Apparatus for manufacturing water electrolysis membrane and method for manufacturing water electrolysis membrane using same

Abstract

The present invention relates to an apparatus for manufacturing a water electrolysis membrane and method for manufacturing a water electrolysis membrane using same, and can provide a water electrolysis membrane having excellent physical properties, such as low sheet resistance, low hydrogen permeability, and excellent durability, compared to conventional commercial membranes.

Description

Manufacturing device for electrolytic membrane and manufacturing method for electrolytic membrane using the same

[0001] The present invention relates to a manufacturing device for a separation membrane for electrolysis and a manufacturing method for a separation membrane for electrolysis using the same.

[0002]

[0003] Hydrogen is categorized into gray hydrogen, blue hydrogen, and green hydrogen, depending on its production method and raw materials. Gray hydrogen refers to byproduct hydrogen from the petrochemical and steel industries, as well as extracted hydrogen (reformed hydrogen) produced by reforming natural gas. Gray hydrogen accounts for the largest proportion of hydrogen production methods today and is significantly cheaper than blue and green hydrogen. However, it has the disadvantages of relatively high carbon emissions and limited production of byproduct hydrogen.

[0004] Blue hydrogen refers to hydrogen produced through a process that minimizes carbon emissions by utilizing carbon capture, utilization, and storage (CCUS) technology to capture and store the carbon emitted during gray hydrogen production. While it is more expensive to produce than gray hydrogen, it has the advantage of lower carbon emissions.

[0005] Green hydrogen, which produces no carbon emissions, is considered a future-oriented energy technology essential for a carbon-neutral future. Electricity generated from renewable sources like solar and wind power is added to water to produce hydrogen and oxygen, making it an environmentally friendly energy source with zero carbon dioxide emissions throughout the entire process.

[0006] Producing green hydrogen, an environmentally friendly energy source with zero carbon emissions, requires water electrolysis technology. Water electrolysis is an electrochemical technology that generates hydrogen and oxygen by electrolyzing water and moving ions through a membrane.

[0007] Currently, countries around the world are racing to develop key materials and technologies to ensure the economic feasibility of green hydrogen production. The most crucial material in water electrolysis is the membrane, which prevents the hydrogen and oxygen produced during electrolysis from mixing. Hydrogen is extremely small and light, allowing it to pass through any substance. However, there is a risk of hydrogen and oxygen mixing through the pores of the membrane. Because mixing more than 4% hydrogen with oxygen can cause an explosion, the membrane must have low permeability to both hydrogen and oxygen gases.

[0008] Previously, the Zifron membrane developed by Agfa (Belgium) was used as a commercial membrane. Zifron membranes are composed of zirconia nanopowder (40 nm), polysulfone polymer, and polyphenylene sulfide (PPS) mesh, and have been widely used as alkaline water electrolysis membranes due to their excellent performance. However, commercial membranes have the disadvantages of an uneven distribution of hydrophilic ceramic particles and a loose microstructure, resulting in low ionic conductivity and difficulty in suppressing the mixing of hydrogen and oxygen. Furthermore, the conventional slot-die-based manufacturing process has limitations due to the poor penetration of high-viscosity slurry into the micropores of the porous support.

[0009] Meanwhile, Korean Patent No. 10-1339702 relates to a web-reinforced separator membrane for electrochemical applications, and discloses a process for continuously manufacturing web-reinforced separator diaphragms in which the web is properly embedded within the diaphragm. Specifically, the method involves coating a paste (organo-mineral) onto a web (woven or non-woven) using a roller. However, this coating method has the problem that it is difficult to uniformly coat the entire interior of the web. Furthermore, it is difficult to clearly determine the characteristics and effects of the membrane manufactured depending on the manufacturing process.

[0010] Accordingly, the present invention aims to provide a manufacturing device and manufacturing method for a separation membrane that can contribute to improving the efficiency and stability of electrolysis.

[0011]

[0012] The present invention provides an apparatus for manufacturing a water electrolysis separation membrane having excellent physical properties and a method for continuously manufacturing a water electrolysis separation membrane using the same.

[0013]

[0014] The apparatus for manufacturing a water electrolysis membrane according to the present invention is a chamber-type coating apparatus for a water electrolysis membrane, and may include: a chamber formed inside the coating apparatus; a porous support inlet formed in a first direction of the coating apparatus and connected to the chamber; an outlet formed in a direction opposite to the first direction and connected to the chamber; and one or more slurry inlets formed on one surface of the coating apparatus and connected to the chamber.

[0015] The above chamber can be connected to the porous support inlet, slurry inlet and outlet and liquid sealing by high viscosity slurry.

[0016] The major axis diameter of the above chamber may be larger than the major axis inner diameters of the porous support inlet and outlet.

[0017] The major axis diameter of the above chamber may be larger than the inner diameter of the slurry inlet.

[0018] The short axis diameter of the inlet and outlet of the porous support may be 200 to 1000 μm.

[0019] The major axis diameter of the inlet and outlet of the porous support may be 100 to 2000 mm.

[0020] The above slurry inlet may include two or more.

[0021] The two or more slurry inlets may be positioned in opposite directions to each other.

[0022] The method for manufacturing a water electrolysis membrane using the above-described device for manufacturing a water electrolysis membrane may include the steps of: supplying slurry to one or more slurry inlets formed on one surface of a chamber-type coating device; introducing a film-type porous support into a porous support inlet formed in a first direction of the coating device; coating the porous support with the slurry within a chamber formed inside the coating device; extruding the porous support coated with the slurry through an outlet formed in a direction opposite to the first direction; and solidifying the porous support extruded through the outlet to manufacture a water electrolysis membrane.

[0023] The above slurry may have a solid content in the organic solvent of 30 to 80 wt%.

[0024] The organic solvent may include at least one selected from the group consisting of N-methyl-2-pyrrolidone (NMP), dimethylformamide (DMF), dimethylacetamide (DMAC), and dimethyl sulfoxide (DMSO).

[0025] The above solid content may include 60 to 95 wt% of nanoparticles and 5 to 40 wt% of polymer.

[0026] The above nanoparticles may include at least one selected from the group consisting of ZrO2, ZrSiO3, Zr(HPO2)4, TiO2, BaTiO3, CeO2, SiO2, Al2O3, CaCO3 and mixtures thereof.

[0027] The above polymer may include at least one selected from the group including polysulfone, polyamide, polyimide, polyester, polypropylene, polyethylene, polybenzimidazole, polyvinylidene difluoride, and polyacrylic.

[0028] The above porous support may include at least one selected from the group consisting of PPS (polyphenylene sulfide) mesh, PP (polypropylene) mesh, PE (polyethylene) mesh, and PTFE (polytetrafluoroethylene) mesh.

[0029] The porous support may have a porosity of 30 to 70%.

[0030] The transport speed of the above porous support may be 1.0 to 20.0 mm / s.

[0031] The chamber can be connected to the porous support inlet, slurry inlet and outlet and liquid sealing by the slurry.

[0032] When the porous support passes through a chamber filled with the slurry, the slurry can be uniformly coated throughout the interior of the porous support by the internal pressure of the chamber.

[0033] Coagulation of the above porous support can be performed under non-solvent conditions by a non-solvent-induced phase separation phenomenon.

[0034] In the above non-solvent conditions, the non-solvent may include one or more selected from the group consisting of distilled water, 2-pyrrolidone (2P), N-methyl-2-pyrrolidone (NMP), dimethylformamide (DMF), dimethylacetamide (DMAC), dimethyl sulfoxide (DMSO), and mixtures thereof.

[0035] In addition, the electrolytic membrane manufactured by the above method for manufacturing the electrolytic membrane may include 60 to 95 wt% of nanoparticles and 5 to 40 wt% of polymer.

[0036] The above nanoparticles may include at least one selected from the group consisting of ZrO2, ZrSiO3, Zr(HPO2)4, TiO2, BaTiO3, CeO2, SiO2, Al2O3, CaCO3 and mixtures thereof.

[0037] The above polymer may include at least one selected from the group including polysulfone, polyamide, polyimide, polyester, polypropylene, polyethylene, polybenzimidazole, polyvinylidene difluoride, and polyacrylic.

[0038] Characteristic viscosity (μ) c ,) can have values ​​from 2.5 to 20.

[0039] Effective feed ratio (F) e ) can have values ​​from 0.8 to 5.

[0040] The pressure at the bubble point can have a value of 2.16 to 10 bar.

[0041] Area resistance is 0.05 to 0.26 Ω cm 2 can have a value of .

[0042] Hydrogen permeability (H2crossover) is 1·10 -13 18.5·10 -12 mol cm -1 s -1 bar -1 can have a value of .

[0043] The Figure of Merit can have a value between 8.3 and 50.

[0044]

[0045] The apparatus for manufacturing a water electrolysis membrane according to the present invention and the method for manufacturing a water electrolysis membrane using the same have excellent economic feasibility by continuously manufacturing a water electrolysis membrane, and can greatly contribute to the development of domestic membrane manufacturing technology by enabling domestic production of membranes that were previously dependent on imports.

[0046] The electrolytic separation membrane according to the present invention has low surface resistance, low hydrogen permeability, and excellent durability, and thus can provide a electrolytic separation membrane having superior physical properties compared to conventional commercial separation membranes.

[0047]

[0048] Figure 1 is a conceptual diagram showing a manufacturing device for a water electrolysis separation membrane according to the present invention and a manufacturing method for a water electrolysis separation membrane using the same.

[0049] Figures 2 and 3 show the coating coverage according to the effective feed ratio.

[0050] Figure 4 shows the Figure of Merit (FoM) according to the characteristic viscosity.

[0051] Figure 5 shows the thickness and bubble point according to position.

[0052] Figure 6 shows the change in physical properties according to the effective feed ratio.

[0053] Figure 7 shows the change in physical properties according to the gap distance.

[0054] Figure 8 shows the cross-section and surface of the membrane according to solid content.

[0055] Figure 9 shows the cross-section and surface of the separation membrane according to the gap distance.

[0056]

[0057] The embodiments described herein may be modified in various different forms, and the technology according to one embodiment is not limited to the embodiments described below. In addition, the embodiments of one embodiment are provided to more completely explain the present disclosure to a person with average knowledge in the relevant technical field. In this case, unless there is a different definition for the technical and scientific terms used, they have the meaning commonly understood by a person with ordinary skill in the technical field to which this invention belongs, and in the following description and the attached drawings, descriptions of well-known functions and configurations that may unnecessarily obscure the gist of the present invention are omitted.

[0058] Additionally, the singular forms used in this specification and the appended claims are intended to include the plural forms as well, unless the context clearly dictates otherwise.

[0059] Additionally, in this specification and the appended claims, the terms first, second, etc. are not used in a limiting sense, but are used for the purpose of distinguishing one component from another.

[0060] Additionally, in this specification and the appended claims, when a part such as a film (layer), region or component is said to be located “on,” “above,” “upper,” “below,” “lower,” or “lower” another part, this includes not only cases where one part is in contact with another part, but also cases where another part exists between the two parts.

[0061] In addition, the terms "about," "substantially," and the like used in this specification and the appended claims are used in a meaning that is at or close to the numerical value when manufacturing and material tolerances inherent in the meanings stated are presented, and are used to prevent unscrupulous infringers from unfairly utilizing the disclosure in which exact or absolute values ​​are stated to aid in the understanding of this specification and the appended claims.

[0062] Additionally, the numerical ranges used herein include lower and upper limits and all values ​​within that range, increments logically derived from the shape and width of the defined range, all doubly defined values, and all possible combinations of upper and lower limits of numerical ranges defined in different shapes.

[0063] Furthermore, in this specification and the appended claims, terms such as “include” or “have” mean that a feature or component described in the specification is present, and unless specifically limited, do not preclude the possibility that one or more other features or components may be added.

[0064]

[0065] Hereinafter, the manufacturing apparatus for a water electrolysis separation membrane of the present invention and the manufacturing method for a water electrolysis separation membrane using the same will be described in detail with reference to the attached drawings.

[0066]

[0067] Figure 1 is a conceptual diagram showing a manufacturing device for a water electrolysis separation membrane according to the present invention and a manufacturing method for a water electrolysis separation membrane using the same.

[0068] According to one embodiment of the present invention, a manufacturing device for a water electrolysis separation membrane is a chamber-type coating device, comprising: a chamber formed inside the coating device; a porous support inlet formed in a first direction of the coating device and connected to the chamber; an outlet formed in a direction opposite to the first direction and connected to the chamber; and one or more slurry inlets formed on one surface of the coating device and connected to the chamber.

[0069] The above chamber-type coating device is designed for the present invention, and can easily control the coating thickness in the range of tens of nanometers to hundreds of micrometers by adjusting the spacing of the discharge ports.

[0070] In the above coating device, the first direction is not particularly limited, and is preferably from the top to the bottom of the coating device.

[0071] The chamber is connected to the porous support inlet, the slurry inlet, and the outlet through a liquid seal by a high viscosity slurry. When the porous support supplied through the porous support inlet passes through the chamber filled with the slurry, the slurry is uniformly coated throughout the interior of the porous support by the internal pressure of the chamber.

[0072] The major axis diameter of the chamber is larger than the major axis inner diameters of the porous support inlet and outlet, and is also larger than the inner diameter of the slurry inlet.

[0073] The short axis diameter of the porous support inlet and outlet is 200 to 1000 μm, preferably 400 to 800 μm, more preferably 550 to 650 μm. The long axis diameter of the porous support inlet and outlet is 100 to 2000 mm, preferably 100 to 1000 mm, more preferably 200 to 500 mm, and even more preferably 300 to 400 mm.

[0074] The above slurry inlet may include two or more, and the two or more slurry inlets are positioned in directions opposite to each other.

[0075]

[0076] A method for manufacturing a water electrolysis membrane using the manufacturing device for the water electrolysis membrane according to one embodiment of the present invention includes the steps of: supplying slurry to at least one slurry inlet formed on one surface of a chamber-type coating device; supplying a film-type porous support to a porous support inlet formed in a first direction of the coating device; coating the porous support with the slurry within a chamber formed inside the coating device; extruding the porous support coated with the slurry through an outlet formed in a direction opposite to the first direction; and solidifying the porous support extruded through the outlet to manufacture a water electrolysis membrane.

[0077] The above slurry is a solid dispersion containing nanoparticles and polymers in an organic solvent, and the solid content is 30 to 80 wt%, preferably 50 to 70 wt%. If the solid content is lower than 30 wt%, the pores of the manufactured porous membrane are excessively large, resulting in insufficient strength and gas barrier properties. If the solid content is higher than 80 wt%, the viscosity of the slurry is too high, resulting in poor quality of the porous membrane.

[0078] The organic solvent may be used without limitation on type as long as it can dissolve the solid. For example, it may include at least one selected from the group consisting of N-methyl-2-pyrrolidone (NMP), dimethylformamide (DMF), dimethylacetamide (DMAC), and dimethyl sulfoxide (DMSO), and preferably, N-methyl-2-pyrrolidone (NMP) may be used, but is not limited thereto.

[0079] The above solid content may comprise 60 to 95 wt% of nanoparticles and 5 to 40 wt% of polymer, and preferably 80 to 90 wt% of nanoparticles and 10 to 20 wt% of polymer.

[0080] The above nanoparticles include at least one selected from the group consisting of ZrO2, ZrSiO3, Zr(HPO2)4, TiO2, BaTiO3, CeO2, SiO2, Al2O3, CaCO3 and mixtures thereof, and ZrO2 may be preferably used, but is not limited thereto.

[0081] The above polymer includes at least one selected from the group including polysulfone, polyamide, polyimide, polyester, polypropylene, polyethylene, polybenzimidazole, polyvinylidene difluoride, and polyacrylic, and preferably, polysulfone (PSU) can be used, but is not limited thereto.

[0082] The above porous support includes at least one selected from the group consisting of PPS (polyphenylene sulfide) mesh, PP (polypropylene) mesh, PE (polyethylene) mesh, and PTFE (polytetrafluoroethylene) mesh, and preferably, PPS mesh can be used, but is not limited thereto.

[0083] The porous support has a porosity of 30 to 70%, 45 to 55%, and a thickness of 50 to 500 μm, preferably 250 to 350 μm.

[0084] The porous support is supplied through the porous support inlet, and the transport speed of the porous support is 1.0 to 20.0 mm / s, preferably 1.5 to 10.0 mm / s, and more preferably 1.8 to 2.0 mm / s.

[0085] The chamber is connected to the porous support inlet, the slurry inlet, and the outlet through a liquid seal by the slurry. When the porous support supplied through the porous support inlet passes through the chamber filled with the slurry, the slurry is uniformly coated throughout the interior of the porous support by the internal pressure of the chamber.

[0086] The porous support coated with the above slurry is extruded through the outlet of the coating device and solidified under non-solvent conditions. This is called non-solvent induced phase separation (NIPS), and a polymer solution dissolved in an appropriate solvent is brought into contact with a non-solvent, and the polymer precipitates through mutual material exchange between the solvent and non-solvent, thereby producing a separation membrane.

[0087] In the above non-solvent conditions, the non-solvent includes at least one selected from the group consisting of distilled water, 2-pyrrolidone (2P), N-methyl-2-pyrrolidone (NMP), dimethylformamide (DMF), dimethylacetamide (DMAC), dimethylsulfoxide (DMSO), and mixtures thereof, and preferably, distilled water can be used, but is not limited thereto.

[0088] In the above non-solvent conditions, the temperature and time are not particularly limited, and the temperature may be 10 to 100°C, but is preferably 20 to 30°C, and the time is, for example, 1 to 24 hours, preferably 4 to 6 hours.

[0089]

[0090] Referring to Figure 1, dimensionless parameters according to the present invention are as follows: F i is the feed rate of the slurry (mL s) -1), t is the thickness of the porous support (thickness of support, mm), ρ is the porosity of the porous support (porosity of support, %), d is the gap distance (gap distance, mm), w is the width of the porous support (width of support, mm), V is the transport speed of the porous support (roll speed, mm s -1 )am.

[0091] Characteristic viscosity (μ) reflecting the structural characteristics of the chamber-type coating device designed for the present invention c ) was introduced. The characteristic viscosity represents the fluid flow of high viscosity slurry inside the chamber and is defined by the following [Equation 1]. Since the viscosity of the slurry has the characteristic of changing very greatly depending on the solid content, the viscosity of the slurry was corrected using a logarithmic function.

[0092] Characteristic viscosity (μ) of a water electrolysis separation membrane according to one embodiment of the present invention c ) is 2.5 to 20, preferably 4 to 10, more preferably 5 to 6.

[0093]

[0094]

[0095]

[0096] In the above [Formula 1], F e is the effective feed ratio, and is defined by the following [Equation 2]. The effective feed ratio represents the actual feed rate compared to the theoretical required feed rate. If this value is greater than 1, a high pressure is applied inside the chamber, so that the entire inside of the porous support is uniformly coated. Conversely, if it is less than 1, the pressure inside the chamber is reduced, so that the inside of the porous support is not uniformly coated.

[0097] Effective supply speed (F) of a water electrolysis separation membrane according to one embodiment of the present invention e) is 0.8 to 5, preferably 0.9 to 2, more preferably 1.0 to 1.2.

[0098]

[0099]

[0100]

[0101] In the above [Formula 1], L c is the characteristic length and is defined by the following [Equation 3]. The characteristic length is the thickness (gap between outlets) of the slurry coated on the porous support relative to the thickness of the porous support, and is a parameter that reflects the geometric characteristics of the electrolysis membrane.

[0102]

[0103]

[0104]

[0105] According to the present invention, the supply speed of the slurry (F i ) and the porous support transport speed (V), the coating coverage can be controlled, and the thickness of the membrane can be adjusted by the gap distance. In addition, the properties of the membrane ultimately obtained vary depending on the viscosity and solid content of the slurry.

[0106] The bubble point pressure refers to the gas permeability of a membrane against a force induced by differential pressure. A higher pressure indicates a better ability to withstand the gas pressure difference between the cathode and anode of an alkaline water electrolysis system. According to one embodiment of the present invention, the bubble point pressure is 2.16 to 10 bar, preferably 3 to 8 bar, and more preferably 5 to 6 bar.

[0107] In a thin film with a uniform thickness overall, if the thickness is very small, it can be considered as a two-dimensional surface, and the resistance per unit area is called area resistance. A lower area resistance value means better conductivity. The area resistance according to one embodiment of the present invention is 0.05 to 0.26 Ω cm. 2 , preferably 0.1 to 0.2 Ω cm 2 , more preferably 0.15 to 0.17 Ω cm 2 am.

[0108] In water electrolysis, a membrane acts as a barrier to prevent hydrogen and oxygen from meeting. However, some hydrogen may pass through the membrane and mix with oxygen, causing an explosion. Therefore, the membrane must have low hydrogen gas permeability. A lower hydrogen permeability (H2crossover) value indicates lower hydrogen gas permeability. The hydrogen permeability of a water electrolysis membrane according to one embodiment of the present invention is 1·10 -13 18.5·10 -12 mol cm -1 s -1 bar -1 , preferably 1·10 -13 10 / 10 -12 mol cm -1 s -1 bar -1 , more preferably 1·10 -13 May 10th -12 mol cm -1 s -1 bar -1 am.

[0109] The figure of merit (Figure of Merit) indicates the properties of the coating area and quality, with a higher figure of merit indicating better properties. The figure of merit of the electrolysis membrane according to one embodiment of the present invention is 8.3 to 50, preferably 20 to 40, and more preferably 30 to 35.

[0110] Hereinafter, specific examples and experimental examples will be described. However, the examples and experimental examples described below are only illustrative, and the technology described in this specification is not limited thereto.

[0111]

[0112] <Example 1>

[0113] ZrO2 nanoparticles and polysulfone were mixed at a weight ratio of 85:15 using a planetary mixer to prepare a solid. The solid was dissolved in NMP (N-Methyl-2-pyrrolidone) to prepare a slurry so that the solid content was 50 wt%. The slurry was coated on both sides of a porous support using the manufacturing apparatus of the present invention. The porous support is a PPS mesh with a porosity of 50%, a thickness of 300 μm, and a width of 350 nm. In the manufacturing apparatus, the outlet spacing is 600 μm, the transport speed of the porous support is 1.9 mm / s, and the effective supply speed is 0.46. The porous support coated with the slurry was solidified by immersing it in a water bath filled with distilled water at 25°C for more than 5 hours to prepare a separation membrane for water electrolysis.

[0114]

[0115] <Example 2>

[0116] It was manufactured in the same manner as Example 1, except that the effective supply speed was changed to 0.80.

[0117]

[0118] <Example 3>

[0119] It was manufactured in the same manner as in Example 1, except that the effective supply speed was changed to 1.07.

[0120]

[0121] <Example 4>

[0122] It was manufactured in the same manner as in Example 1, except that the effective supply speed was changed to 1.60.

[0123]

[0124] <Example 5>

[0125] It was prepared in the same manner as in Example 1, except that the slurry was diluted with NMP so that the solid content of the slurry became 52 wt%.

[0126]

[0127] <Example 6>

[0128] It was manufactured in the same manner as Example 5, except that the effective supply speed was changed to 0.80.

[0129]

[0130] <Example 7>

[0131] It was manufactured in the same manner as Example 5, except that the outlet spacing was changed to 500 μm and the effective supply speed was changed to 1.07.

[0132]

[0133] <Example 8>

[0134] It was manufactured in the same manner as Example 5, except that the effective supply speed was changed to 1.07.

[0135]

[0136] <Example 9>

[0137] It was manufactured in the same manner as Example 5, except that the outlet spacing was changed to 700 μm.

[0138]

[0139] <Example 10>

[0140] It was manufactured in the same manner as Example 5, except that the effective supply speed was changed to 1.60.

[0141]

[0142] <Example 11>

[0143] It was prepared in the same manner as in Example 1, except that the slurry was diluted with NMP so that the solid content of the slurry became 54 wt%.

[0144]

[0145] <Example 12>

[0146] It was manufactured in the same manner as Example 11, except that the effective supply rate was changed to 0.80 in Example 11.

[0147]

[0148] <Example 13>

[0149] It was manufactured in the same manner as Example 11, except that the effective supply speed was changed to 1.07.

[0150]

[0151] <Example 14>

[0152] It was manufactured in the same manner as Example 11, except that the effective supply speed was changed to 1.60.

[0153]

[0154] [Table 1] shows the process conditions according to Examples 1 to 14.

[0155]

[0156] Solids Content (%) Viscosity (cP, shear rate = 1) Effective Feed Speed ​​Outlet Spacing (μm) Example 150 134, 900 0.46600 Example 250 134, 900 0.80600 Example 350 134, 900 1.07600 Example 450 134, 900 1.60600 Example 55 2203 2000.46600 Example 65 2203 2000.80600 Example 75 2203 2001.07500 Example 85 2203 2001.07600 Example 95 2203 2001.07700 Example 1052203,2001.60600 Example 1154301,6000.46600 Example 1254301,6000.80600 Example 1354301,6001.07600 Example 1454301,6001.60600

[0157]

[0158] The surface resistance, bubble point, and hydrogen permeability of the membranes manufactured in Examples 1 to 14 were measured.

[0159]

[0160] <Experimental Example 1> Area resistance measurement

[0161] Sheet resistance was measured using an impedance measuring device, ZIVE MP2A (ZIVE), and an H-cell SB100B (Neoscience). Using the H-cell, the sample was kept in a 30% KOH solution at 30°C for 1 hour, and then measured using the two-probe method. A lower sheet resistance value indicates better conductivity.

[0162]

[0163] <Experimental Example 2> Bubble point measurement

[0164] The bubble point was measured using a bubble point check device. After placing the membrane in a pressure cell, nitrogen gas was pressurized under the membrane. The membrane was submerged in water to prevent gas from passing through any portion of the membrane other than the portion that passes through it. The pressure at which nitrogen gas penetrated the membrane and bubbles were generated was measured. The bubble point pressure represents the membrane's gas permeability against the force induced by the differential pressure. A higher pressure indicates a greater ability to withstand the gas pressure difference between the cathode and anode of an alkaline water electrolysis system.

[0165]

[0166] <Experimental Example 3> Measurement of hydrogen permeability (H2 crossover)

[0167] Hydrogen permeability was measured using a membrane permeation device (HY-SM-C-1109). After placing the membrane in the hydrogen permeability measurement cell, a 30% KOH aqueous solution was added. The 30% KOH aqueous solution was added to the hydrogen permeability measurement device, and the operating temperature was set to 30°C. The weight of the permeated 30% KOH aqueous solution was measured within each differential pressure range of 0.1 bar to 0.5 bar, and the hydrogen permeability was calculated based on the following [Equations 4] and [Equations 5]. A lower hydrogen permeability value indicates lower permeability to hydrogen gas.

[0168]

[0169]

[0170]

[0171] In the above [Formula 4] is the hydrogen solubility, is the hydrogen partial pressure, is the volumetric permeability, which is defined by the following [Equation 5].

[0172]

[0173]

[0174]

[0175] In the above [Formula 5] is the water flux, is the pressure difference.

[0176]

[0177] <Experimental Example 4> Measurement of coating coverage

[0178] The coating application area represents the area on the porous support where the slurry is actually coated depending on the effective supply rate, and is defined by [Equation 6] below.

[0179]

[0180]

[0181]

[0182] <Experimental Example 5> Measurement of the Figure of Merit (FOM)

[0183] The performance index was calculated using the values ​​measured in <Experimental Example 1>, <Experimental Example 2>, and <Experimental Example 4>, and is defined by [Formula 7] below.

[0184]

[0185]

[0186]

[0187] [Table 2] shows the measurement results of Examples 1 to 14.

[0188]

[0189] Coating coverage (%) Bubble point (Bar) Surface resistance (Ω cm) 2 )Hydrogen permeability (10 -12 mol cm -1 s -1 bar -1) Performance Index Characteristics Viscosity Example 1701.960.1767.055.42.35 Example 21002.410.2666.939.14.10 Example 31003.410.1266.25275.49 Example 41003.280.2516.9713.18.23 Example 521.41.80.1277.581.82.44 Example 694.32.4360.1066.2219.34.25 Example 71003.8320.1934.7919.98.52 Example 81005.1940.1602.2232.55.68 Example 91004.4560.2403.5218.64.26Example 101002.630.1616.0316.38.49Example 1161.43.290.1195.487.72.52Example 1288.63.4880.0834.9727.54.38Example 131002.8940.1334.8921.85.86Example 141003.0060.1455.1320.78.77Conventional commercial membrane-2.160.2618.58.3-

[0190]

[0191] Referring to [Table 2], the hydrogen permeability (H2 crossover) of Examples 1 to 14 is 18.5·10 that of conventional commercial membranes. -12 mol cm -1 s -1 bar -1 It was measured lower. Therefore, it was confirmed that Examples 1 to 14 had lower hydrogen permeability than conventional commercial separation membranes.

[0192] Figures 2 and 3 show the coating coverage according to the effective feed ratio. Effective feed ratio (F e ) the area on the support where the slurry is actually coated varies. F e When F was 0.46, the area of ​​slurry coated on the support was small, and F e Even when F was 0.80, the slurry was not completely coated on the support. However, F eWhen F is 1.07 and 1.6, the slurry is completely coated on the support. Therefore, F e The coating application range can be controlled through .

[0193] Figure 4 shows the Figure of Merit (FoM) according to the characteristic viscosity. Characteristic viscosity (μ c ) was less than 2.5, the performance index decreased rapidly, and when it exceeded 2.5, it showed a higher performance index than the conventional commercial separation membrane.

[0194] Figure 5 shows the thickness and bubble point according to position. As the solid content of the slurry increases, the thickness increases, and the difference according to position is not large, so it was confirmed that the coating was constant. The bubble point is constant and does not have a large difference according to position when the solid content of the slurry is 52%, and F e The highest value was confirmed when 1.07 was used.

[0195] Figure 6 shows the change in physical properties according to the effective feed ratio. The thickness is F at the solid concentration of all slurries. e As the temperature increases, the bubble point and surface resistance tend to increase. e There was no direct correlation with .

[0196] Figure 7 shows the changes in physical properties according to the gap distance. The slurry solids content was 52 wt%, and the effective feed rate was 1.07, and the bubble point and sheet resistance were measured according to the gap distance. The sheet resistance was lowest at 600 μm, and the bubble point was highest at 600 μm. Therefore, the best physical properties were observed when the gap distance was 600 μm.

[0197] Figure 8 shows the cross-section and surface of the membrane according to the solid content. The effective feed rate is 1.07. When the solid content of the slurry is 50 wt%, the membrane surface is uneven, and ZrO2 particles are observed on the membrane surface. When the solid content of the slurry is 52 wt%, it can be confirmed that the epitaxial layer on the membrane surface is formed best.

[0198] Figure 9 illustrates the cross-section and surface of the membrane according to the outlet gap distance. The effective feed rate is 1.07, and the slurry solids content is 52 wt%. It was confirmed that the epitaxial layer on the membrane surface was formed most densely at an outlet gap distance of 600 μm.

[0199]

[0200] Although the present invention has been described in this specification with specific details and limited examples, these are provided only to help a more general understanding of the present invention, and the present invention is not limited to the above examples, and those skilled in the art to which the present invention pertains can make various modifications and variations based on these descriptions. Therefore, the ideas described in this specification should not be limited to the described examples, and all things that are equivalent or equivalent to the claims below, as well as the claims, are considered to fall within the scope of the ideas described in this specification.

Claims

1. A chamber-type coating device for a water electrolysis membrane, A chamber formed inside the above coating device; A porous support inlet formed in the first direction of the coating device and connected to the chamber; An outlet formed in a direction opposite to the first direction and connected to the chamber; and One or more slurry inlets formed on one surface of the coating device and connected to the chamber; A manufacturing device for a water electrolysis separation membrane including:

2. In paragraph 1, The above chamber is a manufacturing device for a separation membrane for electrolysis, which is connected to the porous support inlet, the slurry inlet and the outlet and the liquid seal by the high viscosity slurry.

3. In paragraph 1, A manufacturing device for a water electrolysis separation membrane, wherein the major axis diameter of the chamber is larger than the major axis inner diameters of the inlet and outlet of the porous support.

4. In paragraph 1, A manufacturing device for a separation membrane for electrolysis, wherein the major axis diameter of the chamber is larger than the inner diameter of the slurry inlet.

5. In paragraph 1, A manufacturing device for a water electrolysis separation membrane, wherein the short axis diameters of the inlet and outlet of the porous support are 200 to 1000 μm.

6. In paragraph 1, A manufacturing device for a water electrolysis separation membrane, wherein the major axis diameters of the inlet and outlet of the porous support are 100 to 2000 mm.

7. In paragraph 1, A manufacturing device for a water electrolysis separation membrane comprising two or more slurry inlets.

8. In paragraph 7, A manufacturing device for a water electrolysis separation membrane, wherein the two or more slurry inlets are positioned in opposite directions to each other.

9. A step of supplying slurry to one or more slurry inlets formed on one surface of a chamber-type coating device; A step of introducing a film-shaped porous support into a porous support inlet formed in the first direction of the coating device; A step of coating the porous support with the slurry within a chamber formed inside the coating device; A step of extruding a porous support coated with the above slurry through an outlet formed in a direction opposite to the first direction; and A step of manufacturing a separation membrane for water electrolysis by solidifying a porous support extruded through the above outlet; A method for manufacturing a water electrolysis separation membrane comprising:

10. In paragraph 9, The above slurry is a method for manufacturing a separation membrane for water electrolysis having a solid content of 30 to 80 wt% in an organic solvent.

11. In paragraph 10, A method for producing a membrane for electrolysis, wherein the organic solvent comprises at least one selected from the group consisting of N-methyl-2-pyrrolidone (NMP), dimethylformamide (DMF), dimethylacetamide (DMAC), and dimethyl sulfoxide (DMSO).

12. In paragraph 10, A method for producing a water electrolysis separation membrane, wherein the solid content comprises 60 to 95 wt% of nanoparticles and 5 to 40 wt% of polymer.

13. In paragraph 12, The above nanoparticles are ZrO 2 , ZrSiO 3 , Zr(HPO 2 ) 4 , TiO 2 , BaTiO 3 , CeO 2 , SiO 2 , Al 2 O 3 , CaCO 3 A method for producing a water electrolysis membrane comprising at least one selected from the group consisting of: and mixtures thereof.

14. In paragraph 12, A method for manufacturing a water electrolysis separation membrane, wherein the polymer comprises at least one selected from the group consisting of polysulfone, polyamide, polyimide, polyester, polypropylene, polyethylene, polybenzimidazole, polyvinylidene difluoride, and polyacrylic.

15. In paragraph 9, A method for manufacturing a separation membrane for water electrolysis, wherein the porous support comprises at least one selected from the group consisting of PPS (polyphenylene sulfide) mesh, PP (polypropylene) mesh, PE (polyethylene) mesh, and PTFE (polytetrafluoroethylene) mesh.

16. In paragraph 15, The above porous support is a method for manufacturing a separation membrane for water electrolysis having a porosity of 30 to 70%.

17. In paragraph 15, A method for manufacturing a water electrolysis separation membrane, wherein the transport speed of the porous support is 1.0 to 20.0 mm / s.

18. In paragraph 9, A method for manufacturing a water electrolysis separation membrane, wherein the chamber is connected to the porous support inlet, the slurry inlet and the outlet and the liquid seal by the slurry.

19. In paragraph 18. A method for manufacturing a water electrolysis separation membrane, wherein when the porous support passes through a chamber filled with the slurry, the slurry is uniformly coated throughout the entire inside of the porous support by the internal pressure of the chamber.

20. In paragraph 19, A method for manufacturing a membrane for electrolysis, wherein coagulation of the porous support is performed under non-solvent conditions by a non-solvent-induced phase separation phenomenon.

21. In paragraph 20, A method for producing a membrane for water electrolysis, wherein the nonsolvent, under the above nonsolvent conditions, comprises at least one selected from the group consisting of distilled water, 2-pyrrolidone (2P), N-methyl-2-pyrrolidone (NMP), dimethylformamide (DMF), dimethylacetamide (DMAC), dimethyl sulfoxide (DMSO), and mixtures thereof.

22. A water electrolysis separation membrane manufactured by the method of any one of claims 9 to 21.

23. In paragraph 22, A membrane for water electrolysis comprising 60 to 95 wt% of nanoparticles and 5 to 40 wt% of polymer.

24. In paragraph 23, The above nanoparticles are ZrO 2 , ZrSiO 3 , Zr(HPO 2 ) 4 , TiO 2 , BaTiO 3 , CeO 2 , SiO 2 , Al 2 O 3 , CaCO 3 A membrane for electrolysis comprising at least one selected from the group consisting of: and mixtures thereof.

25. In paragraph 23, A water electrolysis separation membrane comprising at least one polymer selected from the group consisting of polysulfone, polyamide, polyimide, polyester, polypropylene, polyethylene, polybenzimidazole, polyvinylidene difluoride, and polyacrylic.

26. In paragraph 22, Characteristic viscosity (μ) c ) is a water electrolysis separation membrane having a value of 2.5 to 20.

27. In paragraph 22, Effective feed ratio (F) e ) is a water electrolysis separation membrane having a value of 0.8 to 5.

28. In paragraph 22, A membrane for electrolysis of water having a bubble point pressure of 2.16 to 10 bar.

29. In paragraph 22, Area resistance is 0.05 to 0.26 Ω cm. 2 A membrane for electrolysis having a value of .

30. In paragraph 22, Hydrogen permeability (H 2 crossover) is 1·10 -13 18.5·10 -12 mol cm -1 s -1 bar -1 A membrane for electrolysis having a value of .

31. In paragraph 22, A water electrolysis membrane having a figure of merit value of 8.3 to 50.

Images