Method for manufacturing hybrid-structured titanium porous transport layer, and hybrid type titanium porous transport layer manufactured using same

Abstract

The present invention relates to a method for manufacturing a titanium porous transport layer. Disclosed in one embodiment of the present invention is the method for manufacturing a hybrid-structured titanium porous transport layer, comprising: a first step of preparing slurries by mixing, for each titanium powder classified by particle size, a plasticizer, an antifoaming agent, a dispersant and an organic binder; a second step of performing ball milling in order to mix each of the slurries; a third step of evaluating, after the second step, whether the viscosity of each of the slurries is suitable; a fourth step of producing a green sheet by laminating, in two layers, slurries having different titanium powder particle sizes; and a fifth step of degreasing and sintering the green sheet.

Description

Method for manufacturing a titanium porous transfer membrane with a hybrid structure and a hybrid type titanium porous transfer membrane manufactured therefrom

[0001] The present invention relates to a method for manufacturing a titanium porous transfer membrane, and more specifically, to a method for manufacturing a titanium porous transfer membrane having differences in roughness and pore size on both sides of a sintered product using titanium powder having different particle sizes, and to a titanium porous transfer membrane produced thereby.

[0002] Global demand for hydrogen is expected to increase significantly to reduce carbon emissions, and various technologies are being researched to produce it. Among these technologies, proton exchange membrane water electrolysis systems are attracting attention due to their ability to produce high-purity hydrogen, ease of high-pressure operation, and high efficiency.

[0003] However, proton exchange membrane (PEM) water electrolysis systems have the disadvantages of high cost and short lifespan due to the use of precious metal catalysts. Therefore, continuous research is required on electrode materials that reduce the amount of precious metal catalysts used in PEM systems while possessing high electrolysis performance and long-term durability.

[0004] In proton exchange membrane (MEA) water electrolysis systems, the porous transport layer (PTL) adopts a porous structure for the flow of fluids and gases. The PTL must possess high conductivity for efficient electron transfer and low surface roughness to avoid damaging the catalyst layer of the MEA. To develop such porous structures, research and development of porous sintered products utilizing various metal materials, such as mesh, fiber, and powder, is being conducted.

[0005] The present invention aims to provide a method for manufacturing a hybrid type titanium porous transfer membrane that secures sufficient porosity through the difference in physical properties between the two surfaces of the titanium porous transfer membrane, thereby enabling the smooth flow of water, which is a raw material for a water electrolysis system, increases the specific surface area between the titanium porous transfer membrane and the catalyst contact surface, and seeks to reduce interfacial resistance.

[0006] Meanwhile, a titanium porous transfer membrane manufactured according to this manufacturing method is presented.

[0007] Other detailed objectives of the present invention will be clearly understood and grasped by experts or researchers in the art through the specific details described below.

[0008] To solve the above problem, the present invention provides, as an example, a method for manufacturing a titanium porous transfer membrane of a hybrid structure comprising: a first step of preparing a slurry by mixing a plasticizer, an antifoaming agent, a dispersant, and an organic binder for titanium powders classified by different particle sizes; a second step of performing a ball milling process for mixing each of the slurries; a third step of evaluating whether the viscosity of each of the slurries is suitable after the second step; a fourth step of producing a green sheet by stacking slurries of different titanium powder particle sizes in two layers; and a fifth step of degreasing and sintering the green sheet.

[0009] Here, the titanium powders with different particle sizes are divided into a large particle group with large particle sizes and a small particle group with small particle sizes, the small particle group may consist of titanium powder with a particle size of 10 μm to 25 μm, and the large particle group may consist of powders with a particle size of 35 μm to 60 μm.

[0010] Meanwhile, the above fourth step can form the green sheet by utilizing lamination and rolling processes.

[0011] In addition, the above fourth step can form the green sheet by utilizing a tape casting process.

[0012] In addition, the fourth step above may form the green sheet through a spray coating process in which a spray solution is prepared by mixing a slurry : solvent = 1 : n (where n = 1 to 3) and the spray solution is sprayed onto a sintered layer created with one of the slurries.

[0013] Furthermore, the solvent may be a mixture of ethanol and toluene with a viscosity that can pass through a spray nozzle.

[0014] In addition, the above fifth step may degrease and sinter the green sheet at a temperature between 1000℃ and 1150℃.

[0015] Meanwhile, to solve the above problem, the present invention provides, as an example, a titanium porous transport membrane of a hybrid structure comprising a double structure in which a small particle layer and a large particle layer composed of titanium powders of different particle sizes are stacked, wherein the small particle layer comprises titanium powder with a particle size of 10 to 25 μm and the large particle layer comprises titanium powder with a particle size of 35 to 60 μm.

[0016] Here, the difference in roughness between the small particle layer and the large particle layer is 2.5 μm or more, and the roughness of the small particle layer may be less than 3 μm.

[0017] Furthermore, the porosity including the small particle layer and the large particle layer may be 45–65%, the bending strength may be 150–300 MPa, and the electrical conductivity may be 2.5 × 10⁻⁶ 3 It may be greater than S / cm.

[0018] Meanwhile, the above-mentioned small particle layer may be located on the surface in contact with the catalyst layer, and the above-mentioned large particle layer may be located on the surface in the direction of water inflow.

[0019] The present invention enables the smooth flow of water by ensuring sufficient porosity on each surface, thereby realizing a difference in physical properties between the two surfaces of a hybrid-type titanium porous transfer membrane utilizing powder sintering. Furthermore, it exhibits the effect of increasing the specific surface area between the titanium porous transfer membrane and the catalyst contact surface and reducing interfacial resistance.

[0020] Other effects of the present invention will be clearly grasped and understood by experts or researchers in the art through the specific details described below or during the process of implementing the present invention.

[0021] FIG. 1 is a flowchart illustrating a method for manufacturing a titanium porous transfer membrane according to an embodiment of the present invention.

[0022] FIG. 2 is a schematic diagram showing each processing method for forming a double-structured titanium porous transfer membrane.

[0023] FIG. 3 shows enlarged images of each part of a transfer membrane produced according to an embodiment of the present invention.

[0024] The features and effects of the present invention described above will become clearer through the following detailed description in conjunction with the attached drawings, and accordingly, a person skilled in the art to which the present invention pertains will be able to easily implement the technical concept of the present invention. Since the present invention is susceptible to various modifications and may take various forms, specific embodiments are illustrated in the drawings and described in detail in the text. However, this is not intended to limit the present invention to specific disclosed forms, and it should be understood that it includes all modifications, equivalents, and substitutions that fall within the spirit and scope of the present invention. The terms used in this application are used merely to describe specific embodiments and are not intended to limit the present invention.

[0025] Hereinafter, a method for manufacturing a titanium porous transfer membrane with a hybrid structure according to one embodiment of the present invention and a titanium porous transfer membrane with a hybrid structure manufactured therefrom will be described in detail with reference to the drawings.

[0026] FIG. 1 is a flowchart showing a method for manufacturing a titanium porous transfer membrane with a hybrid structure according to an embodiment of the present invention.

[0027] A method for manufacturing a titanium porous transfer membrane of a hybrid structure according to an embodiment of the present invention comprises: i) a first step of manufacturing slurries with titanium powders classified by different particle sizes; ii) a second step of performing ball mill processing; iii) a third step of evaluating whether the viscosity of the slurry is suitable; iv) a fourth step of manufacturing a green sheet of a double structure with different slurries; and v) a fifth step of degreasing and sintering the green sheet.

[0028] Specifically, the first step involves preparing a slurry by mixing a plasticizer, an antifoaming agent, a dispersant, and an organic binder for titanium powders classified by different particle sizes.

[0029] Titanium powder can be prepared by dividing it into a large particle group with a large particle size and a small particle group with a small particle size, ranging from 10㎛ to 100㎛. For example, the small particle group can be composed of titanium powder with a particle size of 10㎛ to 25㎛, and the large particle group can be composed of powders with a particle size of 35㎛ to 60㎛.

[0030] The size ranges of titanium powders specifying the small particle group and the large particle group can be made so that they do not overlap, thereby clearly revealing the difference in particle size between the small particle group and the large particle group. These particle size ranges of the small particle group and the large particle group can be varied depending on the required physical properties, etc.

[0031] Plasticizers combine with organic binders to improve the processability of the entire mixture, which can help ensure a uniform thickness during the molding process. For example, diethylhexyl phthalate (DEHP) or dibutyl phthalate (DBP) can be used.

[0032] Meanwhile, the vesicle suppresses bubbles to prevent density non-uniformity during the molding process, and polydimethylsiloxane (PDMS) or alkyl esters can be used.

[0033] Polyvinyl alcohol (PVA) or polyethylene glycol (PEG) can be used as dispersants to eliminate aggregation of titanium powder and increase flowability and safety.

[0034] Polyvinyl acetal (PVA), polypropylene (PP), or cellulose-based binders can be used as organic binders to help bind titanium powder and form a green sheet.

[0035] At this time, it is preferable that the solid content of the slurry produced through the first step be 50% to 90%.

[0036] The solid content affects the viscosity of the slurry and the pore size in the sintered product. If the solid content is less than 50%, the viscosity is too low, making it difficult to form a green sheet, and if the solid content exceeds 90%, the viscosity is too high, making it difficult to form a thin green sheet.

[0037] The second stage, the ball milling process, is a process of uniformly mixing titanium powder by dispersing it through physical impact and friction; it modifies the surface of the particles through mechanical action and induces uniform mixing.

[0038] After going through the second step, a third step is performed to evaluate whether the viscosity of each of the above slurries is suitable.

[0039] The slurry produced through the ball milling of the second stage must have an appropriate level of viscosity according to the specific method for producing a green sheet with a two-layer structure having different titanium powder particle sizes in the fourth stage.

[0040] For example, the suitable viscosity of the mixed slurry can be set to a range of 100 cP to 2000 cP suitable for coating.

[0041] The processing method of the fourth stage is one of the lamination and rolling process, double tape casting process, and spray coating process, and in the third stage, the operator evaluates whether each selected process has the appropriate viscosity required for it.

[0042] Referring to Fig. 2, in the fourth step, a green sheet with a two-layer structure having different particle sizes of titanium powder is manufactured.

[0043] In FIG. 2(a), the lamination and rolling process first produces each slurry into green sheets with thicknesses ranging from 10 µm to 80 µm and 200 µm to 350 µm through a tape casting coating process.

[0044] After manufacturing green sheets with different titanium particle sizes, each green sheet is dried and the solvent used is removed first. To do this, they can be sufficiently dried in a drying oven at approximately 80°C for more than 1 hour.

[0045] Afterward, the dried green sheets (a, b) are stacked vertically and then passed through a rolling roller in a lamination and rolling process to produce a double-structured green sheet with different titanium powder particle sizes on the upper and lower surfaces.

[0046] Referring to Figure 2(b), a tape casting process can be used as another process for producing a green sheet.

[0047] First, a small particle green sheet (b) with a thickness of 10㎛ to 80㎛ can be manufactured by first applying a slurry having small particles using a tape casting coating process. At this time, the tape-cast green sheet is dried inside the equipment during the process. In addition, an appropriate temperature can be set for this purpose.

[0048] After manufacturing a green sheet (b) of small particles, a slurry composed of large particles is applied secondarily on top of it to manufacture a green sheet (a, b) with a total thickness of 200㎛ to 400㎛.

[0049] Afterwards, the green sheets (a, b) can be sufficiently dried in a drying oven at approximately 80°C for more than 1 hour to dry the sheets and remove the solvent used.

[0050] Referring to Figure 2(c), a spray coating process can be used as another green sheet manufacturing process.

[0051] To do this, a single layer sintered body (a) having large particles is first prepared, and then a slurry (b) having small particles can be spray-coated on it.

[0052] At this time, the ink for spray coating is composed of a solvent mixed with a slurry, and can be prepared as a spray solution mixed with a slurry : solvent = 1 : n (where n = 1 to 3). This spray solution is sprayed onto a single layer of sintered layer having large particles to form a layer on the sintered layer.

[0053] Meanwhile, the solvent may be a mixture of ethanol and toluene with a viscosity that can pass through the spray nozzle.

[0054] Through these three processes, a hybrid titanium porous transport membrane can be formed by stacking layers of large particles and layers of small particles.

[0055] Step 5 is a degreasing and sintering heat treatment process, in which the green sheet produced in Step 4 is processed at 900°C to 1200°C with a profile adjusted to ensure sufficient sinterability. At this time, the temperature and heating time can be adjusted according to the desired thickness and porosity of the sintered product. To ensure better performance, degreasing and sintering heat treatment can be performed in a temperature range of 1000°C to 1150°C.

[0056] If the process is carried out at a temperature below 1000℃, the brittleness may increase due to insufficient sintering, and if it exceeds 1150℃, over-sintering may occur in the small particles because two different particles are used.

[0057] A hybrid titanium porous transfer membrane can be manufactured through such a process. The manufactured titanium porous transfer membrane is in a hybrid form in which a layer of large particles and a layer of small particles are stacked, and Figure 3 shows enlarged images of each part of the transfer membrane produced according to an embodiment of the present invention.

[0058] Next, an example of a method for manufacturing a titanium porous transfer membrane with a hybrid structure according to one embodiment of the present invention will be described in detail. The following example is merely illustrative of one form of the present invention, and the scope of the present invention is not limited by the following example.

[0059] Example 1

[0060] Among titanium powders with a particle size of 10㎛ to 100㎛, the powder was divided into a small particle group with a particle size of 10㎛ to 20㎛ and a large particle group with a particle size of 50㎛ to 60㎛, and a slurry was prepared using each powder, and a single layer green sheet with a thickness of 10㎛ to 80㎛ and 200㎛ to 350㎛, respectively, was prepared using each slurry.

[0061] A hybrid type green sheet was produced by laminating the manufactured green sheets and rolling them by 3% to 15%. This was heat-treated at a temperature between 1000°C and 1150°C to produce a hybrid type titanium porous transfer membrane with a difference in roughness on both sides.

[0062] Example 2

[0063] A hybrid type titanium porous transfer membrane was manufactured using the same process as in Example 1, except that among titanium powders with particle sizes of 10㎛ to 100㎛, the powder was divided into a small particle group with particle sizes of 10㎛ to 20㎛ and a large particle group with particle sizes of 35㎛ to 45㎛, and a slurry was prepared using each powder.

[0064] Example 3

[0065] A hybrid type titanium porous transfer membrane was manufactured using the same process as in Example 1, except that among titanium powders with a particle size of 10㎛ to 100㎛, the powder was divided into a small particle group with a particle size of 15㎛ to 25㎛ and a large particle group with a particle size of 50㎛ to 60㎛, and a slurry was prepared using each powder.

[0066] Comparative Example 1

[0067] A hybrid type titanium porous transfer membrane was manufactured using the same process as in Example 1, except that among titanium powders with a particle size of 10㎛ to 100㎛, the powder was divided into a small particle group with a particle size of 15㎛ to 25㎛ and a large particle group with a particle size of 30㎛ to 40㎛, and a slurry was prepared using each powder.

[0068] Example 4

[0069] A slurry was prepared using small particles with a particle size of 10㎛ to 20㎛ among titanium powders with a size of 10㎛ to 100㎛. The viscosity of the prepared slurry must be sufficiently thin (<300 cP, 25 ℃), and a green sheet with a thickness of 10㎛ to 50㎛ was produced using tape casting coating equipment.

[0070] Meanwhile, a slurry is prepared using large particles with a particle size of 50㎛ to 60㎛. The viscosity of the prepared slurry is 1000cP to 3000cP, and a green sheet with a thickness of 200 to 350㎛ is produced on a green sheet prepared with small particles using this.

[0071] This was dried at 80°C and heat-treated at a temperature between 1000°C and 1150°C to produce a hybrid type titanium porous transfer membrane with a double structure having different particles on the upper and lower surfaces.

[0072] Example 5

[0073] A hybrid type titanium porous transfer membrane was prepared using the same process as in Example 4, except that among titanium powders with a size of 10㎛ to 100㎛, a slurry was prepared using small particles with a particle size of 15㎛ to 25㎛, while a slurry was prepared using large particles with a particle size of 50 to 60㎛.

[0074] Comparative Example 2

[0075] A hybrid type titanium porous transfer membrane was prepared using the same process as in Example 4, except that among titanium powders with a size of 10㎛ to 100㎛, a slurry was prepared using small particles with a particle size of 15㎛ to 25㎛, while a slurry was prepared using large particles with a particle size of 30 to 40㎛.

[0076] Example 6

[0077] Particle size (D 50A slurry is prepared using titanium powder having a thickness of 50㎛ to 60㎛, and a green sheet is produced through a tape casting process. The sheet is then heat-treated at a temperature between 1000℃ and 1150℃ to first produce a single sintered layer. The thickness of the single sintered layer produced in this way is 150㎛ to 180㎛.

[0078] After that, particle size (D 50 Another slurry is prepared using titanium powder with a small particle size of 10㎛ to 20㎛, and then a solvent is mixed to prepare a spray solution for spray coating.

[0079] The solvent used at this time is a mixed solvent of ethanol and toluene, and a spray solution with a viscosity of 100 cP or less is prepared by setting the ratio of slurry to solvent to approximately 1:n (n = 1 to 3). First, a spray solution is applied to a thickness of 10 to 80 μm using a spray coating process on a single-layer sintered layer (titanium powder particle size of 50 μm to 60 μm) prepared earlier, and then heat treatment is performed at a temperature of 1000°C to 1150°C for 1 to 3 hours to produce a hybrid titanium porous transport membrane with a double structure having different particle sizes.

[0080] Comparative Example 3

[0081] Particle size (D 50 A slurry is prepared using titanium powder having a particle size of 30㎛ to 40㎛, and a green sheet is produced through a tape casting process, and the particle size (D) is prepared. 50 A dual-structure hybrid titanium porous transport membrane having different particle sizes was prepared using the same process as in Example 6, except that another slurry was prepared using titanium powder with a small particle size of 10㎛ to 20㎛.

[0082] Comparative Example 4

[0083] Particle size (D 50A slurry is prepared using titanium powder having a particle size of 25㎛ to 35㎛, and a green sheet is produced through a tape casting process, and the particle size (D) 50 A dual-structure hybrid titanium porous transport membrane having different particle sizes was prepared using the same process as in Example 6, except that another slurry was prepared using titanium powder with a small particle size of 10㎛ to 20㎛.

[0084] In this way, by utilizing two types of titanium powders with different particle sizes in the embodiments of the present invention, it is possible to manufacture a hybrid titanium porous transfer membrane having low roughness in the catalyst layer and high roughness in the direction of flow channel input, as the physical properties of both sides differ depending on the required thickness and porosity.

[0085] Evaluation example

[0086] The physical properties of the hybrid type titanium porous transfer membranes prepared according to the examples and comparative examples were measured and evaluated. The mechanical strength of the hybrid type titanium porous transfer membranes was measured by cutting them according to ASTM D790 standards (Product name: AG-X plus Manufacturer: SHIMADZU EUROPA), and the porosity was calculated based on the density values.

[0087] First, the thickness, density, electrical conductivity, strength, and porosity of Examples 1 to 3 and Comparative Example 1, which were manufactured through the same lamination and rolling processes, were measured and are shown in Table 1.

[0088] Separated powder particles (D 50 , μm) Thickness (μm) Density (g / cm³) 3 ) Illuminance (㎛) Electrical conductivity (10 3S / cm) Strength (MPa) Porosity (%) Microparticles Alleles Microparticles Alleles Example 1 10~20 50~60 250~260 2.38 2.79 5.42 4.52 175~185 47.1 Example 2 10~20 35~45 265~275 2.44 2.85 5.5 14.41 165~175 46.0 Example 3 15~25 50~60 255~265 2.23 2.96 5.53 4.07 150~155 50.5 Comparative Example 1 15~25 30~40 240~250 2.96 2.34 3.07 6.91 435~440 34.0

[0089]

[0090] Since the manufactured titanium porous transfer membrane has different roughness on both sides, it can be arranged so that the catalyst layer has low roughness and the side where water is injected has high roughness to facilitate smooth flow.

[0091] At this time, it is preferable to set the roughness of the layer formed by the fine particles to less than 3 μm and the difference in roughness to 2.5 μm or more. By doing so, the contact resistance with the catalyst layer is reduced, and the flow of independent materials in each layer is promoted. The examples confirmed that this is satisfied.

[0092] Meanwhile, the examples have a porosity range of 45–65%, a strength range of 150–300 MPa, and an electrical conductivity of 2.5 × 10⁻⁶ 3 It was confirmed that the examples satisfied this when the S / cm level was set to above. On the other hand, the comparative example is expected to have poor material flow due to the small difference in roughness and low porosity.

[0093] In addition, the examples were found to have a strength of 150 to 185 MPa and a porosity of 46 to 50.5%, confirming that the strength and porosity were relatively well-balanced.

[0094] Meanwhile, for Example 4, Comparative Example 2, and Comparative Example 3 manufactured by the tape casting coating method, the thickness, density, electrical conductivity, strength, and porosity were measured and are shown in Table 2.

[0095] Separated powder particles (D 50, μm) Thickness (μm) Density (g / cm³) 3 ) Illuminance (㎛) Electrical conductivity (10 3 S / cm) Strength (MPa) Porosity (%) Microparticles Alleles Microparticles Alleles Example 4 10~20 50~60 300~310 2.5 0 2.6 5 6.0 6 5.2 2230~235 45.6 Example 5 15~25 50~60 275~285 2.3 42.9 15.5 9 4.2 01 65~175 48.1 Comparative Example 2 15~25 30~40 230~240 2.5 6 2.4 6 3.8 75.1 2260~270 43.2

[0096] In the examples of hybrid type transfer membranes manufactured through double tape casting, the strength is 165 to 235 MPa and the porosity is 45.6 to 48.1%. It was also confirmed to have appropriate roughness and electrical conductivity. In contrast, Comparative Example 2 was found to have a small difference in roughness and low porosity.

[0097] Meanwhile, for Example 6, Comparative Example 3, and Comparative Example 4 manufactured by spray coating, thickness, density, electrical conductivity, strength, and porosity were measured and are shown in Table 3.

[0098] Separated powder particles (D 50 , μm) Thickness (μm) Density (g / cm³) 3 ) Illuminance (㎛) Electrical conductivity (10 3 S / cm) Strength (MPa) Porosity (%) Alloles Microparticles Microparticles Alloles Example 6 10~20 50~60 230 1.65 2.45 5.10 2.73 150~160 63.3 Comparative Example 3 10~20 30~40 270 2.65 2.78 4.69 5.53 185~195 41.2 Comparative Example 4 10~20 25~35 240 2.94 1.95 3.79 6.31 315~325 34.8

[0099] The titanium porous transfer membrane prepared according to Example 6 has a strength of 150 to 160 MPa depending on the thickness and a porosity of 63.3%. In this way, it was confirmed that the porosity of the titanium porous transfer membrane of Example 3, prepared through a spray coating process, can be significantly increased. On the other hand, the comparative examples have low porosity, so material transport is expected to be inefficient.

[0100] Overall, observing the physical properties of the examples and comparative examples, there is a tendency for strength to increase and porosity to decrease as the size difference between small and large particles decreases. Additionally, it was confirmed that as the density of the manufactured hybrid titanium porous transport membrane increases, both strength and electrical conductivity tend to increase.

[0101] In addition, among various physical properties, the roughness of small particles is set to less than 3㎛ and the roughness difference to 2.5㎛ or more, while the porosity range standard is set to 45~65% and the strength range standard is set to 150~300MPa, and the electrical conductivity standard is 2.5×10⁻⁶ 3 It was confirmed that the examples satisfy this when set to S / cm or higher.

[0102] Although the detailed description of the present invention described above has been explained with reference to preferred embodiments of the invention, those skilled in the art or those with ordinary knowledge in the relevant technical field will understand that various modifications and changes can be made to the present invention without departing from the spirit and technical scope of the invention as described in the claims set forth below.

Claims

1. A first step of preparing a slurry by mixing a plasticizer, an antifoaming agent, a dispersant, and an organic binder according to titanium powders classified by different particle sizes, A second step of performing a ball mill process for mixing each of the above slurries, A third step of evaluating whether the viscosity of each of the above slurries is suitable after undergoing the above second step, Step 4, which involves producing a green sheet by stacking slurries of titanium powder with different particle sizes into two layers, and A fifth step comprising degreasing and sintering the above green sheet Method for manufacturing a titanium porous transfer membrane with a hybrid structure.

2. In Paragraph 1, The above titanium powders, which differ in particle size, are divided into a large particle group with large particle size and a small particle group with small particle size, and The small particle group consists of titanium powder with a particle size of 10㎛ to 25㎛, and the large particle group consists of powders with a particle size of 35㎛ to 60㎛. Method for manufacturing a titanium porous transfer membrane with a hybrid structure.

3. In Paragraph 1, The above fourth step is characterized by forming the green sheet using lamination and rolling processes. Method for manufacturing a titanium porous transfer membrane with a hybrid structure.

4. In Paragraph 1, The above fourth step is characterized by forming the green sheet using a tape casting process. Method for manufacturing a titanium porous transfer membrane with a hybrid structure.

5. In Paragraph 1, The above fourth step is A spray solution is prepared by mixing slurry : solvent = 1 : n (where n = 1 to 3), and Characterized by forming the green sheet through a spray coating process in which the spray solution is sprayed onto a sintered layer formed from a certain slurry. Method for manufacturing a titanium porous transfer membrane with a hybrid structure.

6. In Paragraph 5, The above solvent is characterized by being a mixture of ethanol and toluene with a viscosity that can pass through a spray nozzle. Method for manufacturing a titanium porous transfer membrane with a hybrid structure.

7. In Paragraph 1, The above 5th step is Characterized by degreasing and sintering the above green sheet at a temperature between 1000℃ and 1150℃. Method for manufacturing a titanium porous transfer membrane with a hybrid structure.

8. It includes a double structure comprising a stacked small particle layer and a large particle layer composed of titanium powders of different particle sizes, and The above-mentioned small particle layer comprises titanium powder with a particle size of 10 to 25 μm, and The above-mentioned large particle layer comprises titanium powder with a particle size of 35 to 60 μm. Hybrid structure titanium porous transfer membrane.

9. In Paragraph 8, A titanium porous transport membrane of a hybrid structure characterized in that the difference in roughness between the small particle layer and the large particle layer is 2.5 μm or more, and the roughness of the small particle layer is less than 3 μm.

10. In Paragraph 9, A titanium porous transport membrane of a hybrid structure characterized by a porosity of 45 to 65% including the small particle layer and the large particle layer.

11. In Paragraph 10, A titanium porous transfer membrane of a hybrid structure characterized by a bending strength of 150 to 300 MPa.

12. In Paragraph 11, Electrical conductivity is 2.5×10 3 A titanium porous transfer membrane of a hybrid structure characterized by having a S / cm or higher.

13. In Paragraph 8, The above small particle layer is located on the surface in contact with the catalyst layer, and the above large particle layer is located on the surface in the direction of water inflow. Hybrid structure titanium porous transfer membrane.

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