CN114432906A - High-temperature-resistant alkaline water electrolysis tank composite diaphragm and preparation method thereof - Google Patents

High-temperature-resistant alkaline water electrolysis tank composite diaphragm and preparation method thereof Download PDF

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CN114432906A
CN114432906A CN202210131101.7A CN202210131101A CN114432906A CN 114432906 A CN114432906 A CN 114432906A CN 202210131101 A CN202210131101 A CN 202210131101A CN 114432906 A CN114432906 A CN 114432906A
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composite
composite diaphragm
polysulfone
membrane
temperature
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朱红
代雅洁
王智谦
汪中明
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Beijing University of Chemical Technology
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Beijing University of Chemical Technology
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/12—Composite membranes; Ultra-thin membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0079—Manufacture of membranes comprising organic and inorganic components
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/10—Supported membranes; Membrane supports
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/02—Inorganic material
    • B01D71/024—Oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/66—Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
    • B01D71/68—Polysulfones; Polyethersulfones
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/02—Hydrogen or oxygen
    • C25B1/04—Hydrogen or oxygen by electrolysis of water
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B13/00—Diaphragms; Spacing elements
    • C25B13/02—Diaphragms; Spacing elements characterised by shape or form
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B13/00—Diaphragms; Spacing elements
    • C25B13/04—Diaphragms; Spacing elements characterised by the material
    • C25B13/08—Diaphragms; Spacing elements characterised by the material based on organic materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/22—Thermal or heat-resistance properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/24—Mechanical properties, e.g. strength
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/30—Chemical resistance
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/36—Hydrophilic membranes

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)

Abstract

The invention relates to a high-temperature resistant alkaline water electrolysis bath composite diaphragm and a preparation method thereof, belonging to the technical field of electrolyzed water, and comprising the following steps: (1) preparing a casting solution: selecting polysulfone and ZrO2Preparing slurry as a raw material; (2) belt supportPreparing a composite membrane: selecting PPS mesh fiber as a support, soaking the PPS mesh fiber in the slurry, determining the thickness, then carrying out blade coating, carrying out phase conversion by using deionized water after pre-evaporation, and washing by using deionized water for multiple times to obtain the PPS mesh supported polysulfone-ZrO2A composite membrane. The preparation method has the advantages of simple preparation process, easy industrial implementation, simple and convenient operation, low cost, reliable product performance and stable quality.

Description

High-temperature-resistant alkaline water electrolysis tank composite diaphragm and preparation method thereof
Technical Field
The invention relates to preparation of an alkaline electrolyzed water composite membrane, in particular to a high-temperature-resistant alkaline water electrolysis cell composite membrane and a preparation method thereof, and belongs to the technical field of electrolyzed water.
Technical Field
With the development of technology and economy and the growth of population, people have more and more demand for energy. At present, fossil fuels represented by petroleum and coal bring serious environmental pollution on one hand, and bring serious energy crisis on the other hand due to the non-renewable property and limited reserves of the fossil fuels. Therefore, the development of clean and renewable new energy is more and more urgent.
Hydrogen energy is considered as the most ideal energy carrier because of its advantages of cleanliness, no pollution, high efficiency, storage and transportation, etc. Hydrogen, a combustible gas, is used not only as a pollution-free energy source but also in many fields such as electronics, military, aerospace, chemical engineering, metallurgy, building materials, weather, and automobiles.
There are many methods for producing hydrogen, among which, the hydrogen production technology by water electrolysis is developed most mature and has wider application.
When the two electrodes are energized with direct current and immersed in water, the water is decomposed and hydrogen and oxygen are generated at the cathode and anode, respectively, and this process is electrolysis of water, and such a device is called a water electrolyzer.
At present, the electrolytic cells on the market can be divided into three types: alkaline electrolysis cell, proton exchange membrane electrolysis cell and solid oxide electrolysis cell. Alkaline electrolyzers, the earliest commercialized electrolyzer technology, are inexpensive and still widely used at present, although not the most efficient, especially in the large-scale hydrogen production industry, and have the disadvantages of low efficiency and the use of asbestos as a diaphragm.
The membrane, which is an important part of the alkaline cell, is placed between the anode and the cathode to prevent the mixing of oxygen on the anode side and hydrogen on the cathode side to improve gas purity, current efficiency and safety. In the alkaline water electrolysis hydrogen production process, 25 to 30 percent of potassium hydroxide or sodium hydroxide is generally adopted; wherein, the diaphragm has good alkali corrosion resistance; the purity of the gas prepared by electrolysis and the safety of the electrolytic cell are ensured, and the diaphragm is required to strictly separate the hydrogen from the oxygen, so that the gas has good air tightness; the ions in the solution are allowed to freely move between the cathode and the anode, and the electrolyte has good electrolyte permeation performance and as low resistance as possible.
Due to technical limitation, at present, domestic main hydrogen production equipment manufacturers still adopt asbestos cloth as a diaphragm, the asbestos diaphragm has excellent corrosion resistance, but has higher resistance, and is easy to dissolve when the temperature is too high and the pressure is increased, so that the pollution to electrolyte is caused; and asbestos has carcinogenicity, causes pollution to the environment during mining and processing and causes harm to human bodies, and many countries have proposed to prohibit the use of asbestos in alkaline electrolytic cells, so that the search for new diaphragm materials is urgent and necessary.
The Leysen project group prepares zirconium dioxide and polysulfone composite membranes (Zirfon membranes) by an immersion precipitation phase inversion method. The diaphragm is a porous diaphragm, the shape of the hole is similar to that of a pure polysulfone membrane, the surface of the diaphragm is a compact skin layer, the inside of the diaphragm is a finger-shaped hole, the ion conduction performance is better, and the diaphragm can be used in an alkaline water electrolyzer for a long time, but the diaphragm has the following defects: the strength is not sufficient; if the diaphragm strength is enhanced, asbestos diaphragms may be substituted.
Therefore, the development of the high-temperature resistant alkaline water electrolyzer composite diaphragm which has simple process, easy large-area and large-scale production, uniform and flat surface and good corrosion resistance and strength and the preparation method thereof become the technical problem which needs to be solved urgently in the technical field.
Disclosure of Invention
One of the purposes of the invention is to provide a high-temperature resistant alkaline water electrolyzer composite diaphragm which has simple process, easy large-area and large-scale production, uniform and flat surface and good corrosion resistance and strength.
In order to achieve the above purpose of the invention, the following technical scheme is adopted:
the composite diaphragm for high temperature resistant alkaline water electrolyzer has support body of polyphenyl thioether net and composite polysulfone-zirconium dioxide film containing metal salt or composite metal salt.
Preferably, the weight ratio of the polysulfone to the zirconium dioxide is 2: 1-1: 2.
preferably, the weight ratio of the polysulfone to the metal salt is 15: 1-5: 1.
preferably, the thickness of the composite membrane is 0.2-0.5 mm.
Preferably, the thickness of the composite membrane is 0.3-0.35 mm.
Preferably, the thickness of the composite membrane is 0.4-0.45 mm.
Preferably, the tensile strength of the composite membrane is 16-20 MPa.
Preferably, the elongation at break of the composite separator is 28 to 32%.
The invention also aims to provide a preparation method of the high-temperature-resistant alkaline water electrolyzer composite diaphragm.
A preparation method of a high-temperature-resistant alkaline water electrolysis bath composite diaphragm comprises the following steps:
(1) preparing a casting solution:
dissolving 5-25 wt% of polysulfone resin in 45-65 wt% of N-methyl pyrrolidone, and stirring to obtain uniformly dispersed polysulfone solution; then adding 5-25 wt% of polyvinylpyrrolidone, and stirring at room temperature at 300r/min to completely dissolve the polyvinylpyrrolidone; then adding 5-25 wt% of zirconium dioxide and 0.1-5 wt% of metal salt, continuing stirring for 24h until the zirconium dioxide and the metal salt are completely and uniformly dispersed, reducing the stirring speed to 60r/min, stirring for 24h, and performing degassing treatment to obtain a milky membrane casting solution;
the metal salt comprises magnesium oxide, aluminum oxide, zinc oxide, silicon dioxide, borax, lithium oxide, calcium oxide, magnesium sulfate, magnesium carbonate, aluminum carbonate, sodium carbonate, calcium phosphate and/or kaolin and other metal salts and composite salts thereof;
(2) preparing a composite membrane with a support:
soaking a polyphenylene sulfide (PPS) net in the casting solution obtained in the step (1), so that the casting solution is fully soaked in the polyphenylene sulfide (PPS) net as a support, then carrying out blade coating by using a scraper to determine the thickness, standing the membrane after membrane scraping in the air, carrying out pre-evaporation, finally, putting the membrane into deionized water for phase conversion, and carrying out soaking and cleaning on the composite membrane with the deionized water for multiple times until the water is transparent and not turbid, thereby obtaining the membrane (the composite membrane of the polyphenylene sulfide (PPS) net supporting polysulfone-zirconium dioxide) for the high-temperature alkaline electrolysis water.
Preferably, the polysulfone is added to the polysulfone solution in step (1) in an amount of 15 wt%.
Preferably, the polyvinylpyrrolidone is added in the step (1) in an amount of 10 wt%.
Preferably, the amount of zirconium dioxide added in step (1) is 18% by weight.
Preferably, the metal oxide is added in step (1) in an amount of 2 wt%.
Preferably, the N-methylpyrrolidone is added in step (1) in an amount of 55 wt%.
Preferably, in the step (1), the dissolving temperature of the polysulfone resin is 0-20 ℃; the dissolution time is not less than 5 hours.
Preferably, in the step (1), the dissolving temperature of the polyvinylpyrrolidone is 0-20 ℃; the dissolution time is not less than 5 hours.
Preferably, in the step (2), the time of the pre-evaporation is 5-25 s; preferably 15 s.
Preferably, in the step (2), the temperature of the deionized water is 5-25 ℃; preferably 15 deg.c.
Has the advantages that:
the high-temperature-resistant alkaline water electrolyzer composite diaphragm and the preparation method thereof utilize the PPS mesh fiber which has high thermal stability, excellent chemical corrosion resistance and extremely high flame retardance and has good mechanical property as a support, so that the mechanical strength of the diaphragm can be greatly improved; polysulfone which maintains excellent mechanical properties, electrical properties and chemical stability at high temperature is used as an adhesive; the hydrophilic performance of the polysulfone composite membrane can be effectively improved by adding the zirconium dioxide, and the permeability of water is accelerated; the added metal salt or metal composite salt is used as a structural reinforcing agent, and the electrochemical performance and the high-temperature resistance of the composite membrane can be obviously improved.
The preparation method of the high-temperature-resistant alkaline water electrolysis bath composite diaphragm has the following advantages:
(1) the film casting process is simple, and large-area and large-batch production is easy to realize;
(2) the prepared diaphragm for the high-temperature-resistant alkaline electrolyzed water has the advantages of uniform and flat surface, adjustable thickness and current density of 6400A/m2Can meet the requirements of the electrolytic water tank on various aspects of the alkaline diaphragm;
(3) the prepared diaphragm for the high-temperature-resistant alkaline electrolyzed water has good corrosion resistance, and the alkali loss is less than 1%.
The method is simple and efficient, and the prepared alkaline diaphragm has good comprehensive performance.
The invention is further illustrated by the following specific examples, which are not intended to limit the scope of the invention.
Detailed Description
Unless otherwise stated, the raw materials in the examples of the present invention are conventional raw materials available on the market, the equipment used is equipment commonly used in the art, and the reaction conditions are normal conditions; the identification of the product is identified by conventional methods.
A preparation method of a high-temperature-resistant alkaline water electrolysis bath composite diaphragm comprises the following steps:
(1) preparing a casting solution:
dissolving polysulfone resin in N-methyl pyrrolidone, and stirring to obtain uniformly dispersed polysulfone solution; then adding polyvinylpyrrolidone, and stirring at room temperature at 300r/min to completely dissolve the polyvinylpyrrolidone; adding zirconium dioxide and metal salt, and continuously stirring for 24h until the zirconium dioxide and the metal salt are completely and uniformly dispersed; reducing the stirring speed to 60r/min, stirring for 24h, and degassing to obtain milky membrane casting solution;
(2) preparing a composite membrane with a support:
and (2) soaking polyphenylene sulfide (PPS) in the casting solution obtained in the step (1) to enable the casting solution to be fully soaked in a support, then carrying out blade coating by using a scraper to determine the thickness, standing the membrane subjected to membrane scraping in the air, carrying out pre-evaporation, finally placing the membrane into deionized water for phase inversion, and carrying out multiple soaking and cleaning on the composite membrane supported by the belt by using the deionized water until the water is transparent and not turbid, thus obtaining the composite membrane (polyphenylene sulfide (PPS) net supported polysulfone-zirconium dioxide composite membrane) of the high-temperature-resistant alkaline water electrolysis bath.
Example 1
A preparation method of a high-temperature-resistant alkaline water electrolysis bath composite diaphragm comprises the following steps:
(1) preparing a casting solution:
150mg of polysulfone resin is dissolved in 550mg of N-methyl pyrrolidone, and the mixture is stirred for 5 hours at 300r/min to prepare uniformly dispersed yellow transparent viscous polysulfone solution; then 100mg of polyvinylpyrrolidone is added, and the mixture is stirred at room temperature at 300r/min to be completely dissolved, so that a white viscous mixture is obtained; finally, 180mg of ZrO were added2Continuously stirring 20mg of metal salt (magnesium oxide) for 24 hours until the metal salt is completely and uniformly dispersed to obtain a milky viscous mixture, reducing the stirring speed to 60r/min, stirring for 24 hours, and degassing to obtain a milky membrane casting solution;
(2) preparing a composite membrane with a support:
soaking 40-mesh polyphenylene sulfide (PPS) in the casting solution obtained in the step (1) to enable the casting solution to be fully immersed in the support, then carrying out blade coating by using a scraper, selecting the thickness of 0.3-0.35mm, standing the membrane after membrane scraping in the air, carrying out pre-evaporation for 15s, finally placing the membrane into deionized water at 15 ℃, carrying out phase conversion, carrying out soaking and cleaning on the composite membrane with deionized water for multiple times until the water is transparent and not turbid, and obtaining the high-temperature alkaline water electrolysis bath composite membrane (the polyphenylene sulfide (PPS) net supported polysulfone-ZrO) mesh supported composite membrane2Composite membranes).
The product performance of the embodiment of the invention meets the use requirement of the alkaline electrolytic cell, and the thinner thickness ensures that the electrolytic voltage is relatively minimum under the same current density. The tensile strength of the product of example 1 according to the invention is at a high level (16.52 MPa) due to the addition of the support, showing a good elongation at break (31.36%), indicating that the material is very soft and elastic. The alkali loss of the invention is also small, wherein, the polysulfone, the zirconium dioxide and the PPS net have stronger corrosion resistance.
Example 2
A preparation method of a high-temperature-resistant alkaline water electrolysis cell composite diaphragm comprises the following steps:
(1) preparing a casting solution:
300mg of polysulfone resin is dissolved in 1100mg of N-methyl pyrrolidone and stirred for 5 hours at 300r/min to prepare uniformly dispersed yellow transparent viscous polysulfone solution; then 300mg of polyvinylpyrrolidone is added and stirred at room temperature at 300r/min to be completely dissolved, so as to obtain a white viscous mixture; finally, 300mg of ZrO were added230mg of metal salt (aluminum oxide), continuously stirring for 24 hours until the metal salt is completely and uniformly dispersed to obtain a milky viscous mixture, reducing the stirring speed to 60r/min, stirring for 24 hours, and degassing to obtain a milky casting solution;
(2) preparing a composite membrane with a support:
soaking 60-mesh polyphenylene sulfide (PPS) in the casting solution obtained in the step (1) to enable the casting solution to be fully immersed in the support, then carrying out blade coating by using a scraper, selecting the thickness of 0.4-0.45mm, standing the membrane after membrane scraping in the air, carrying out pre-evaporation for 15s, finally placing the membrane into deionized water at 15 ℃ for phase conversion, carrying out multiple soaking and cleaning on the supported composite membrane by using the deionized water until the water is transparent and not turbid, and obtaining the high-temperature-resistant alkaline water electrolysis bath composite membrane (polyphenylene sulfide (PPS) net supported polysulfone-ZrO)2Composite membranes).
The invention selects the reticular polyphenylene sulfide (PPS) fiber with strong acid and alkali corrosion resistance and high strength as a support; meanwhile, the polymer polysulfone which can maintain excellent mechanical property, electrical property and chemical stability at high temperature is selected as the adhesive, and the polysulfone membrane has the advantages of excellent permeability, temperature resistance, solvent resistance, high mechanical strength and the like; however, due to the defects of strong hydrophobicity and strong rigidity of the polyphenylene sulfide and the polysulfone, the hydrophilic property of the polysulfone composite membrane can be effectively improved by adding the zirconium dioxide, so that the membrane has strong hydrophilic property, enough gas barrier capability, enough strength and excellent corrosion resistance.
Example 3
Otherwise, the same as example 2, the only difference being: the metal salt in the step (1) is zinc oxide.
Example 4
Otherwise, the same as example 2, the only difference being: the metal salt in the step (1) is borax.
Example 5
Otherwise, the same as example 2, the only difference being: the metal salt in the step (1) is lithium oxide.
Example 6
Otherwise, the same as example 2, the only difference being: the metal salt in the step (1) is calcium oxide.
Example 7
Otherwise, the same as example 2, the only difference being: the metal salt in step (1) is magnesium sulfate.
Example 8
Otherwise, the same as example 2, the only difference being: the metal salt in the step (1) is magnesium carbonate.
Example 9
Otherwise, the same as example 2, the only difference being: the metal salt in the step (1) is aluminum carbonate.
Example 10
Otherwise, the same as example 2, the only difference being: the metal salt in step (1) is sodium carbonate.
Example 11
Otherwise, the same as example 2, the only difference being: the metal salt in the step (1) is calcium carbonate.
Example 12
Otherwise, the same as example 2, the only difference being: the metal salt in the step (1) is calcium phosphate.
Example 13
Otherwise, as in example 2, the only differences are: the metal salt in the step (1) is kaolin.
The thickness of the diaphragm in the embodiment of the invention can be kept between 0.2 mm and 0.5 mm.
The invention aims to minimize the thickness of the product as much as possible under the condition of ensuring the strength of the product, and the prepared high-temperature-resistant alkaline electrolyzed water diaphragm (namely the polyphenylene sulfide (PPS) net supported polysulfone-ZrO)2Composite film) has a current density of 6400A/m at 80 DEG C2Loss of alkali<1％。
The performance of the products of the embodiments 2-13 of the invention all meet the use requirements of the alkaline electrolytic cell, and the thinner thickness thereof enables the electrolytic voltage to be relatively minimum under the same current density; the tensile strength of the products of examples 2-13 of the present invention was at a high level (16-18MPa) due to the addition of the support, and showed good elongation at break (31-33%), indicating that the materials had good softness and elasticity. The alkali loss of the invention is also small, wherein, the polysulfone, the zirconium dioxide and the PPS net have stronger corrosion resistance.
The above-mentioned embodiments are further detailed to explain the objects, technical solutions and advantages of the present invention, but the present invention is not limited thereto, and any modifications, equivalent substitutions, improvements and the like made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

1. A composite diaphragm of a high-temperature-resistant alkaline water electrolyzer is characterized in that a support body is a polyphenylene sulfide net, and the composite diaphragm is a polysulfone-zirconium dioxide composite membrane and contains metal salt or composite metal salt.
2. The composite diaphragm of claim 1, wherein: the weight ratio of the polysulfone to the zirconium dioxide is 2: 1-1: 2; the weight ratio of the polysulfone to the metal salt is 15: 1-5: 1.
3. the composite diaphragm of claim 1, wherein: the thickness of the composite diaphragm is 0.2-0.5 mm.
4. The composite diaphragm of claim 1, wherein: the thickness of the composite diaphragm is 0.3-0.35 mm.
5. The composite diaphragm of claim 1, wherein: the thickness of the composite diaphragm is 0.4-0.45 mm.
6. The composite diaphragm of claim 1, wherein: the tensile strength of the composite diaphragm is 16-20 MPa.
7. The composite diaphragm of claim 1, wherein: the elongation at break of the composite membrane is 28-32%.
8. The preparation method of the high-temperature resistant alkaline water electrolyzer composite diaphragm of any one of claims 1 to 7, which comprises the following steps:
(1) preparing a casting solution:
dissolving 5-25 wt% of polysulfone resin in 45-65 wt% of N-methyl pyrrolidone, and stirring to obtain uniformly dispersed polysulfone solution; then adding 5-25 wt% of polyvinylpyrrolidone, and stirring at room temperature at 300r/min to completely dissolve the polyvinylpyrrolidone; adding 5-25 wt% of zirconium dioxide and 0.1-5 wt% of metal salt, continuously stirring for 24h until the zirconium dioxide and the metal salt are completely and uniformly dispersed, reducing the stirring speed to 60r/min, stirring for 24h, and performing degassing treatment to obtain a milky membrane casting solution;
(2) preparing a composite membrane with a support:
soaking a polyphenylene sulfide net in the casting solution obtained in the step (1) to enable the casting solution to be fully soaked in the polyphenylene sulfide net as a support, then carrying out blade coating by using a scraper to determine the thickness, standing the membrane after membrane scraping in the air, carrying out pre-evaporation, finally, putting the membrane into deionized water for phase inversion, and carrying out soaking and cleaning on the composite membrane with the support for multiple times by using the deionized water until the water is transparent and not turbid to obtain the membrane for the high-temperature alkaline resistant electrolyzed water.
9. The method for preparing the composite diaphragm of the high-temperature resistant alkaline water electrolyzer, as claimed in claim 8, characterized in that: in the step (1), the adding amount of polysulfone in the polysulfone solution is 15 wt%, the adding amount of polyvinylpyrrolidone is 15 wt%, the adding amount of zirconium dioxide is 15 wt%, the adding amount of N-methyl pyrrolidone is 55 wt%, and the dissolving temperature of polysulfone resin is 0-20 ℃; the dissolving time is not less than 5 hours, and the dissolving temperature of the polyvinylpyrrolidone is 0-20 ℃; the dissolving time is not less than 5 hours; the metal salt comprises magnesium oxide, aluminum oxide, zinc oxide, silicon dioxide, borax, lithium oxide, calcium oxide, magnesium sulfate, magnesium carbonate, aluminum carbonate, sodium carbonate, calcium phosphate and/or kaolin and composite salts thereof.
10. The method for preparing the composite diaphragm of the high-temperature resistant alkaline water electrolyzer according to claim 1, which is characterized in that: in the step (2), the time of the pre-evaporation is 5-25 s; the temperature of the deionized water is 5-25 ℃.
CN202210131101.7A 2022-02-13 2022-02-13 High-temperature-resistant alkaline water electrolysis tank composite diaphragm and preparation method thereof Pending CN114432906A (en)

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CN115029732A (en) * 2022-06-06 2022-09-09 清华大学 Diaphragm for alkaline water electrolysis and preparation method and application thereof
CN115074763A (en) * 2022-07-01 2022-09-20 中国华能集团清洁能源技术研究院有限公司 Preparation method of alkaline water electrolysis hydrogen production diaphragm and diaphragm
CN115125582A (en) * 2022-06-17 2022-09-30 中国华能集团清洁能源技术研究院有限公司 Preparation method of organic-inorganic composite membrane in alkaline electrolysis device
CN115819818A (en) * 2022-12-23 2023-03-21 乐凯胶片股份有限公司 Composite diaphragm for hydrogen production by alkaline water electrolysis and preparation method thereof
CN115896863A (en) * 2022-10-25 2023-04-04 清华大学 Ultrathin composite diaphragm for alkaline water electrolysis, preparation method thereof and alkaline water electrolysis device
CN116219492A (en) * 2022-12-28 2023-06-06 嘉庚创新实验室 Composite diaphragm for producing hydrogen by alkaline water electrolysis and preparation method thereof
CN116238174A (en) * 2023-02-27 2023-06-09 海卓迈博(苏州)新材料有限公司 Method for continuously preparing alkaline electrolyzed water composite membrane
CN117512692A (en) * 2023-11-17 2024-02-06 武汉理工大学 Coating type alkaline water electrolysis hydrogen production diaphragm
WO2024140890A1 (en) * 2022-12-28 2024-07-04 嘉庚创新实验室 Organic-inorganic composite separator for production of hydrogen by alkaline water electrolysis, and preparation method therefor
CN118374835A (en) * 2024-04-18 2024-07-23 北京元泰能材科技有限公司 Composite diaphragm and preparation method and application thereof

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CN115029732A (en) * 2022-06-06 2022-09-09 清华大学 Diaphragm for alkaline water electrolysis and preparation method and application thereof
CN115125582A (en) * 2022-06-17 2022-09-30 中国华能集团清洁能源技术研究院有限公司 Preparation method of organic-inorganic composite membrane in alkaline electrolysis device
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CN115074763B (en) * 2022-07-01 2024-01-30 中国华能集团清洁能源技术研究院有限公司 Preparation method of alkaline electrolyzed water hydrogen production diaphragm and diaphragm
CN115896863A (en) * 2022-10-25 2023-04-04 清华大学 Ultrathin composite diaphragm for alkaline water electrolysis, preparation method thereof and alkaline water electrolysis device
CN115896863B (en) * 2022-10-25 2023-09-12 清华大学 Composite diaphragm for ultrathin alkaline water electrolysis, preparation method thereof and alkaline water electrolysis device
WO2024087747A1 (en) * 2022-10-25 2024-05-02 清华大学 Ultrathin composite diaphragm for alkaline water electrolysis, preparation method therefor, and alkaline water electrolysis apparatus
CN115819818A (en) * 2022-12-23 2023-03-21 乐凯胶片股份有限公司 Composite diaphragm for hydrogen production by alkaline water electrolysis and preparation method thereof
CN116219492B (en) * 2022-12-28 2023-10-24 嘉庚创新实验室 Composite diaphragm for producing hydrogen by alkaline water electrolysis and preparation method thereof
CN116219492A (en) * 2022-12-28 2023-06-06 嘉庚创新实验室 Composite diaphragm for producing hydrogen by alkaline water electrolysis and preparation method thereof
WO2024140890A1 (en) * 2022-12-28 2024-07-04 嘉庚创新实验室 Organic-inorganic composite separator for production of hydrogen by alkaline water electrolysis, and preparation method therefor
WO2024140892A1 (en) * 2022-12-28 2024-07-04 嘉庚创新实验室 Composite diaphragm for hydrogen production by alkaline electrolyzed water, and preparation method for composite diaphragm
CN116238174A (en) * 2023-02-27 2023-06-09 海卓迈博(苏州)新材料有限公司 Method for continuously preparing alkaline electrolyzed water composite membrane
CN117512692A (en) * 2023-11-17 2024-02-06 武汉理工大学 Coating type alkaline water electrolysis hydrogen production diaphragm
CN117512692B (en) * 2023-11-17 2024-05-03 武汉理工大学 Coating type alkaline water electrolysis hydrogen production diaphragm
CN118374835A (en) * 2024-04-18 2024-07-23 北京元泰能材科技有限公司 Composite diaphragm and preparation method and application thereof

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