Preparation method of polyphenylene sulfide fabric separator, polyphenylene sulfide fabric separator and its application

Abstract

This invention provides a method for preparing a polyphenylene sulfide (PPS) fabric separator, the PPS fabric separator itself, and its applications, specifically relating to the field of separator material technology. The preparation method includes the following steps: A) sulfonating PPS yarn, then impregnating the sulfonated PPS yarn in an organic solvent containing a polysulfone polymer, followed by a first induced phase separation to obtain yarn containing a polysulfone polymer layer; B) weaving the yarn containing the polysulfone polymer layer into a fabric, subjecting the fabric to a second impregnation, a second induced phase separation, washing, and drying to obtain the PPS fabric separator. This invention introduces hydrophilic functional groups into the PPS yarn through sulfonation treatment, enhancing the fiber's hydrophilicity and adhesion to the coating. The yarn is then impregnated in a polysulfone polymer solution to form a polysulfone polymer coating. After fabrication, another induced phase separation is performed to form a network polysulfone polymer structure, reducing the pore size of the PPS fabric separator and improving its airtightness.

Description

Technical Field

[0001] This invention relates to the field of membrane material technology, and in particular to a method for preparing a polyphenylene sulfide fabric membrane, the polyphenylene sulfide fabric membrane, and its applications. Background Technology

[0002] The diaphragm plays a crucial role in alkaline water electrolyzers. Located between the anode and cathode, its main function is to prevent the oxygen generated at the anode from mixing with the hydrogen generated at the cathode, thereby ensuring gas purity and improving current efficiency and overall safety.

[0003] PPS (polyphenylene sulfide), as a high-performance fiber material, possesses excellent thermal stability, chemical stability, and dimensional stability, as well as a large specific surface area. These properties make it an ideal material for manufacturing diaphragms for alkaline water electrolysis to produce hydrogen. However, PPS fabric diaphragms still face some challenges in practical applications:

[0004] 1. Requirement for Hydrophilic Modification: PPS is inherently hydrophobic, which does not meet the hydrophilicity requirements of water electrolyzers. To improve this property, PPS needs hydrophilic modification treatment. Currently, methods such as plasma treatment and concentrated sulfuric acid treatment are widely used to enhance the hydrophilicity of PPS. These treatments can introduce hydrophilic functional groups onto the fabric surface, thereby improving the hydrophilicity of the membrane. However, during electrolysis, especially in environments with strong bubble formation, the hydrophilicity of the fabric may gradually decrease over time, potentially leading to a gradual increase in energy consumption.

[0005] 2. Pore size and airtightness issues: Fabrics made from PPS fibers have relatively large pore sizes, resulting in poor airtightness. The key function of the diaphragm is to strictly isolate the hydrogen and oxygen generated at the cathode and anode, while allowing OH-... - Ions move freely within the electrolyzer. If the membrane is not airtight enough, hydrogen and oxygen may interpenetrate, causing safety issues. A common method to improve membrane airtightness is to increase the thickness of the fabric. However, this increases the membrane's sheet resistance, thus increasing energy consumption.

[0006] Despite the many advantages of PPS materials in membrane manufacturing, issues such as hydrophilic modification and airtightness improvement still need to be addressed to enhance their performance and safety in alkaline water electrolyzers.

[0007] In view of this, the present invention is hereby proposed. Summary of the Invention

[0008] One of the objectives of this invention is to provide a method for preparing a polyphenylene sulfide fabric separator, which aims to solve at least one of the above-mentioned technical problems in the prior art.

[0009] The second objective of this invention is to provide a polyphenylene sulfide fabric separator.

[0010] The third objective of this invention is to provide an application of polyphenylene sulfide fabric separators.

[0011] To solve the above-mentioned technical problems, the present invention adopts the following technical solution:

[0012] A first aspect of the present invention provides a method for preparing a polyphenylene sulfide fabric separator, comprising the following steps:

[0013] A. Sulfonate the polyphenylene sulfide yarn, then impregnate the sulfonated polyphenylene sulfide yarn in an organic solvent of polysulfone polymer, and separate the first induced phase to obtain a yarn containing a polysulfone polymer layer.

[0014] B. The yarn containing the polysulfone polymer layer is woven into a fabric, and the fabric is subjected to a second impregnation, a second induced phase separation, washing and drying to obtain a polyphenylene sulfide fabric diaphragm.

[0015] Furthermore, the sulfonation treatment is performed using a sulfonating agent.

[0016] Preferably, the sulfonating agent comprises concentrated sulfuric acid.

[0017] Preferably, the concentrated sulfuric acid has a mass concentration of 90-98%.

[0018] Preferably, the sulfonation treatment is performed at a temperature of 70–90°C for a time of 5–40 minutes.

[0019] Furthermore, the mass concentration of the organic solution of the polysulfone polymer is ≤40%, preferably 10-40%.

[0020] Preferably, the polysulfone polymer includes at least one of polysulfone, sulfonated polysulfone, polyphenylsulfone, sulfonated polyphenylsulfone, sulfonated polyethersulfone, and polyethersulfone.

[0021] Preferably, the organic solvent of the polysulfone polymer includes at least one of N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, N-ethylpyrrolidone, acetonitrile, and dimethyl sulfoxide.

[0022] Preferably, the temperature of the first impregnation is 60-80°C and the time is 5-30 minutes.

[0023] Furthermore, the first induced phase separation and the second induced phase separation are each independently induced phase separations using non-solvent methods.

[0024] Preferably, the non-solvent is a solvent that cannot dissolve polysulfone polymers.

[0025] Preferably, the non-solvent includes water.

[0026] Furthermore, the non-solvent-induced phase separation process includes: immersing the impregnated yarn or fabric in a water bath in pure water to obtain the phase-separated yarn or fabric.

[0027] Furthermore, the second impregnation reagent includes at least one of N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, N-ethylpyrrolidone, acetonitrile, and dimethyl sulfoxide.

[0028] Preferably, the temperature of the second impregnation is 40-60°C and the time is 5-30 minutes.

[0029] Preferably, the water bath temperature is 70–90°C and the time is 1–5 minutes.

[0030] Furthermore, the fabric has a warp density of 25 to 80 threads per inch and a weft density of 15 to 50 threads per inch.

[0031] Preferably, the fabric comprises a plain woven fabric.

[0032] Furthermore, the manufacturing process of the polyphenylene sulfide yarn is as follows:

[0033] The polyphenylene sulfide fiber is spun into the polyphenylene sulfide yarn through a cotton spinning process of cotton cleaning, carding, drawing, roving, spinning, winding, twisting, and heat setting.

[0034] Preferably, the length of the polyphenylene sulfide fiber is 30-60 mm.

[0035] Preferably, the fineness of the polyphenylene sulfide fiber is 0.5 to 3.0 dtex.

[0036] A second aspect of the present invention provides a polyphenylene sulfide fabric separator, which is prepared by the preparation method described in the first aspect.

[0037] The third aspect of the present invention provides the application of the polyphenylene sulfide fabric diaphragm in an alkaline water electrolyzer.

[0038] Compared with the prior art, the present invention has at least the following beneficial effects:

[0039] The preparation method provided by this invention first involves sulfonating the polyphenylene sulfide (PPS) yarn, introducing highly polar functional groups such as sulfoxide (-SO-) and sulfone (-SO2-) groups onto the fiber surface. This not only enhances the hydrophilicity of the PPS fiber but also strengthens the adhesion between the fiber and subsequent coatings due to their strong polarity. Next, the sulfonated PPS yarn is impregnated in an organic solution of a polysulfone polymer. As an amorphous polymer, the sulfone and sulfoxide groups in the main chain of the polysulfone polymer impart superior hydrophilicity and good acid and alkali resistance to PPS. After impregnation in the polysulfone polymer solution, a polysulfone polymer coating is formed on the fiber surface using a solvent-inducible phase separation technique. Subsequently, the yarn coated with the polysulfone polymer is fabricated. To further optimize the airtightness of the diaphragm, the fabric was immersed in a solvent and subjected to non-solvent-induced phase separation again. This resulted in a network structure formed inside and on the surface of the fabric by the polysulfone polymer coating, which made the pore size of the fabric diaphragm smaller and significantly improved its airtightness.

[0040] The polyphenylene sulfide (PPS) fabric separator provided by this invention achieves two major technological breakthroughs: high airtightness and superhydrophilicity. The average pore size of the separator is controlled at a fine scale of less than 5 μm. This characteristic is crucial for preventing the interpenetration of hydrogen and oxygen, thereby ensuring the safety of the electrolysis process. The sheet resistivity of this separator is less than 0.15 Ω / cm. 2 It has a rapid hydrophilic response, which significantly reduces the internal resistance of the application environment and improves efficiency.

[0041] The application of the polyphenylene sulfide (PPS) fabric diaphragm provided by this invention, given its surface structure and chemical stability, enables it to maintain stable hydrophilicity during alkaline water electrolysis, reducing energy consumption and extending service life. This combination of technical advantages not only improves the economics of hydrogen production through water electrolysis but also provides a reliable guarantee for the long-term stable operation of the electrolyzer. Detailed Implementation

[0042] To make the objectives, technical solutions, and advantages of this invention clearer, the technical solutions in the embodiments of this invention will be clearly and completely described below in conjunction with the embodiments of this invention. Obviously, the described embodiments are only some embodiments of this invention, and not all embodiments. The components of the embodiments of this invention can be arranged and designed in various different configurations.

[0043] A first aspect of the present invention provides a method for preparing a polyphenylene sulfide fabric separator, comprising the following steps:

[0044] A. Sulfonate the polyphenylene sulfide yarn, then impregnate the sulfonated polyphenylene sulfide yarn in an organic solvent of polysulfone polymer, and separate the first induced phase to obtain a yarn containing a polysulfone polymer layer.

[0045] B. The yarn containing the polysulfone polymer layer is woven into a fabric, and the fabric is subjected to a second impregnation, a second induced phase separation, washing and drying to obtain a polyphenylene sulfide fabric diaphragm.

[0046] The preparation method provided by this invention first involves sulfonating the polyphenylene sulfide (PPS) yarn, introducing highly polar functional groups such as sulfoxide (-SO-) and sulfone (-SO2-) groups onto the fiber surface. This not only enhances the hydrophilicity of the PPS fiber but also strengthens the adhesion between the fiber and subsequent coatings due to their strong polarity. Next, the sulfonated PPS yarn is impregnated in an organic solution of a polysulfone polymer. As an amorphous polymer, the sulfone and sulfoxide groups in the main chain of the polysulfone polymer impart superior hydrophilicity and good acid and alkali resistance to PPS. After impregnation in the polysulfone polymer solution, a polysulfone polymer coating is formed on the fiber surface using a solvent-inducible phase separation technique. Subsequently, the yarn coated with the polysulfone polymer is fabricated. To further optimize the airtightness of the diaphragm, the fabric was immersed in a solvent and subjected to non-solvent-induced phase separation again. This resulted in a network structure formed inside and on the surface of the fabric by the polysulfone polymer coating, which made the pore size of the fabric diaphragm smaller and significantly improved its airtightness.

[0047] This invention directly sulfonates the yarn, achieving a more uniform modification effect before the fibers are woven into fabric. This is because the uniformity of the yarn structure allows the sulfonating agent to act more evenly on each fiber, ensuring consistent modification results. This uniform modification not only improves processing efficiency (due to the smaller treatment area of ​​the yarn, allowing for faster chemical penetration) but also reduces production costs by decreasing the amount of sulfonating agent used and the processing time. Furthermore, the modification effect of the sulfonated yarn is fixed before it is woven into fabric, facilitating quality control during subsequent weaving and coating processes and ensuring the consistency and reliability of the final product.

[0048] After polyphenylene sulfide (PPS) yarn is impregnated in an organic solution of polysulfone polymers, a polysulfone polymer layer is formed on the fiber surface through non-solvent-induced phase separation. Non-solvent-induced phase separation introduces a non-solvent that does not dissolve the polysulfone polymer but causes it to precipitate from the solution, forming a uniform coating on the fiber surface, thereby improving the fiber's hydrophilicity and chemical resistance.

[0049] Furthermore, the sulfonation treatment is performed using a sulfonating agent.

[0050] Preferably, the sulfonating agent comprises concentrated sulfuric acid.

[0051] Preferably, the concentrated sulfuric acid has a mass concentration of 90-98%.

[0052] Typical, but not limiting, the mass concentration of concentrated sulfuric acid can be 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, or 98%, or any value within the range of 90% to 98%.

[0053] Preferably, the sulfonation treatment is performed at a temperature of 70–90°C for a time of 5–40 minutes.

[0054] Typically, but not limitingly, the sulfonation treatment temperature can be 70°C, 71°C, 72°C, 73°C, 74°C, 75°C, 76°C, 77°C, 78°C, 79°C, or 90°C, and the time can be 5 min, 6 min, 7 min, 8 min, 9 min, 10 min, 11 min, 12 min, 13 min, 14 min, 15 min, or 16 min.

[0055] 17min, 18min, 19min, 20min, 21min, 22min, 23min, 24min, 25min, 26min, 27min, 28min, 29min, 30min, 31min, 32min, 33min, 34min,

[0056] 35min, 36min, 37min, 38min, 39min or 40min, that is, the temperature and time can be any value within the range of 70℃~90℃ and 5min~40min.

[0057] Furthermore, the mass concentration of the organic solution of the polysulfone polymer is ≤40%, preferably 10-40%.

[0058] Typical, but not limiting, the mass concentration of the organic solution of polysulfone polymers can be 10%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30%, 31%, 32%, 33%, 34%, 35%, 36%, 37%, 38%, 39%, or 40%, that is, the concentration can take any value in the range of 10% to 40%.

[0059] The polysulfone polymers include at least one of polysulfone, sulfonated polysulfone, polyphenylsulfone, sulfonated polyphenylsulfone, sulfonated polyethersulfone, and polyethersulfone.

[0060] Preferably, the organic solvent of the polysulfone polymer includes at least one of N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, N-ethylpyrrolidone, acetonitrile, and dimethyl sulfoxide.

[0061] Preferably, the temperature of the first impregnation is 60-80°C and the time is 5-30 minutes.

[0062] Typically, but not limitingly, the temperature of the first immersion can be 60°C, 61°C, 62°C, 63°C, 64°C, 65°C, 66°C, 67°C, 68°C, 69°C, 70°C, or 80°C, and the time can be 5 min, 6 min, 7 min, 8 min, 9 min, 10 min, 11 min, 12 min, 13 min, 14 min, or 30 min. That is, the temperature and time can be any value within the range of 60°C to 80°C and 5 min to 30 min.

[0063] Furthermore, the first induced phase separation and the second induced phase separation are each independently induced phase separations using non-solvent methods.

[0064] Preferably, the non-solvent is a solvent that cannot dissolve polysulfone polymers.

[0065] Preferably, the non-solvent includes water.

[0066] Furthermore, the non-solvent-induced phase separation process includes: immersing the impregnated yarn or fabric in a water bath in pure water to obtain the phase-separated yarn or fabric.

[0067] Furthermore, the second impregnation reagent includes at least one of N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, N-ethylpyrrolidone, acetonitrile, and dimethyl sulfoxide.

[0068] Preferably, the temperature of the second impregnation is 40-60°C and the time is 5-30 minutes.

[0069] Typically, but not limitingly, the temperature of the second immersion can be 40°C, 41°C, 42°C, 43°C, 44°C, 45°C, 46°C, 47°C, 48°C, 49°C, or 50°C, 51°C, 52°C, 53°C, 54°C, 55°C, 56°C, 57°C, 58°C, 59°C, or 60°C, and the time can be 5 min, 6 min, 7 min, 8 min, 9 min, 10 min, 11 min, 12 min, 13 min, or 30 min. That is, the temperature and time can be any value within the range of 40°C to 60°C and 5 min to 30 min.

[0070] Preferably, the water bath temperature is 70–90°C and the time is 1–5 minutes.

[0071] Typically, but not limitingly, the water bath temperature can be 70℃, 71℃, 72℃, 73℃, 74℃, 75℃, 76℃, 77℃, 78℃, 79℃ or 80℃, 81℃, 82℃, 83℃, 84℃, 85℃, 86℃, 87℃, 88℃, 89℃ or 90℃, and the time can be 1min, 2min, 3min, 4min or 5min, that is, the temperature and time can be any value within the range of 70℃~90℃ and 1min~5min.

[0072] Furthermore, the fabric has a warp density of 25 to 80 threads per inch and a weft density of 15 to 50 threads per inch.

[0073] Typical, but not limiting, warp density of the fabric can be 25, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69 or 70, 71, 72, 73, 74, 75, 76, 7... The warp and weft yarn densities can be 7, 78, 79, or 80 yarns per inch, and the weft density can be 15, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, or 50 yarns per inch. In other words, the warp and weft yarn densities can take any value within the range of 25 to 80 yarns per inch and 15 to 50 yarns per inch, respectively.

[0074] Preferably, the fabric comprises a plain woven fabric.

[0075] Furthermore, the manufacturing process of the polyphenylene sulfide yarn is as follows:

[0076] The polyphenylene sulfide fiber is spun into the polyphenylene sulfide yarn through a cotton spinning process of cotton cleaning, carding, drawing, roving, spinning, winding, twisting, and heat setting.

[0077] Preferably, the length of the polyphenylene sulfide fiber is 30-60 mm.

[0078] Typical, but not limiting, the length of polyphenylene sulfide fibers can be 30mm, 31mm, 32mm, 33mm, 34mm, 35mm, 36mm, 37mm, 38mm, 39mm, 40mm, 41mm, 42mm, 43mm, 44mm, 45mm, 46mm, 47mm, 48mm, 49mm, 50mm, 51mm, 52mm, 53mm, 54mm, 55mm, 56mm, 57mm, 58mm, 59mm or 60mm, and the length can take any value in the range of 30mm to 60mm.

[0079] Preferably, the fineness of the polyphenylene sulfide fiber is 0.5 to 3.0 dtex.

[0080] Typical, but not limiting, polyphenylene sulfide fibers can have a fineness of 0.5 dtex, 0.8 dtex, 1.0 dtex, 1.5 dtex, 1.6 dtex, 1.7 dtex, 1.8 dtex, 1.9 dtex, 2.0 dtex, 2.1 dtex, 2.2 dtex, 2.3 dtex, 2.4 dtex, 2.5 dtex, or 3.0 dtex, that is, the fineness can take any value in the range of 0.5 to 3.0 dtex.

[0081] A second aspect of the present invention provides a polyphenylene sulfide fabric separator, which is prepared by the preparation method described in the first aspect.

[0082] The polyphenylene sulfide (PPS) fabric separator provided by this invention achieves two major technological breakthroughs: high airtightness and superhydrophilicity. The average pore size of the separator is controlled at a fine scale of less than 5 μm. This characteristic is crucial for preventing the interpenetration of hydrogen and oxygen, thereby ensuring the safety of the electrolysis process. The sheet resistivity of this separator is less than 0.15 Ω / cm. 2 It has a rapid hydrophilic response, which significantly reduces the internal resistance of the application environment and improves efficiency.

[0083] The third aspect of the present invention provides the application of the polyphenylene sulfide fabric diaphragm in an alkaline water electrolyzer.

[0084] The application of the polyphenylene sulfide (PPS) fabric diaphragm provided by this invention, given its surface structure and chemical stability, enables it to maintain stable hydrophilicity during alkaline water electrolysis, reducing energy consumption and extending service life. This combination of technical advantages not only improves the economics of hydrogen production through water electrolysis but also provides a reliable guarantee for the long-term stable operation of the electrolyzer.

[0085] The following detailed description of some embodiments of the present invention is provided in conjunction with examples. Unless otherwise specified, the following embodiments and features can be combined with each other. Unless otherwise specified, the raw materials used in the following embodiments and comparative examples were all commercially available.

[0086] Example 1

[0087] This embodiment provides a polyphenylene sulfide fabric separator, the preparation process of which is as follows:

[0088] (1) Polyphenylene sulfide fibers with a length of 51 mm and a fineness of 1.56 dtex are spun through a cotton spinning process of cotton cleaning-carding-drawing-roving-spinning-winding-drawing-twisting-heat setting to obtain polyphenylene sulfide yarn.

[0089] (2) The polyphenylene sulfide yarn was sulfonated in 95% concentrated sulfuric acid at a temperature of 80°C for 10 minutes. After sulfonation, it was washed and dried.

[0090] (3) The sulfonated polyphenylene sulfide yarn was immersed in a polysulfone solution (concentration of 20wt%, solvent of NMP) at an immersion temperature of 70℃ for 15min.

[0091] (4) The impregnated polyphenylene sulfide yarn is placed in a water bath at 80°C for 2 minutes.

[0092] (5) After the water bath, the polyphenylene sulfide yarn is washed and dried to obtain yarn with a polysulfone polymer layer. The yarn with the polysulfone polymer layer is woven on a rapier loom to obtain a plain weave fabric with a warp density of 40 yarns / inch and a weft density of 28 yarns / inch.

[0093] (6) Immerse the fabric in NMP at 50°C for 15 minutes. Then immerse it in pure water at 80°C for 2 minutes, and finally wash and dry it to obtain a polyphenylene sulfide fabric membrane.

[0094] Example 2

[0095] This embodiment provides a polyphenylene sulfide fabric separator, the preparation process of which is as follows:

[0096] (1) Polyphenylene sulfide fibers with a length of 51 mm and a fineness of 2.22 dtex are spun through a cotton spinning process of cotton cleaning-carding-drawing-roving-spinning-winding-drawing-twisting-heat setting to obtain polyphenylene sulfide yarn.

[0097] (2) The polyphenylene sulfide yarn was sulfonated in 90% concentrated sulfuric acid at a temperature of 80°C for 20 minutes. After sulfonation, it was washed and dried.

[0098] (3) The sulfonated polyphenylene sulfide yarn was immersed in a polysulfone polymer solution (concentration of 30wt%, solvent of dimethyl sulfoxide) at a temperature of 60℃ for 20min.

[0099] (4) The impregnated polyphenylene sulfide yarn is placed in a water bath at 80°C for 5 minutes.

[0100] (5) After the water bath, the polyphenylene sulfide yarn is washed and dried to obtain yarn with a polysulfone polymer layer. The yarn with the polysulfone polymer layer is woven on a rapier loom to obtain a plain weave fabric with a warp density of 36 yarns / inch and a weft density of 25 yarns / inch.

[0101] (6) Immerse the fabric in dimethyl sulfoxide at 60°C for 30 minutes. Then bathe it in pure water at 80°C for 5 minutes. Finally, wash and dry to obtain a polyphenylene sulfide fabric membrane.

[0102] Example 3

[0103] This embodiment provides a polyphenylene sulfide fabric separator, the preparation process of which is as follows:

[0104] (1) Polyphenylene sulfide fibers with a length of 51 mm and a fineness of 0.89 dtex are spun through a cotton spinning process of cotton cleaning-carding-drawing-roving-spinning-winding-drawing-twisting-heat setting to obtain polyphenylene sulfide yarn.

[0105] (2) The polyphenylene sulfide yarn was sulfonated in 95% concentrated sulfuric acid at a temperature of 80°C for 5 minutes. After sulfonation, it was washed and dried.

[0106] (3) The sulfonated polyphenylene sulfide yarn was immersed in a polysulfone polymer solution (concentration of 10wt%, solvent of NMP) at an immersion temperature of 80℃ for 5min.

[0107] (4) The impregnated polyphenylene sulfide yarn is placed in a water bath at 80°C for 2 minutes.

[0108] (5) After the water bath, the polyphenylene sulfide yarn is washed and dried to obtain yarn with a polysulfone polymer layer. The yarn with the polysulfone polymer layer is woven on a rapier loom to obtain a plain weave fabric with a warp density of 78 yarns / inch and a weft density of 45 yarns / inch.

[0109] (6) Immerse the fabric in NMP at 40°C for 5 minutes. Then bathe it in pure water at 80°C for 2 minutes. Finally, wash and dry to obtain a polyphenylene sulfide fabric membrane.

[0110] Comparative Example 1

[0111] This comparative example provides a polyphenylene sulfide fabric separator, and the preparation process is as follows:

[0112] (1) Polyphenylene sulfide fibers with a length of 51 mm and a fineness of 1.56 dtex are spun through a cotton spinning process of cotton cleaning-carding-drawing-roving-spinning-winding-drawing-twisting-heat setting to obtain polyphenylene sulfide yarn.

[0113] (2) Polyphenylene sulfide yarn is woven by a rapier loom to obtain a plain weave fabric with a warp density of 40 yarns / inch and a weft density of 28 yarns / inch, which serves as the polyphenylene sulfide fabric diaphragm.

[0114] Comparative Example 2

[0115] This comparative example provides a polyphenylene sulfide fabric separator, and the preparation process is as follows:

[0116] (1) Polyphenylene sulfide fibers with a length of 51 mm and a fineness of 1.56 dtex are spun through a cotton spinning process of cotton cleaning-carding-drawing-roving-spinning-winding-drawing-twisting-heat setting to obtain polyphenylene sulfide yarn.

[0117] (2) The polyphenylene sulfide yarn is sulfonated in 95% concentrated sulfuric acid at a temperature of 80°C for 10 minutes. After sulfonation, it is washed and dried, and then woven on a rapier loom to obtain a plain weave fabric with a warp density of 40 yarns / inch and a weft density of 28 yarns / inch, which serves as the polyphenylene sulfide fabric diaphragm.

[0118] Comparative Example 3

[0119] This comparative example provides a polyphenylene sulfide fabric separator, and the preparation process is as follows:

[0120] (1) Polyphenylene sulfide fibers with a length of 51 mm and a fineness of 0.89 dtex are spun through a cotton spinning process of cotton cleaning-carding-drawing-roving-spinning-winding-drawing-twisting-heat setting to obtain polyphenylene sulfide yarn.

[0121] (2) The polyphenylene sulfide yarn was sulfonated in 95% concentrated sulfuric acid at a temperature of 80°C for 5 minutes. After sulfonation, it was washed and dried.

[0122] (3) The sulfonated polyphenylene sulfide yarn was immersed in a polysulfone polymer solution (concentration of 10wt%, solvent of NMP) at an immersion temperature of 80℃ for 5min.

[0123] (4) The impregnated polyphenylene sulfide yarn is placed in a water bath at 80°C for 2 minutes.

[0124] (5) After the water bath, the polyphenylene sulfide yarn is washed and dried to obtain yarn with a polysulfone polymer layer. The yarn with the polysulfone polymer layer is woven on a rapier loom to obtain a plain weave fabric with a warp density of 78 yarns / inch and a weft density of 45 yarns / inch.

[0125] Comparative Example 4

[0126] This comparative example provides a polyphenylene sulfide fabric separator, and the preparation process is as follows:

[0127] (1) Polyphenylene sulfide fibers with a length of 51 mm and a fineness of 2.22 dtex are spun through a cotton spinning process of cotton cleaning-carding-drawing-roving-spinning-winding-drawing-twisting-heat setting to obtain polyphenylene sulfide yarn.

[0128] (2) The polyphenylene sulfide yarn was immersed in a polysulfone polymer solution (concentration of 30wt%, solvent of dimethyl sulfoxide) at a temperature of 60℃ for 20min.

[0129] (3) The impregnated polyphenylene sulfide yarn is placed in a water bath at 80°C for 5 minutes.

[0130] (4) After the water bath, the polyphenylene sulfide yarn is washed and dried to obtain yarn with a polysulfone polymer layer. The yarn with the polysulfone polymer layer is woven on a rapier loom to obtain a plain weave fabric with a warp density of 36 yarns / inch and a weft density of 25 yarns / inch.

[0131] (5) Immerse the fabric in dimethyl sulfoxide at 60°C for 30 minutes. Then bathe it in pure water at 80°C for 5 minutes. Finally, wash and dry to obtain a polyphenylene sulfide fabric membrane.

[0132] Test case

[0133] The polyphenylene sulfide fabric separators obtained in the examples and comparative examples were subjected to the following tests:

[0134] (1) Thickness: The thickness of the fabric was tested according to the method of JIS L1096-2010 "Test methods for fabrics and knitted fabrics".

[0135] (2) Weight: The weight of the fabric is tested according to GB / T 4669-2008 "Determination of mass per unit length and mass per unit area of ​​textile woven fabric".

[0136] (3) Average pore size: According to ASTM F316-03, "Standard Test Method for Determining the Pore Size Characteristics of Membrane Filters by Bubble Point and Pore Average Flow Rate", the average pore size of the fabric was measured using a capillary flow porosimeter.

[0137] (4) Air tightness: The air tightness of the fabric diaphragm was tested according to the Chinese building materials industry standard JC / T 211-2009 "Diaphragm Asbestos Cloth".

[0138] (5) Sheet resistance: The sheet resistance of the fabric separator was tested according to SJ / T 10171-2016 "General Test Method for Basic Performance of Alkaline Battery Separators". Before testing, the prepared fabric separator was immersed in a 30wt% KOH aqueous solution for 24 hours. The test solution was a 30wt% KOH aqueous solution at 23℃±2℃. The resistance was measured using an AC low impedance meter. The formula for calculating the sheet resistance Rs of the composite separator is as follows:

[0139] R s = (R1-R0)×A

[0140] Where R1 is the resistance of the solution when the membrane is applied, and R0 is the resistance of the blank solution.

[0141] (6) Alkali resistance stability test of the diaphragm: Take fabric diaphragms of the same size and put them into a 30wt% KOH aqueous solution at 90℃. Stir at 300rpm for 30 days, then take them out, wash them with water and dry them. Test the air tightness of the fabric diaphragms before and after hot alkali treatment according to relevant standards, and calculate the change rate of air tightness using the following formula.

[0142]

[0143] The results are shown in Table 1 below.

[0144] Table 1

[0145]

[0146] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, and not to limit them. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some or all of the technical features therein. Such modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. A method for preparing a polyphenylene sulfide fabric separator, characterized in that, Includes the following steps: A. Sulfonate the polyphenylene sulfide yarn with concentrated sulfuric acid of 90-98% by mass, and then impregnate the sulfonated polyphenylene sulfide yarn in an organic solvent of polysulfone polymer. The first induced phase is separated to obtain yarn containing a polysulfone polymer layer. B. The yarn containing the polysulfone polymer layer is woven into a fabric, and the fabric is subjected to a second impregnation, a second induced phase separation, washing and drying to obtain a polyphenylene sulfide fabric diaphragm; The reagent used for the second impregnation includes at least one of N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, N-ethylpyrrolidone, acetonitrile, and dimethyl sulfoxide. The first induced phase separation and the second induced phase separation are each independently induced phase separation using non-solvent; the process of non-solvent induced phase separation includes: immersing the impregnated yarn or fabric in a water bath in pure water to obtain the phase-separated yarn or fabric.

2. The preparation method according to claim 1, characterized in that, The sulfonation treatment is performed at a temperature of 70-90°C for 5-40 minutes.

3. The preparation method according to claim 1, characterized in that, The mass concentration of the organic solution of the polysulfone polymer is ≤40%; The polysulfone polymers include at least one of polysulfone, sulfonated polysulfone, polyphenylsulfone, sulfonated polyphenylsulfone, sulfonated polyethersulfone, and polyethersulfone; The organic solvent of the polysulfone polymer includes at least one of N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, N-ethylpyrrolidone, acetonitrile, and dimethyl sulfoxide; The temperature of the first impregnation is 60~80℃, and the time is 5~30min.

4. The preparation method according to any one of claims 1 to 3, characterized in that, The second impregnation temperature is 40~60℃, and the time is 5~30min; The water bath temperature is 70~90℃, and the time is 1~5min.

5. The preparation method according to any one of claims 1 to 3, characterized in that, The fabric has a warp density of 25-80 threads per inch and a weft density of 15-50 threads per inch. The fabric includes plain woven fabric.

6. The preparation method according to any one of claims 1 to 3, characterized in that, The manufacturing process of the polyphenylene sulfide yarn is as follows: The polyphenylene sulfide fiber is spun into the polyphenylene sulfide yarn through a cotton spinning process of cotton cleaning, carding, drawing, roving, spinning, winding, drawing, twisting and heat setting. The polyphenylene sulfide fiber has a length of 30~60mm and a fineness of 0.5~3.0dtex.

7. A polyphenylene sulfide fabric separator, characterized in that, It is prepared by the preparation method described in any one of claims 1 to 6.

8. The application of the polyphenylene sulfide fabric diaphragm according to claim 7 in an alkaline water electrolyzer.

Images