CN117403276A - Preparation method of alkaline water electrolysis composite diaphragm and alkaline water electrolysis composite diaphragm - Google Patents

Preparation method of alkaline water electrolysis composite diaphragm and alkaline water electrolysis composite diaphragm Download PDF

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Publication number
CN117403276A
CN117403276A CN202311236181.3A CN202311236181A CN117403276A CN 117403276 A CN117403276 A CN 117403276A CN 202311236181 A CN202311236181 A CN 202311236181A CN 117403276 A CN117403276 A CN 117403276A
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alkaline water
water electrolysis
net
polyphenylene sulfide
preparing
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陆利斌
刘毅
黄后强
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Tonyshare Suzhou Electronic Materials Technology Co ltd
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Tonyshare Suzhou Electronic Materials Technology Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
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    • 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
    • B01D67/0002—Organic membrane manufacture
    • B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
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    • B01D67/0002—Organic membrane manufacture
    • B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
    • B01D67/0013—Casting processes
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    • 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
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
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    • B01D69/10—Supported membranes; Membrane supports
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    • 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
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    • 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
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01D71/06—Organic material
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01D71/06—Organic material
    • B01D71/66—Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01D71/06—Organic material
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    • 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
    • C25B13/04—Diaphragms; Spacing elements characterised by the material
    • C25B13/08—Diaphragms; Spacing elements characterised by the material based on organic materials
    • 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
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/17—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
    • C25B9/19—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01D2325/36—Hydrophilic membranes
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    • C08J2381/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen, or carbon only; Polysulfones; Derivatives of such polymers
    • C08J2381/06—Polysulfones; Polyethersulfones
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08J2401/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
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    • C08J2401/04—Oxycellulose; Hydrocellulose
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    • C08K3/22—Oxides; Hydroxides of metals
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    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives

Abstract

The invention discloses a preparation method of an alkaline water electrolysis composite diaphragm and the alkaline water electrolysis composite diaphragm, which comprises the following steps: s1, preparing a casting film liquid: preparing slurry by taking polysulfone, ceria nano-particles and cellulose crystals as raw materials; s2, carrying out hot-pressing treatment by taking a polyphenylene sulfide net as a support body, and carrying out hot-pressing treatment on the support body by using a hot-pressing method; s3, preparing a composite film with a support: and (3) soaking the polyphenylene sulfide net subjected to hot pressing in the prepared casting solution in a casting machine with a scraper device, preparing a diaphragm with certain thickness, pre-evaporating for a proper time, and then performing a phase conversion method by using deionized water, and repeatedly cleaning the composite diaphragm in the deionized water to obtain the alkaline water electrolysis composite diaphragm which is high in high temperature resistance, corrosion resistance, high in mechanical strength and good in hydrophilicity. The alkaline water electrolysis composite diaphragm has the advantages of simple method, lower cost, easy realization of industrial development, and capability of ensuring reliable performance and online quality of products.

Description

Preparation method of alkaline water electrolysis composite diaphragm and alkaline water electrolysis composite diaphragm
Technical Field
The invention relates to the technical field of diaphragm preparation, in particular to a preparation method of an alkaline water electrolysis composite diaphragm and the alkaline water electrolysis composite diaphragm.
Background
With the continuous development of economy and the development of the aim of 'double carbon', people pay more and more attention to energy sources, because the energy sources are not only important factors for human survival and development, but also important material foundations and guarantees for national economy and social development. Today, the use of traditional fossil energy sources such as coal, oil and natural gas in large quantities will cause the energy sources to be increasingly exhausted, and at the same time cause serious pollution to the environment. The development of renewable energy sources is therefore of great importance. The hydrogen energy is an ideal, clean and efficient secondary energy which is paid more attention to worldwide, and the advantages of simple operation, recycling, high energy density and the like are effective ways for solving the current energy.
Currently, the sources of hydrogen are mainly classified into three types, gray hydrogen, blue hydrogen and green hydrogen. Wherein, the ash hydrogen is hydrogen generated by burning fossil fuel, and simultaneously generates carbon dioxide emission, which accounts for about 95% of global emission; blue hydrogen is produced by reforming natural gas with steam methane or natural steam, and although natural gas belongs to fossil fuel, blue hydrogen is produced and greenhouse gas is also produced; while green hydrogen is hydrogen produced by renewable energy sources (wind, nuclear, solar) which do not produce carbon emissions at all, it is limited by current technology and costs and has not been applied on a large scale. However, the alkaline water electrolysis hydrogen production technology is relatively mature, the operation is simple, the corrosion to equipment is small, the purity of the prepared hydrogen is high, and the hydrogen production method for realizing wide large-scale application is realized.
In an alkaline water electrolysis cell, a cathode and an anode respectively generate hydrogen and oxygen, wherein the existence of a diaphragm is important, and the diaphragm can effectively block the mixture of the hydrogen and the oxygen, so that the aim of producing pure hydrogen is fulfilled. Therefore, the quality of the diaphragm directly influences the purity of hydrogen and oxygen and the electricity consumption problem, and the problem of the purity and the electricity consumption of the hydrogen and the oxygen is gradually becoming a hot point of research. The ideal separator material should possess four characteristics: first, good ionic conductivity, high porosity, low resistivity; secondly, high hydrophilicity, high diaphragm gas property and corrosion resistance; thirdly, the pore is small, the thickness is thin, and the dimensional stability is good; fourth, long service life and low preparation cost.
According to domestic and foreign reports, the alkaline water electrolysis diaphragm is mainly divided into two main types, namely an asbestos diaphragm and a non-asbestos diaphragm. Most of early manufacturers adopt asbestos cloth as a diaphragm, and the diaphragm has the defects of low price and good insulativity, for example, during the electrolysis process, asbestos is easy to expand so as to greatly shorten the service life, and the impact of gas is easy to generate holes along the thickness method, so that the purity of hydrogen gas is reduced, and the asbestos is also a cancerogenic substance and causes great threat to the health and safety of human bodies. The non-asbestos diaphragm is mainly divided into two main categories of fabrics formed by weaving organic polymer fibers and organic-inorganic composite diaphragms. The fabric formed by weaving the organic polymer fibers mainly comprises polyphenylene sulfide (PPS) and Polysulfones (PSF), the chemical property of the material is stable, and the material is resistant to high temperature and alkali, but the polymer is hydrophobic, so that grafting, sulfonation treatment or post-treatment of the material or the fabric is needed, and the membrane is kept to have better wettability. CN112159989a discloses a porous support and a porous polymer membrane impregnated into the support from one surface of the support, and the membrane has a significantly reduced mechanical strength and a certain thickness after hydrophilic treatment, although the porous polymer membrane exhibits a good electrolytic effect. CN110869538B discloses an alkaline hydrolysis reinforced separator, which is characterized in that two sides of a porous support body comprise different porous polymer layers, gas blocking is achieved, bubble traps do not occur, electrolyte is fully permeated in the separator to ensure ionic conductivity, however, the porous polymer layers at two sides of the support body need to be prepared in steps, and the preparation is complex. In another organic-inorganic composite diaphragm, the diaphragm with corresponding requirements is obtained by combining an organic film material with an inorganic material. But there are also often incompatibilities between the polymer matrices, reduced mechanical stability of the resulting materials over time, complex manufacturing processes, etc.
Therefore, based on the technical defects, the development of the alkaline water electrolysis composite membrane and the preparation method thereof, which have the advantages of simple preparation process, large-scale production, uniform and complete membrane surface, good corrosion resistance, mechanical strength and hydrophilicity, are very important, and have profound significance for the development of the alkaline water electrolysis hydrogen production technology.
Disclosure of Invention
The invention solves the technical problem of providing a preparation method of an alkaline water electrolysis composite diaphragm, and the alkaline water electrolysis composite diaphragm prepared by the method has excellent high specific strength and heat stability and excellent hydrophilic performance.
The technical scheme adopted for solving the technical problems is as follows: a preparation method of an alkaline water electrolysis composite diaphragm comprises the following steps,
s1, preparing a casting film liquid: dissolving polysulfone resin in N-methyl pyrrolidone, and fully stirring to obtain a uniformly dispersed polysulfone solution; then adding polyvinylpyrrolidone, and fully stirring at room temperature to completely and uniformly dissolve the solute; adding cerium oxide nano particles and cellulose crystals, continuously stirring until the mixture is uniform, and then carrying out degassing treatment to obtain uniform casting solution;
s2, preparing a support composite film: casting the casting solution on a clean glass substrate, soaking a polyphenylene sulfide net in the casting solution obtained in the step S1, scraping off redundant casting solution on the surface of the polyphenylene sulfide net by using a stainless steel scraper, and then sequentially placing the polyphenylene sulfide net soaked in the casting solution into a plurality of water tanks containing deionized water for repeated soaking and cleaning for phase inversion until the deionized water in the water tanks is not turbid, thereby obtaining the alkaline water electrolytic composite diaphragm.
Further is: the following steps are added between the step S1 and the step S2: and carrying out hot pressing treatment on the polyphenylene sulfide net.
Further is: in step S1, polysulfone resin is dissolved in N-methylpyrrolidone, wherein the mass part of the polysulfone resin is 10-40 parts, and the mass part of the N-methylpyrrolidone is 40-150 parts.
Further is: in step S1, polyvinylpyrrolidone is added into a polysulfone solution containing N-methylpyrrolidone, wherein the mass part of polyvinylpyrrolidone is 10-40 parts.
Further is: the nano size of the cerium oxide nano particles is 10nm, 30nm, 50nm or 100nm, and the mass parts of the cerium oxide nano particles are 10-35 parts.
Further is: the mass portion of the cellulose crystal is 2-4.
Further is: the mesh number of the polyphenylene sulfide net is 40 meshes or 60 meshes.
Further is: in the step S2, the polyphenylene sulfide net is subjected to hot pressing treatment, wherein the hot pressing temperature is 50-110 ℃, and the hot pressing time is 3-10min.
The invention also discloses an alkaline water electrolysis composite diaphragm, which comprises a polyphenylene sulfide net, wherein the polyphenylene sulfide net is used as a base material, and the alkaline water electrolysis composite diaphragm is prepared by the preparation method of the alkaline water electrolysis composite diaphragm, and the thickness of the alkaline water electrolysis composite diaphragm is 0.5+/-0.05 mm.
The beneficial effects of the invention are as follows: the alkaline water electrolysis composite diaphragm prepared by the invention has the advantages of high temperature resistance, corrosion resistance, high mechanical strength and good hydrophilicity and the preparation method thereof. The polyphenylene sulfide net with high thermal stability, chemical corrosion resistance, good flame retardance and good mechanical property is used as a support, so that the mechanical strength of the diaphragm is greatly improved; the ceria has better mechanical strength and excellent oxygen ion transmission performance, and improves the corrosion resistance, mechanical performance and conductivity of the polymer to different degrees; an electrochemically stable polysulfone as a binder; the cellulose nanocrystals have a crystal structure with high hydroxyl content, not only have excellent high specific strength and thermal stability, but also have excellent hydrophilic performance, and the hydrophilic performance, thermal performance and mechanical performance of the polysulfone composite membrane are effectively improved.
Drawings
FIG. 1 is a schematic flow chart of a method for preparing an alkaline water electrolysis composite membrane according to an embodiment of the present application.
Marked in the figure as:
Detailed Description
In order that the above objects, features and advantages of the invention will be readily understood, a more particular description of the invention will be rendered by reference to the appended drawings.
As shown in fig. 1, the embodiment of the present application discloses a method for preparing an alkaline water electrolysis composite membrane, comprising the following steps,
s1, preparing a casting film liquid: dissolving polysulfone resin in N-methyl pyrrolidone, and fully stirring to obtain a uniformly dispersed polysulfone solution; then adding polyvinylpyrrolidone, and fully stirring at room temperature to completely and uniformly dissolve the solute; adding cerium oxide nano particles and cellulose crystals, continuously stirring until the mixture is uniform, and then carrying out degassing treatment to obtain uniform casting solution;
s2, carrying out hot-pressing treatment on the polyphenylene sulfide net;
s3, preparing a support composite film: casting the casting solution on a clean glass substrate, soaking the polyphenylene sulfide net treated in the step S2 in the casting solution obtained in the step S1, scraping the redundant casting solution on the surface of the polyphenylene sulfide net by using a stainless steel scraper, and then sequentially placing the polyphenylene sulfide net soaked in the casting solution into a plurality of water tanks containing deionized water for repeated soaking and cleaning for phase conversion until the deionized water in the water tanks is not turbid, thereby obtaining the alkaline water electrolysis composite diaphragm.
Specifically, the casting solution prepared in the step S1 is in a viscous state, so that it can be well adhered to the polyphenylene sulfide mesh and the mesh holes in the polyphenylene sulfide mesh are filled.
In order to solve the problem that the flatness of the PPS net is reduced along with the reduction of the thickness, so that the PPS net is exposed on the surface of the composite film, and the air permeability of the composite film is further improved, the PPS net is subjected to heat treatment by adopting a hot pressing method, and the flatness of the PPS net is improved.
In the method, the polyphenylene sulfide net has the characteristics of high thermal stability, chemical corrosion resistance, good flame retardance and good mechanical property, is used as a support of the composite diaphragm, so that the mechanical strength of the composite diaphragm is greatly improved, the ceria has good mechanical strength and excellent oxygen ion transmission property, the corrosion resistance, the mechanical property and the conductivity of the polymer are improved to different degrees, the polysulfone resin is used as an adhesive, the electrochemical property is stable, and meanwhile, the cellulose crystal has a crystal structure with high hydroxyl content, has excellent high specific strength and thermal stability, has excellent hydrophilic property, and effectively improves the hydrophilic property, the thermal property and the mechanical property of the composite diaphragm.
Therefore, the diaphragm has the characteristics of good high temperature resistance and corrosion resistance, high mechanical strength and good hydrophilicity.
In this embodiment, in step S1, polysulfone resin is dissolved in N-methylpyrrolidone, wherein the mass part of the polysulfone resin is 10 parts to 40 parts, specifically 10 parts, 30 parts, 40 parts, etc., and the mass part of the N-methylpyrrolidone is 40 parts to 150 parts, specifically 40 parts, 60 parts, 100 parts, 150 parts, etc.
In this embodiment, in step S1, polyvinylpyrrolidone is added to the polysulfone solution to which N-methylpyrrolidone is added, and the mass part of polyvinylpyrrolidone is 10 parts to 40 parts, specifically 10 parts, 30 parts, 40 parts, etc.
In this embodiment, the nano size of the ceria nanoparticle is 10nm, 30nm, 50nm or 100nm, and the mass portion of the ceria nanoparticle is 10 to 35, specifically 10, 20, 35, etc.
In this embodiment, the mass portion of the cellulose crystal is 2-4, specifically 2, 3, 4, etc.
In this embodiment, the mesh number of the polyphenylene sulfide mesh is 40 mesh or 60 mesh.
In this embodiment, in step S2, the polyphenylene sulfide mesh is subjected to a hot pressing treatment at a hot pressing temperature of 50-110 ℃, specifically 50 ℃, 80 ℃, 110 ℃, etc., for a hot pressing time of 3-10min, specifically 3min, 8min, 10min, etc.
The invention also discloses an alkaline water electrolysis composite diaphragm, which comprises a polyphenylene sulfide net, wherein the polyphenylene sulfide net is used as a base material, and the alkaline water electrolysis composite diaphragm is prepared by the preparation method of the alkaline water electrolysis composite diaphragm, and the thickness of the alkaline water electrolysis composite diaphragm is 0.5+/-0.05 mm.
The following are specific examples of the present method:
example 1
The preparation method of the alkaline water electrolysis composite diaphragm comprises the following steps:
s1, preparing a casting film liquid:
dissolving 12 parts of polysulfone resin in 50 parts of N-methylpyrrolidone (NMP), and fully stirring at 350r/min to obtain a uniformly dispersed polysulfone solution; adding 12 parts of polyvinylpyrrolidone (PVP), and stirring at the same rotation speed at room temperature to completely and uniformly dissolve the solute to obtain a white viscous mixture; 15 parts of 10 nm-sized cerium oxide (CeO) were added 2 ) The nanoparticles and 3 parts of cellulose crystals (CNC) were mixed and stirred until homogeneousThen stirring for 24 hours at a rotating speed of 80r/min, and carrying out degassing treatment to obtain uniform casting solution.
S2, carrying out hot pressing treatment on the support body:
and carrying out heat treatment on the 40-mesh PPS net by adopting a hot pressing method so as to improve the planeness of the PPS net. The hot pressing temperature is set to 60 ℃; the hot pressing time was set to 5min.
S3, preparation of support composite membrane
Casting the casting solution on a clean glass substrate, soaking the polyphenylene sulfide net treated in the step S2 in the casting solution obtained in the step S1, scraping the redundant casting solution on the surface of the polyphenylene sulfide net by using a stainless steel scraper, controlling the thickness to be 0.5+/-0.05 mm, standing the scraped membrane in air, performing 20S pre-evaporation, sequentially placing the polyphenylene sulfide net soaked in the casting solution in a plurality of pools containing deionized water for repeated soaking and cleaning, and performing phase conversion until the deionized water in the pools is not turbid, thereby obtaining the alkaline water electrolysis composite membrane (polyphenylene sulfide (PPS) net supporting polysulfone/ceria and cellulose crystal composite membrane with high temperature resistance, corrosion resistance, good mechanical strength and good hydrophilicity).
Example 2
The preparation method of the alkaline water electrolysis composite diaphragm comprises the following steps:
s1, preparing a casting film liquid:
32 parts of polysulfone resin is dissolved in 120 parts of N-methyl pyrrolidone (NMP) and fully stirred at 350r/min to obtain a uniformly dispersed polysulfone solution; adding 35 parts of polyvinylpyrrolidone (PVP), and stirring at the same rotation speed at room temperature to completely and uniformly dissolve the solute to obtain a white viscous mixture; 30 parts of cerium oxide (CeO) are added 2 ) (size 10 nm) nanoparticles and 3.5 parts of cellulose crystals (CNC) were mixed and stirred until uniform, and then stirred at a rotation speed of 80r/min for 24 hours, and subjected to degassing treatment to obtain a uniform casting solution.
S2, carrying out hot pressing treatment on the support body:
and carrying out heat treatment on the 60-mesh PPS net by adopting a hot pressing method so as to improve the planeness of the PPS net. The hot pressing temperature is set to 100 ℃; the hot pressing time was set to 6min.
S3, preparation of support composite membrane
Casting the casting solution on a clean glass substrate, soaking the polyphenylene sulfide net treated in the step S2 in the casting solution obtained in the step S1, scraping the redundant casting solution on the surface of the polyphenylene sulfide net by using a stainless steel scraper, controlling the thickness to be 0.5+/-0.05 mm, standing the scraped membrane in air, performing 25 seconds of pre-evaporation, sequentially placing the polyphenylene sulfide net soaked in the casting solution in a plurality of pools containing deionized water for repeated soaking and cleaning, and performing phase conversion until the deionized water in the pools is not turbid, thereby obtaining the alkaline water electrolysis composite membrane (polyphenylene sulfide (PPS) net supporting polysulfone/ceria and cellulose crystal composite membrane with high temperature resistance, corrosion resistance, good mechanical strength and good hydrophilicity).
Example 3
The preparation method of the alkaline water electrolysis composite diaphragm comprises the following steps:
s1, preparing a casting film liquid:
32 parts of polysulfone resin is dissolved in 120 parts of N-methyl pyrrolidone (NMP) and fully stirred at 350r/min to obtain a uniformly dispersed polysulfone solution; adding 35 parts of polyvinylpyrrolidone (PVP), and stirring at the same rotation speed at room temperature to completely and uniformly dissolve the solute to obtain a white viscous mixture; 30 parts of cerium oxide (CeO) are added 2 ) (30 nm in size) nanoparticles and 3.5 parts of cellulose crystals (CNC) were mixed and stirred until uniform, and then stirred at a rotation speed of 80r/min for 24 hours, and subjected to degassing treatment to obtain a uniform casting solution.
S2, carrying out hot pressing treatment on the support body:
and carrying out heat treatment on the 60-mesh PPS net by adopting a hot pressing method so as to improve the planeness of the PPS net. The hot pressing temperature is set to 100 ℃; the hot pressing time was set to 6min.
S3, preparation of support composite membrane
Casting the casting solution on a clean glass substrate, soaking the polyphenylene sulfide net treated in the step S2 in the casting solution obtained in the step S1, scraping the redundant casting solution on the surface of the polyphenylene sulfide net by using a stainless steel scraper, controlling the thickness to be 0.5+/-0.05 mm, standing the scraped membrane in air, performing 25 seconds of pre-evaporation, sequentially placing the polyphenylene sulfide net soaked in the casting solution in a plurality of pools containing deionized water for repeated soaking and cleaning, and performing phase conversion until the deionized water in the pools is not turbid, thereby obtaining the alkaline water electrolysis composite membrane (polyphenylene sulfide (PPS) net supporting polysulfone/ceria and cellulose crystal composite membrane with high temperature resistance, corrosion resistance, good mechanical strength and good hydrophilicity).
Example 4
The preparation method of the alkaline water electrolysis composite diaphragm comprises the following steps:
s1, preparing a casting film liquid:
32 parts of polysulfone resin is dissolved in 120 parts of N-methyl pyrrolidone (NMP) and fully stirred at 350r/min to obtain a uniformly dispersed polysulfone solution; adding 35 parts of polyvinylpyrrolidone (PVP), and stirring at the same rotation speed at room temperature to completely and uniformly dissolve the solute to obtain a white viscous mixture; 30 parts of cerium oxide (CeO) are added 2 ) (50 nm in size) nanoparticles and 3.5 parts of cellulose crystals (CNC) were mixed and stirred until uniform, and then stirred at a rotation speed of 80r/min for 24 hours, and subjected to degassing treatment to obtain a uniform casting solution.
S2, carrying out hot pressing treatment on the support body:
and carrying out heat treatment on the 60-mesh PPS net by adopting a hot pressing method so as to improve the planeness of the PPS net. The hot pressing temperature is set to 100 ℃; the hot pressing time was set to 6min.
S3, preparation of support composite membrane
Casting the casting solution on a clean glass substrate, soaking the polyphenylene sulfide net treated in the step S2 in the casting solution obtained in the step S1, scraping the redundant casting solution on the surface of the polyphenylene sulfide net by using a stainless steel scraper, controlling the thickness to be 0.5+/-0.05 mm, standing the scraped membrane in air, performing 25 seconds of pre-evaporation, sequentially placing the polyphenylene sulfide net soaked in the casting solution in a plurality of pools containing deionized water for repeated soaking and cleaning, and performing phase conversion until the deionized water in the pools is not turbid, thereby obtaining the alkaline water electrolysis composite membrane (polyphenylene sulfide (PPS) net supporting polysulfone/ceria and cellulose crystal composite membrane with high temperature resistance, corrosion resistance, good mechanical strength and good hydrophilicity).
Example 5
The preparation method of the alkaline water electrolysis composite diaphragm comprises the following steps:
s1, preparing a casting film liquid:
32 parts of polysulfone resin is dissolved in 120 parts of N-methyl pyrrolidone (NMP) and fully stirred at 350r/min to obtain a uniformly dispersed polysulfone solution; adding 35 parts of polyvinylpyrrolidone (PVP), and stirring at the same rotation speed at room temperature to completely and uniformly dissolve the solute to obtain a white viscous mixture; 30 parts of cerium oxide (CeO) are added 2 ) (100 nm in size) nanoparticles and 3.5 parts of cellulose crystals (CNC) were mixed and stirred until uniform, and then stirred at a rotation speed of 80r/min for 24 hours, and subjected to degassing treatment to obtain a uniform casting solution.
S2, carrying out hot pressing treatment on the support body:
and carrying out heat treatment on the 60-mesh PPS net by adopting a hot pressing method so as to improve the planeness of the PPS net. The hot pressing temperature is set to 100 ℃; the hot pressing time was set to 6min.
S3, preparation of support composite membrane
Casting the casting solution on a clean glass substrate, soaking the polyphenylene sulfide net treated in the step S2 in the casting solution obtained in the step S1, scraping the redundant casting solution on the surface of the polyphenylene sulfide net by using a stainless steel scraper, controlling the thickness to be 0.5+/-0.05 mm, standing the scraped membrane in air, performing 25 seconds of pre-evaporation, sequentially placing the polyphenylene sulfide net soaked in the casting solution in a plurality of pools containing deionized water for repeated soaking and cleaning, and performing phase conversion until the deionized water in the pools is not turbid, thereby obtaining the alkaline water electrolysis composite membrane (polyphenylene sulfide (PPS) net supporting polysulfone/ceria and cellulose crystal composite membrane with high temperature resistance, corrosion resistance, good mechanical strength and good hydrophilicity).
Comparative example 1
S1, preparing a casting film liquid:
32 parts of polysulfone resin were dissolved in 120 parts of N-methylpyrrolidone (NMP) at 35Stirring thoroughly at 0r/min to obtain polysulfone solution with uniform dispersion; adding 35 parts of polyvinylpyrrolidone (PVP), and stirring at the same rotation speed at room temperature to completely and uniformly dissolve the solute to obtain a white viscous mixture; 30 parts of cerium oxide (CeO) are added 2 ) (100 nm) nano particles, mixing and stirring uniformly, stirring at a rotating speed of 80r/min for 24 hours, and degassing to obtain uniform casting solution.
S2, carrying out hot pressing treatment on the support body:
and carrying out heat treatment on the 60-mesh PPS net by adopting a hot pressing method so as to improve the planeness of the PPS net. The hot pressing temperature is set to 100 ℃; the hot pressing time was set to 6min.
S3, preparation of support composite film
Casting the casting solution on a clean glass substrate, soaking the polyphenylene sulfide net treated in the step S2 in the casting solution obtained in the step S1, scraping the redundant casting solution on the surface of the polyphenylene sulfide net by using a stainless steel scraper, controlling the thickness to be 0.5+/-0.05 mm, standing the scraped membrane in air, performing 25 seconds of pre-evaporation, sequentially placing the polyphenylene sulfide net soaked in the casting solution in a plurality of pools containing deionized water for repeated soaking and cleaning, and performing phase conversion until the deionized water in the pools is not turbid, thereby obtaining the alkaline water electrolysis composite membrane (polyphenylene sulfide (PPS) net supporting polysulfone/ceria and cellulose crystal composite membrane with high temperature resistance, corrosion resistance, good mechanical strength and good hydrophilicity).
Comparative example 2
The product is a Pure Polyphenylene Sulfide (PPS) braided fabric diaphragm, and the gram weight is 600+/-20 g/square meter.
The following are experimental results of the above examples:
average pore diameter (nm) Porosity (%) Water contact angle (°) Breaking strength (MPa) Diaphragm thickness (mum) Resistance value (omega square meter)
Example 1 60.2 70.2 86.3 2.98 532 0.29
Example 2 59.8 65.4 83.2 3.21 530 0.26
Example 3 57.6 63.2 76.5 3.3 531 0.28
Example 4 56.1 60.2 70.9 3.42 528 0.26
Example 5 55.2 59.6 66.8 3.55 529 0.21
Comparative example 1 66.5 72.3 95.4 2.63 545 0.45
Comparative example 2 80.2 216.3 109.4 2.36 600 0.6
The specific test method comprises the following steps:
1. aperture testing
The composite membrane was tested for maximum pore size using the bubbling method. See GB/T2679.14-1996 standard. The testing method comprises the following steps: the compressed nitrogen enters the liquid from one side of the composite membrane through the membrane pores to generate bubbles, and the pressure required is different when the pore sizes are different. The aperture calculated according to the pressure formula is the maximum aperture.
Wherein γ is the liquid surface tension (mN/m); θ is the contact angle (°) between the liquid and the membrane; p is the pressure difference (Pa) across the composite diaphragm.
2. Porosity test
The porosity of the composite membrane was measured by a weighing method. Selecting a diaphragm sample with a certain area, fully soaking the diaphragm sample in absolute ethyl alcohol, and then replacing the diaphragm sample with deionized water. Ultrasonic vibration is adopted to completely wet the pores of the diaphragm by deionized water, and the middle of the diaphragm needs to be replaced by two times of deionized water. Before the test, the moisture adhering to the surface of the membrane was rapidly wiped off with a filter paper, and the mass of the wet membrane was weighed with an electronic balance. The weighed wet film is placed into a vacuum drying oven at 50 ℃ for full drying, and the mass of the dry film is weighed again. The membrane porosity was then calculated according to the formula.
Wherein ω is the porosity of the composite separator; ρ is the density of deionized water (g/mL); a is the area (cm 2) of the membrane; l is the thickness (cm) of the membrane sheet in wet state; m is m w And m d The mass (g) of the separator in wet and dry states, respectively.
3. Water contact angle test
The water contact angle of the composite separator was measured using a DeFeddataphysics OCA25 instrument. Cutting the diaphragm into samples with 20mmx and 20mm, and adding 3 pieces; washing and soaking the cut sample with deionized water for 3 times, and putting the sample into a vacuum drying oven at 50 ℃ for full drying; 1. Mu.L of pure water was dropped on the surface of the film to be measured and an image photograph was rapidly taken. Fitting a liquid drop profile curve in the image, and calculating a contact angle; the average value of the measurement of 3 specimens was taken as the measurement result.
4. Breaking strength test
Diaphragm breaking strength reference standard: GB/T1040.3-2006. The test pieces were cut into long test pieces having a width of 10mm to 25mm and a length of not less than 150mm, and the average value was measured by three groups.
5. Diaphragm thickness test
The thickness of the composite diaphragm is measured by a micrometer, the minimum scale is 0.01mm, and five groups of average values are taken.
6. Composite diaphragm surface resistance test
And testing the resistance value of the composite diaphragm by adopting an alternating current low resistance meter. Cutting a sample to be tested into a composite test clamp plate size, soaking in potassium hydroxide solution for 1h, injecting the potassium hydroxide solution into an electrolytic cell for testing, clamping an electrode of the electrolytic cell by a resistance meter test clamp plate, and measuring a solution resistance value R 1 Placing the diaphragm into an electrolytic cell to be tested, and measuring the total resistance R of the sample and the solution 2 The diaphragm plane resistance was calculated according to the following formula.
R＝(R 2 -R 1 )*S
Wherein R is the area resistance value of the sample, and Ω×cm 2 ；R 1 Is the solution resistance value omega; r is R 2 The total resistance value omega of the sample and the solution; s is the membrane test area cm2.
Conclusion:
compared with the composite membrane of comparative examples 1-5 without cellulose crystal and the Pure Polyphenylene Sulfide (PPS) braided fabric membrane, the result shows that the alkaline water electrolysis composite membrane prepared by the method has smaller average pore diameter and higher porosity, can better block the mixture of oxygen generated by anode measurement and hydrogen generated by cathode measurement, ensures that the purity of the prepared hydrogen is higher, and improves the benefit and safety of the electrolysis process.
The results of the alkaline water electrolysis composite membrane prepared by the method show that the alkaline water electrolysis composite membrane prepared by the method has smaller water contact angle, the composite membrane has better hydrophilic performance, and the water contact angle size is reduced as the size of the cerium oxide nano particles is larger, compared with the composite membrane without added cellulose crystals in comparative example 1-5 and the Pure Polyphenylene Sulfide (PPS) braided fabric membrane.
The results of the alkaline water electrolysis composite membrane prepared by the method show that the alkaline water electrolysis composite membrane prepared by the comparative examples 1-5 has higher breaking strength and thinner membrane thickness compared with the composite membrane without added cellulose crystal, namely the comparative example 1 and the Pure Polyphenylene Sulfide (PPS) braided fabric membrane.
The results of the alkaline water electrolysis organic-inorganic composite membrane prepared by the method show that the resistance value is smaller and the current efficiency is higher compared with the composite membrane without added cellulose crystal of comparative example 1 and the Pure Polyphenylene Sulfide (PPS) braided fabric membrane by the alkaline water electrolysis composite membrane of comparative examples 1-5.
While the foregoing is directed to embodiments of the present invention, other and further details of the invention may be had by the present invention, it should be understood that the foregoing description is merely illustrative of the present invention and that no limitations are intended to the scope of the invention, except insofar as modifications, equivalents, improvements or modifications are within the spirit and principles of the invention.

Claims (9)

1. A preparation method of an alkaline water electrolysis composite diaphragm is characterized in that: comprises the steps of,
s1, preparing a casting film liquid: dissolving polysulfone resin in N-methyl pyrrolidone, and fully stirring to obtain a uniformly dispersed polysulfone solution; then adding polyvinylpyrrolidone, and fully stirring at room temperature to completely and uniformly dissolve the solute; adding cerium oxide nano particles and cellulose crystals, continuously stirring until the mixture is uniform, and then carrying out degassing treatment to obtain uniform casting solution;
s2, preparing a support composite film: casting the casting solution on a clean glass substrate, soaking a polyphenylene sulfide net in the casting solution obtained in the step S1, scraping off redundant casting solution on the surface of the polyphenylene sulfide net by using a stainless steel scraper, and then sequentially placing the polyphenylene sulfide net soaked in the casting solution into a plurality of water tanks containing deionized water for repeated soaking and cleaning for phase inversion until the deionized water in the water tanks is not turbid, thereby obtaining the alkaline water electrolytic composite diaphragm.
2. The method for preparing the alkaline water electrolysis composite diaphragm according to claim 1, wherein the method comprises the following steps: the following steps are added between the step S1 and the step S2: and carrying out hot pressing treatment on the polyphenylene sulfide net.
3. The method for preparing the alkaline water electrolysis composite diaphragm according to claim 1, wherein the method comprises the following steps: in step S1, polysulfone resin is dissolved in N-methylpyrrolidone, wherein the mass part of the polysulfone resin is 10-40 parts, and the mass part of the N-methylpyrrolidone is 40-150 parts.
4. The method for preparing an alkaline water electrolysis composite membrane according to claim 3, wherein: in step S1, polyvinylpyrrolidone is added into a polysulfone solution containing N-methylpyrrolidone, wherein the mass part of polyvinylpyrrolidone is 10-40 parts.
5. The method for preparing the alkaline water electrolysis composite diaphragm according to claim 4, which is characterized in that: the nano size of the cerium oxide nano particles is 10nm, 30nm, 50nm or 100nm, and the mass parts of the cerium oxide nano particles are 10-35 parts.
6. The method for preparing the alkaline water electrolysis composite diaphragm according to claim 4, which is characterized in that: the mass portion of the cellulose crystal is 2-4.
7. The method for preparing the alkaline water electrolysis composite diaphragm according to claim 1, wherein the method comprises the following steps: the mesh number of the polyphenylene sulfide net is 40 meshes or 60 meshes.
8. The method for preparing the alkaline water electrolysis composite diaphragm according to claim 1, wherein the method comprises the following steps: in the step S2, the polyphenylene sulfide net is subjected to hot pressing treatment, wherein the hot pressing temperature is 50-110 ℃, and the hot pressing time is 3-10min.
9. An alkaline water electrolysis composite membrane, includes polyphenylene sulfide net, its characterized in that: the alkaline water electrolysis composite membrane is prepared by using the preparation method of the alkaline water electrolysis composite membrane as claimed in any one of claims 1 to 7, wherein the polyphenylene sulfide mesh is used as a base material, and the thickness of the alkaline water electrolysis composite membrane is 0.5+/-0.05 mm.
CN202311236181.3A 2023-09-25 2023-09-25 Preparation method of alkaline water electrolysis composite diaphragm and alkaline water electrolysis composite diaphragm Pending CN117403276A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117721498A (en) * 2024-02-07 2024-03-19 宁波中科氢易膜科技有限公司 Preparation method of organic-inorganic hybrid ion composite membrane

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117721498A (en) * 2024-02-07 2024-03-19 宁波中科氢易膜科技有限公司 Preparation method of organic-inorganic hybrid ion composite membrane
CN117721498B (en) * 2024-02-07 2024-05-07 宁波中科氢易膜科技有限公司 Preparation method of organic-inorganic hybrid ion composite membrane

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