in a heating bath as described in 1), a compressive stress of 1.8 MPa was applied to the sample while the temperature of the heating medium was increased from room temperature (25° C.) at a rate of 2° C. / min, and the temperature at which each sample was bent by 0.25 mm was measured as the heat deformation temperature (HDT).

[0137] <Measurement of moisture absorption>

[0138] The moisture absorption rates of the inner cases 110 manufactured according to Examples 1 to 5 and the Comparative Example were measured as follows.

[0139] After drying in an oven at 50° C. for 24 hours and cooling in a desiccator, the weight of the samples of the inner case 110 manufactured according to Examples 1 to 5 and the comparative example was measured as the “initial sample weight”. The sample weight after immersing the sample of the inner case 110 having the measured initial sample weight in water at 23° C. for 24 hours and taking the sample out of the water and wiping off the moisture from the surface was measured as the sample weight after moisture absorption. Subsequently, according to ASTM D 570, by comparing the “initial sample weight” with the “sample weight after moisture absorption”, the absorption amount (moisture absorption amount) of the sample of the inner case 110 was measured.

[0140] The moisture absorption rate of the inner case 110 manufactured according to Examples 1 to 5 and the comparative example was calculated according to Formula 1 below.

[0141] [Formula 1]

[0142] <Measurement of Weight Reduction Rate>

[0143] The weight reduction rates (WR) of the inner cases 110 manufactured according to Examples 1 to 5 and the Comparative Example were measured by subjecting samples of the inner cases 110 manufactured according to Examples 1 to 5 and the Comparative Example to a high temperature and high humidity treatment using an autoclave.

[0144] As high temperature and high humidity treatment conditions for measuring the weight reduction rate (WR) according to an embodiment of the present disclosure, a sample of the inner case 110 is placed in an autoclave containing water, the temperature of the autoclave is set to 120°C±3°C, and high temperature and high humidity treatment is performed for 200 hours.

[0145] The weight reduction rate (WR) of the inner case 110 manufactured according to Examples 1 to 5 and the comparative example was calculated according to Formula 2 below.

[0146] [Formula 2]

[0147]

[0148] In Formula 2, W1 is the weight of the sample of the inner case 110 before the high temperature and high humidity treatment, and W2 is the weight of the sample of the inner case 110 after the high temperature and high humidity treatment.

[0149] <Evaluation of stratification characteristics>

[0150] After the hollow fiber membrane cassette 100 manufactured according to Examples 1 to 5 and the comparative example was subjected to high temperature and high humidity treatment using an autoclave, the delamination characteristics of the hollow fiber membrane cassette 100 manufactured according to Examples 1 to 5 and the comparative example were evaluated by inspecting the delamination between the inner shell 110 and the potting parts 131 and 132.

[0151] As high temperature and high humidity treatment conditions for evaluating stratification characteristics according to an embodiment of the present disclosure, the hollow fiber membrane box 100 manufactured according to Examples 1 to 5 and the comparative example is placed in an autoclave containing water, the temperature of the autoclave is set to 120°C±3°C, and high temperature and high humidity treatment is performed for 200 hours.

[0152] When the inner case 110 and the potting parts 131 and 132 are spaced apart from each other or separated from each other, it is evaluated that delamination occurs between the inner case 110 and the potting parts 131 and 132 .

[0153] <Measurement of Coefficient of Thermal Expansion (CTE)>

[0154] The thermal expansion coefficient (CTE) of the inner case 110 manufactured according to Examples 1 to 5 and the comparative example was measured using TMA (TA Instrument, Q400).

[0155] Specifically, according to the TMA method and ASTM D 696, the linear expansion coefficients of the samples of the inner housing 110 manufactured in Examples 1 to 5 and the comparative example were measured twice at -30°C to 30°C, and the average value thereof was taken as the coefficient of thermal expansion (CTE). The size of each sample of the inner housing 110 was 6 mm (W) x 6 mm (L) x 4 mm (T), and the heating rate was 5°C / min.

[0156] <Measurement of specific gravity>

[0157] The specific gravity of the inner case 110 manufactured according to Examples 1 to 5 and the Comparative Example was measured using an underwater substitution method according to ASTM D 792 to calculate the specific gravity of each sample of the inner case 110 by measuring the mass of the sample in air and measuring the apparent mass when immersed in liquid.

[0158] The measurement results are shown in Table 1 below.

[0159] [Table 1]

[0160]

[0161] Referring to Table 1, it can be seen that the inner shell 110 and the hollow fiber membrane box 100 according to Examples 1 to 5 have excellent heat deformation temperature, excellent hydrolysis resistance, low moisture absorption rate, low thermal expansion coefficient, and low specific gravity. On the contrary, it can be seen that the inner shell 110 and the hollow fiber membrane box 100 according to the comparative example have a high thermal expansion coefficient and excellent specific gravity, but have a low heat deformation temperature and a high moisture absorption rate.

[0162] In particular, the weight reduction rate of the sample of the inner case 110 according to the comparative example was 40% after the high temperature and high humidity treatment using an autoclave.

[0163] In addition, after high temperature and high humidity treatment using an autoclave, delamination occurred between the inner case 110 and the potting parts 131 and 132 in the hollow fiber membrane cassette 100 according to the comparative example, indicating a lack of hydrolysis resistance.

[0164] The above description is only for illustrating the technical concept of the present disclosure, and it will be understood by those skilled in the art that various changes and modifications can be made without departing from the essential features of the present disclosure. In addition, the embodiments disclosed in the present disclosure are provided to describe the technical concept of the present disclosure, rather than to limit the technical concept of the present disclosure, and the scope of the technical concept of the present disclosure is not limited by the embodiments. Therefore, the protection scope of the present disclosure should be determined by the attached claims, and the technical concept within the scope equivalent to the attached claims should be interpreted as falling within the scope of the rights of the present disclosure.

[0165] [Explanation of Reference Numerals]

[0166] 100: Hollow fiber membrane box 110: Inner shell

[0167] 120: Hollow fiber membrane 121: Hollow part

[0168] 131: first potting part 132: second potting part

[0169] 200: humidifier of fuel cell 210: intermediate shell

[0170] 211: Exhaust gas inlet 212: Exhaust gas outlet

[0171] 213: resin layer 221: first cover

[0172] 222: Second cover

Claims

1. A hollow fiber membrane box, comprising: An inner shell having an inner space; a plurality of hollow fiber membranes disposed in the interior space of the inner shell; a first potting portion, disposed on one side of the inner shell, the first potting portion being configured to fix one side of each of the plurality of hollow fiber membranes; as well as a second potting portion, disposed on the other side of the inner shell, the second potting portion being configured to fix the other side of each of the plurality of hollow fiber membranes, Wherein, the thermal deformation temperature of the inner shell is above 120° C. and the moisture absorption rate is below 1%.

2. The hollow fiber membrane box according to claim 1, wherein: The moisture absorption rate of the inner shell is less than 0.5%.

3. The hollow fiber membrane box according to claim 1, wherein: The inner shell includes a polymer resin.

4. The hollow fiber membrane box according to claim 3, wherein: The polymer resin includes at least one selected from the group consisting of polyphenylene ether (PPE), polyphenylene sulfone (PPSU), polysulfone (PSU), polyetheretherketone (PEEK), and polyarylate (PAR).

5. The hollow fiber membrane box according to claim 4, wherein: The polyphenylene ether (PPE) is polyphenylene ether (m-PPE) modified by polystyrene-butadiene copolymer (HIPS).

6. The hollow fiber membrane box according to claim 5, wherein: The m-PPE includes 90 wt % to 99 wt % of polyphenylene ether (PPE) and 1 wt % to 10 wt % of polystyrene-butadiene copolymer (HIPS), based on the total weight of the m-PPE.

7. The hollow fiber membrane cassette according to claim 1, wherein: After the high temperature and high humidity treatment, the weight reduction rate of the inner shell is less than 10%, The high temperature and high humidity treatment means that the inner case is placed in an autoclave containing water, the temperature of the autoclave is set to 120° C.±3° C., and the high temperature and high humidity treatment is performed for 200 hours.

8. The hollow fiber membrane box according to claim 1, wherein: The thermal expansion coefficient of the inner shell, i.e., CTE, is 100×10 -6 mm / mm / ℃ or less.

9. The hollow fiber membrane box according to claim 1, wherein: The specific gravity of the inner shell is 1.5 g / cm 3 the following.

10. A humidifier for a fuel cell, the humidifier comprising: An intermediate housing having an inner space, an exhaust gas inlet and an exhaust gas outlet; The hollow fiber membrane box according to any one of claims 1 to 9, wherein the hollow fiber membrane box is arranged in the internal space of the intermediate shell; A first cover coupled to one end of the intermediate housing; and The second cover is combined with the other end of the intermediate housing.

11. A fuel cell comprising: Battery cell stack; as well as The humidifier for a fuel cell according to claim 10, wherein the humidifier is connected to the battery cell stack.

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