CN117385413A - Composite polymer porous membrane and preparation method and application thereof - Google Patents
Composite polymer porous membrane and preparation method and application thereof Download PDFInfo
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N hexane Substances CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 4
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 4
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Classifications
-
- 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
- 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
- C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
- C25B9/60—Constructional parts of cells
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
The invention provides a composite polymer porous membrane, a preparation method and application thereof, wherein the preparation method comprises the following steps: mixing a first solvent, a second solvent, a polymer and hydrophilic inorganic particles to obtain a casting solution; the first solvent is a good solvent of the polymer, the boiling point of the first solvent is less than that of the second solvent, and the surface tension of the first solvent is less than that of the second solvent; coating the casting film liquid on a supporting net to obtain a liquid film containing the supporting net; removing the first solvent in the liquid film to obtain a primary film; and removing the second solvent in the primary membrane to obtain the composite polymer porous membrane. The preparation method is simple and easy to implement, and the three-dimensional through structure with high porosity is formed in the obtained composite polymer porous membrane through the design and mutual compounding of the first solvent, the second solvent and the specific preparation process, so that the preparation method has the characteristics of high mass transfer efficiency, good gas barrier effect, high mechanical property and low resistance, and the performance requirement of the alkaline water electrolysis cell on the membrane is fully met.
Description
Technical Field
The invention belongs to the technical field of membrane materials, and particularly relates to a composite polymer porous membrane, and a preparation method and application thereof.
Background
The energy source is an important driving force for the progress of human society and has a vital role. The traditional fossil energy is used as the main energy source for a long time, and then some serious problems are brought; on one hand, the traditional fossil energy is taken as non-renewable resources, and can not meet the sustainable development of human society; on the other hand, excessive use of fossil fuel leads to emission of greenhouse gases, which has a relatively bad influence on the global ecological environment. Therefore, the development of clean and efficient renewable energy technology realizes sustainable development of human beings, has become the consensus of countries around the world, and energy transformation is a necessary choice for realizing sustainable development of economy and society. The hydrogen energy is regarded as the best energy carrier by virtue of the advantages of high cleanness, high efficiency, easy storage and transportation and the like, is widely used in a plurality of fields such as electronics, chemical industry and the like besides being used as energy, and has an increasing demand.
Among the numerous hydrogen production processes, electrolyzed water is considered to be an efficient, large-scale, clean hydrogen production technology. When two electrodes (a cathode and an anode) which are electrified with direct current are immersed in an electrolyte, water is decomposed and hydrogen and oxygen are respectively generated at the cathode and the anode, the process is to electrolyze water, and the device is called an electrolytic tank. In the conventional alkaline aqueous solution electrolysis process, an asbestos cloth or polyphenylene sulfide (PPS) cloth is generally used as a separator to isolate the electrodes while conducting hydroxyl (OH) groups in the electrolyte - ) Communicating with the internal circuit. Because the aperture of the asbestos cloth or the polyphenylene sulfide (PPS) for isolation is large, in order to avoid potential safety hazards caused by mutual mixing of generated hydrogen and oxygen, the pressure difference between the cathode and anode chambers is strictly limited in the industry. In addition, asbestos cloth and polyphenylene sulfide cloth have poor hydrophilic performance and larger resistance in the groove, thusThe system consumes more energy, resulting in excessive electrolysis cost.
Improving the diaphragm is one of the main methods for optimizing the hydrogen production technology by water electrolysis, for example, the polyphenylene sulfide is subjected to hydrophilic modification, so that the alkali absorption rate and the conductivity of the polyphenylene sulfide are improved; the common hydrophilic modification method is to carry out high-temperature sulfonation treatment in 98% -99% concentrated sulfuric acid to obtain sulfonated polyphenylene sulfide, and the high-concentration sulfuric acid and the high-temperature treatment are unfavorable for industrial production and bring about troublesome environmental problems although the sulfonated and modified polyphenylene sulfide has strong hydrophilicity. CN115029732a discloses a diaphragm for alkaline water electrolysis, which is made of organic polymer resin, pore-forming agent, inorganic nano particles and a support; the preparation process of the membrane is a traditional immersion precipitation method, and mainly utilizes the difference of solubility of polymers in solvents and non-solvents (coagulation baths), wherein the solvent-non-solvent exchange rate is the most important factor for determining the pore structure of the final membrane. The rapid solvent-non-solvent exchange causes the skin to break through creep relaxation of the polymer, thereby allowing faster solvent-non-solvent exchange under the broken skin, more of the lean phase droplets will form and aggregate, creating large voids, giving the separator a large penetrating finger pore structure, giving it good wettability. However, the mechanical strength of the membrane with the asymmetric morphology of the finger-shaped holes is generally poor, the diffusion effect of the electrolyte in the membrane is poor due to the low porosity, the cost of raw materials is high due to the large amount of inorganic nano particles, the acting force between the polymer and the inorganic nano particles is low, and the problem of serious powder falling in the use process is caused, so that the membrane cannot meet the performance requirement of hydrogen production by water electrolysis.
Therefore, the development of the diaphragm material which has high mass transfer efficiency, good gas barrier effect, good mechanical properties, low resistance, simple process and low cost and is suitable for industrial production so as to meet the requirement of hydrogen production by water electrolysis is a problem to be solved in the field.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a composite polymer porous membrane and a preparation method and application thereof, wherein the preparation method is simple and easy to implement, and the three-dimensional through structure with high porosity is formed in the obtained composite polymer porous membrane through the design and mutual compounding of a first solvent, a second solvent and a specific preparation process, so that the composite polymer porous membrane has the characteristics of high mass transfer efficiency, good air isolation effect, high mechanical property and low resistance, and the performance requirements of an alkaline water electrolyzer on a diaphragm are fully met.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a method for preparing a composite polymer porous membrane, the method comprising:
mixing a first solvent, a second solvent, a polymer and hydrophilic inorganic particles to obtain a casting solution;
the first solvent is a good solvent for the polymer, and the second solvent is miscible with the first solvent; the boiling point of the first solvent is less than the boiling point of the second solvent, and the surface tension of the first solvent is less than the surface tension of the second solvent;
Coating the casting film liquid on a supporting net to obtain a liquid film containing the supporting net;
removing the first solvent in the liquid film to obtain a primary film;
and removing the second solvent in the primary membrane to obtain the composite polymer porous membrane.
In the preparation method provided by the invention, a specific first solvent, a specific second solvent, a specific polymer and specific hydrophilic inorganic particles are adopted to prepare a casting solution, the casting solution is coated on a support net to form a liquid film, and then the first solvent and the specific second solvent are removed in a segmented manner to obtain a composite polymer porous film; the specific conception is as follows:
(1) The first solvent is a good solvent of the polymer so as to enable the polymer to be fully dissolved and form casting solution; meanwhile, the second solvent has good compatibility with the first solvent, so that the second solvent can be uniformly distributed in the casting film liquid and the liquid film, polymer precipitation is avoided, and a uniform porous structure is formed in the composite polymer porous film.
(2) The boiling point of the first solvent is smaller than that of the second solvent, so that the first solvent and the second solvent are removed step by step; the second solvent is capable of remaining in the film during removal of the low boiling point first solvent, and the primary film formed includes the support network, the polymer, the hydrophilic inorganic particles, and the second solvent.
(3) The surface tension of the first solvent is less than that of the second solvent, and the surface tension difference is formed, so that most of the polymer in the casting solution still interacts with the second solvent in the process of removing the first solvent, and the formed primary film has the capacity of secondary forming.
(4) In the process of removing the first solvent in the liquid film, when the first solvent evaporates to a certain extent, a thermodynamically unstable system is formed in the liquid film (film casting liquid), so that the liquid film is subjected to phase separation to form a polymer rich phase and a polymer lean phase, wherein the polymer lean phase contains a large amount of the second solvent. Because the boiling point of the second solvent is high, the second solvent is relatively difficult to evaporate compared with the first solvent, when the first solvent is completely evaporated and removed, polymer chain segments start to be arranged and form a network which is completely interconnected with the second solvent, and because the second solvent has strong hygroscopicity, the second solvent is easy to separate from a coagulating bath in the removal stage to form a completely through three-dimensional hole structure, and the structure is favorable for improving mass transfer efficiency, promoting diffusion and conduction of electrolyte in a film, improving conductive performance and reducing resistance.
Meanwhile, in the stage of removing the first solvent in the liquid film, the polymer concentration of the surface layer is increased to form a compact upper surface, the surface tension of the second solvent is larger, and when the first solvent is removed, the second solvent still interacts with most of the polymer due to the higher surface tension, so that the compact cortex formed by the first solvent is very thin, and the compact upper surface (cortex) prevents the second solvent from diffusing; as the upper surface of the casting solution (primary film) is gradually solidified, the second solvent inside diffuses through the bottom surface, and the lean phase gathers at the bottom to form macropores; therefore, the composite polymer porous membrane is provided with the upper surface of the compact small-aperture thin skin layer and the lower surface of the open large-aperture thin skin layer, the upper surface of the thin skin layer can effectively avoid gas crossing, and the lower surface of the open hole enables the composite polymer porous membrane to have good electrolyte wettability.
(5) The membrane casting solution contains hydrophilic inorganic particles, so that a composite polymer porous membrane containing the hydrophilic inorganic particles is formed, the structure and the pore distribution of the membrane can be regulated and controlled, the hydrophilic performance of the composite polymer porous membrane is effectively improved, the infiltration of the electrolyte to the membrane is promoted, and the resistance is reduced. Meanwhile, the inside of the composite polymer porous membrane is provided with high porosity and high specific surface area, so that hydrophilic inorganic particles are uniformly loaded and are not easy to fall off, the addition amount of the hydrophilic inorganic particles can be reduced on the premise of ensuring the hydrophilic performance, and the cost is greatly reduced.
Therefore, the preparation method provided by the invention is simple and easy to implement, and the composite polymer porous membrane with excellent comprehensive performance can be quickly and rapidly obtained through the design and mutual cooperation of the first solvent, the second solvent and specific process steps. The composite polymer porous membrane has the characteristics of compact thin skin layer, three-dimensional through structure, high porosity, large specific surface area, good hydrophilicity and electrolyte wettability, high mass transfer efficiency, good gas barrier effect, high mechanical property and low resistance, and can fully meet the performance requirements of the alkaline water electrolysis cell diaphragm. The preparation method has the advantages of simple and environment-friendly process, easy regulation of the film preparation process, realization of accurate control of the film structure, and suitability for large-scale industrial production.
The following is a preferred technical scheme of the present invention, but not a limitation of the technical scheme provided by the present invention, and the following preferred technical scheme can better achieve and achieve the objects and advantages of the present invention.
Preferably, the polymer comprises any one or a combination of at least two of polysulfone, polyethersulfone, polyetheretherketone, polytetrafluoroethylene, polyphenylsulfone, polybenzimidazole and chitosan. The polymer has the advantages of alkali liquid corrosion resistance, high mechanical strength and the like, and can especially meet the performance requirement of an alkaline water electrolysis process on a diaphragm.
Preferably, the first solvent has a boiling point T 1 The boiling point of the second solvent is T 2 ，T 2 -T 1 More than or equal to 40deg.C, for example, the difference between the two can be at 42deg.C, 45deg.C, 50deg.C, 55deg.CSpecific values of 60, 65, 70, 80, 90, 100, 110, 120, 130, 140, 150, 160 or 170 c and the specific values between the above values are not exhaustive of the specific values included in the range, for reasons of space and for reasons of simplicity, and more preferably 45-165 c.
As a preferred embodiment of the present invention, the boiling point of the second solvent is higher than that of the first solvent by at least 40 ℃, and more preferably 45 to 165 ℃, whereby it can be ensured that the second solvent does not volatilize/not evaporate when the first solvent is removed by a drying method, thereby forming a primary film containing the second solvent.
Preferably, the boiling point T of the first solvent 1 The temperature of 170℃or less may be, for example, 30℃40℃50℃60℃70℃80℃90℃100℃110℃120℃130℃140℃150℃160℃and the specific values between the above values, and the present invention is not intended to be exhaustive of the specific values included in the range, more preferably 40 to 165℃for reasons of space and brevity.
Preferably, the first solvent has a surface tension R 1 The surface tension of the second solvent is R 2 ，R 2 -R 1 For example, the difference between them may be 5dyne/cm, 5.5dyne/cm, 6dyne/cm, 6.5dyne/cm, 7dyne/cm, 7.5dyne/cm, 8dyne/cm, 8.5dyne/cm, 9dyne/cm, 9.5dyne/cm, 10dyne/cm or 10.5dyne/cm, and the specific point values between the above point values are limited to spread and for simplicity, and the present invention is not exhaustive of the specific point values included in the range, and more preferably 5 to 10.5dyne/cm.
Preferably, the first solvent comprises any one or a combination of at least two of N, N-dimethylformamide, N-dimethylacetamide, dimethylsulfoxide, toluene, dichloromethane, dioxane, acetonitrile, N-pentane and N-hexane.
As a preferable technical scheme of the invention, the specific type of first solvent is a good solvent of the polymer, namely, the difference of the solubility parameter delta between the polymer and the first solvent is less than or equal to 0.5, so that the polymer is fully dissolved, and undissolved polymer clusters in the casting solution can be prevented. If undissolved polymer clusters exist in the casting solution, the undissolved polymer clusters are converged into crystal nuclei in the process of separating the liquid film (casting solution), the acting force between the crystal nuclei is smaller, so that the composite polymer porous film has poorer mechanical property, and the first solvent with good solubility is beneficial to preparing the composite polymer porous film with better mechanical property.
Preferably, the second solvent is readily soluble in water and/or alcohol solvents; thus, the primary film can be allowed to be post-formed in a solvent bath (solvent bath of water and/or an alcoholic solvent) and removed by solvent substitution.
Preferably, the second solvent has a boiling point of 180℃or more, for example 190℃200℃210℃220℃230℃240℃250℃260℃270℃280℃290℃300℃and specific values between the above values, the range of specific values being not exhaustive for the sake of brevity and for the sake of brevity, the invention further preferably 190-290 ℃.
Preferably, the second solvent comprises any one or a combination of at least two of N-methyl pyrrolidone, sulfolane, ethylene glycol, triethyl phosphate, trimethyl phosphate, glycerol and dibutyl phthalate.
As a preferred embodiment of the present invention, the second solvent has a specific boiling point difference and a specific surface tension difference with the first solvent, and has excellent compatibility with the solvent in the subsequent solvent bath, so that a suitable exchange rate can be maintained, and the obtained porous composite polymer membrane has a high porosity and an ideal pore structure.
Preferably, the mass of the first solvent is 50% -90%, for example, 55%, 60%, 65%, 70%, 75%, 80% or 85%, and specific point values between the above point values, based on 100% of the total mass of the first solvent and the second solvent, are limited and for simplicity, the present invention does not exhaustively list the specific point values included in the range.
That is, the mass of the second solvent is 10% -50% based on 100% of the total mass of the first solvent and the second solvent, for example, 15%, 20%, 25%, 30%, 35%, 40% or 45%, and specific point values between the above point values, are limited in space and for simplicity, the present invention does not exhaustively list the specific point values included in the range.
As a preferable technical scheme of the invention, the first solvent in the liquid film is removed by a drying method, and then the second solvent in the primary film is removed by a solvent replacement method in a solvent bath. When the first solvent is removed (evaporated/volatilized) to some extent, the liquid film (casting solution) forms a thermodynamically unstable system, causing phase separation of the casting solution to occur, forming a polymer rich phase and a polymer lean phase, and the second solvent has a higher boiling point and is difficult to evaporate/volatilize relative to the first solvent. Therefore, when the first solvent is completely removed, the polymer chain segments start to be arranged and form a network which is completely interconnected with the second solvent, so that the formed primary film has the capacity of secondary forming, and when the second solvent is removed, a completely through three-dimensional structure is left in the film, and the structure is favorable for the diffusion and conduction of electrolyte in the film, and the resistance is reduced. In the stage of removing the first solvent in the liquid film, the concentration of the surface polymer is increased to form a relatively compact upper surface, and the surface tension of the second solvent is larger than that of the first solvent, so that the second solvent still interacts with most of the polymer due to the higher surface tension in the first solvent removing process, and the compact cortex formed by the first solvent is very thin; the dense upper surface prevents further diffusion of the second solvent from the bottom layer through the dense layer to the solvent bath and also prevents penetration of the solvent bath to the primary membrane; along with the gradual solidification of the upper layer of the membrane, the solvent in the membrane can diffuse into the solvent bath through the lower surface, the lean phase gathers at the bottom to form macropores, and the obtained composite polymer porous membrane simultaneously has the upper surface of a thin skin layer (also called as a dense layer) with a dense small pore diameter and the lower surface with an open large pore diameter, the upper surface of the thin skin layer can effectively avoid gas crossing, the safety of the membrane serving as a membrane is improved, and the lower surface with the open large pore diameter enables the composite polymer porous membrane to have good electrolyte wettability, and the resistance is reduced.
Based on the strategy of the step-by-step solvent removal, the use amount of the first solvent and the second solvent has a regulating effect on the surface and the internal structure of the porous composite polymer membrane as a preferable technical scheme of the invention. The content of the first solvent is 50% -90% and the surface tension of the second solvent is greater than the surface tension of the first solvent, so that the second solvent still interacts with most of the polymer in the casting solution in the first solvent removal stage, and the polymer generated by phase separation in the first solvent removal process is rich, so that a dense skin layer formed on the upper surface is very thin (also called as an upper surface dense layer), the thickness of the upper surface dense layer is 0.1-1 mu m, and the pore diameter is less than or equal to 100nm, thereby effectively avoiding gas crossover and better playing a gas isolation effect.
Further, in the process of removing the first solvent, the liquid film forms a thermodynamically unstable system to generate phase separation, so that a polymer rich phase and a polymer lean phase are formed, and in the second solvent removal stage, the residual polymer starts to be phase separated, so that a three-dimensional through porous layer is formed; therefore, the change of the content of the second solvent has a regulating effect on the size of the three-dimensional through hole structure inside the composite polymer porous membrane. When the content of the second solvent is 10% -30% based on 100% of the total amount of the solvent, the lean phase droplets are relatively small, so that when the rich phase droplets are solidified, the large droplets formed by aggregation of the lean phase droplets are relatively small, micropores of the prepared composite polymer porous membrane are relatively small, for example, the pore diameter of the upper surface is 0.1-0.3 mu m, and the pore diameter of the lower surface is 0.5-0.7 mu m. When the content of the second solvent is 30% -50%, the lean phase droplets are relatively more, so when the rich phase droplets are solidified, the large droplets formed by aggregation of the lean phase droplets are relatively larger, and micropores of the prepared composite polymer porous membrane are relatively larger, for example, the pore diameter of the upper surface is 0.3-0.5 mu m, and the pore diameter of the lower surface is 0.7-1 mu m. That is, the microporous structure and size of the composite polymer porous membrane can be controlled by controlling the content ratio of the second solvent in the solvent (first solvent+second solvent).
Preferably, the mass of the polymer is 12% -30% based on 100% of the total mass of the first solvent, the second solvent and the polymer, and may be, for example, 13%, 15%, 17%, 18%, 19%, 20%, 22%, 25% or 28%, and specific point values between the above point values, are limited in length and for brevity, the present invention is not exhaustive of the specific point values included in the range.
As a preferable technical scheme of the invention, the first solvent, the second solvent and the polymer are mixed to prepare a polymer solution, and hydrophilic inorganic particles are dispersed in the polymer solution to obtain the casting solution. The mass percentage of the polymer in the polymer solution is 12-30%, so that the casting solution has proper viscosity on one hand, and is beneficial to the forming of the composite polymer porous membrane; on the other hand, a suitable content of the polymer can inhibit the hydrophilic inorganic particles in the film from being eluted.
Preferably, the hydrophilic inorganic particles include any one or a combination of at least two of alumina, zirconia, silica, zinc oxide, cerium oxide, barium sulfate, magnesium hydroxide.
Preferably, the primary particle diameter of the hydrophilic inorganic particles is 30 to 200nm, and may be, for example, 40nm, 50nm, 70nm, 90nm, 110nm, 120nm, 140nm, 150nm, 160nm or 180nm, and specific point values between the above point values, are limited in space and for the sake of brevity, the present invention is not exhaustive of the specific point values included in the range.
Preferably, the mass ratio of the hydrophilic inorganic particles to the polymer is (3-7): 1, which may be, for example, 3.2:1, 3.5:1, 3.8:1, 4:1, 4.2:1, 4.5:1, 4.8:1, 5:1, 5.2:1, 5.5:1, 5.8:1, 6:1, 6.2:1, 6.5:1, or 6.8:1, etc.
The polymer has certain hydrophobic effect, so that electrolyte has certain obstruction to the infiltration of the inside of the membrane, the membrane resistance is increased, the gas barrier property is deteriorated, and meanwhile, hydrophobic substances are easily accumulated on the surface of the membrane, so that the surface of the membrane is polluted. According to the invention, hydrophilic inorganic particles are added into the membrane casting solution, so that the structure and the pore distribution of the membrane can be changed, and the hydrophilic performance of the membrane can be effectively improved. The preparation method can lead the inside of the porous membrane of the composite polymer to have high specific surface area, so that the hydrophilic inorganic particles are uniformly loaded and are not easy to fall off, and the addition amount of the hydrophilic inorganic particles is reduced on the premise of ensuring the hydrophilic performance, thereby greatly reducing the cost.
Preferably, the preparation method of the casting film liquid specifically comprises the following steps: mixing a first solvent, a second solvent and a polymer to obtain a polymer solution; dispersing the hydrophilic inorganic particles in a polymer solution to obtain the casting solution.
Preferably, the coating method includes a roll coating method, a blade coating method, a dipping method, or a casting method. The liquid film prepared by the coating method is even and smooth, the thickness is adjustable, the even and smooth liquid film enables the subsequent removal of the first solvent to be more thorough, and the finally obtained composite polymer porous film is even and uniform and has no salient points.
Preferably, the support net is immersed in the casting solution in a wound-up and unwound continuous form with tension.
Preferably, the support net is a porous support net, and the material of the support net comprises any one or a combination of at least two of polyphenylene sulfide, polypropylene, polyether ether ketone and polytetrafluoroethylene.
As a preferable technical scheme of the invention, the mechanical property and the strength of the composite polymer porous membrane can be improved by introducing the supporting net; specifically, the composite polymer porous membrane can be prevented from being broken, ruptured, or elongated due to mechanical stress. In the structure in which the porous membrane of the polymer-hydrophilic inorganic particles is provided on both surfaces of the support net, even when damage or pores (pinholes or the like) occur on one surface of the support net, the gas barrier property can be ensured by the porous membrane provided on the other surface of the porous support. In a structure in which porous films are symmetrically provided (deposited) on both sides of a support net, curling of the films and the like can be effectively prevented, and the handling properties at the time of handling or providing the films can be further improved.
Preferably, the method of removing the first solvent from the liquid film comprises drying.
Preferably, the drying temperature is 30-120 ℃, and may be, for example, 40 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃, 100 ℃ or 110 ℃, and specific point values between the above point values, and the present invention is not exhaustive of the specific point values included in the range, more preferably 45-90 ℃, still more preferably 55-80 ℃ for reasons of space and brevity.
Preferably, the drying time is 0.1-1h, for example, 0.2h, 0.3h, 0.4h, 0.5h, 0.6h, 0.7h, 0.8h or 0.9h, and specific point values between the above point values, are limited in length and for brevity, the invention is not intended to be exhaustive of the specific point values included in the range.
Preferably, the method of removing the second solvent in the primary film comprises solvent displacement in a solvent bath.
Preferably, the solvent of the solvent bath comprises water and/or an alcoholic solvent, further preferably any one or a combination of at least two of water, ethanol, isopropanol, n-propanol, tert-butanol.
Preferably, the solvent displacement temperature is 5-60 ℃, such as 10 ℃, 15 ℃, 20 ℃, 25 ℃, 30 ℃, 35 ℃, 40 ℃, 45 ℃, 50 ℃ or 55 ℃, and specific point values between the above point values, are limited in space and for the sake of brevity, the present invention is not exhaustive of the specific point values comprised in the range.
Preferably, the solvent displacement time is 0.3-3h, for example, 0.5h, 0.8h, 1h, 1.2h, 1.5h, 1.8h, 2h, 2.2h, 2.5h or 2.8h, and specific point values between the above point values, are limited in length and for brevity, the present invention is not exhaustive of the specific point values included in the range.
Preferably, the solvent is replaced with a drying step.
Preferably, the temperature of the drying after solvent displacement is 40-60 ℃, for example, 42 ℃, 45 ℃, 48 ℃, 50 ℃, 52 ℃, 55 ℃ or 58 ℃, and specific point values between the above point values, are limited in space and for the sake of brevity, the present invention is not exhaustive of the specific point values included in the range.
Preferably, the drying time after the solvent replacement is 0.1 to 1h, for example, may be 0.2h, 0.3h, 0.4h, 0.5h, 0.6h, 0.7h, 0.8h or 0.9h, and specific point values between the above point values, are limited in length and for brevity, the present invention is not exhaustive to list the specific point values included in the range.
Preferably, the preparation method specifically comprises the following steps:
mixing a first solvent, a second solvent and a polymer to obtain a polymer solution; the mass percentage of the polymer in the polymer solution is 12% -30%;
The first solvent is a good solvent of the polymer, and the boiling point of the first solvent is T 1 Surface tension of R 1 Including any one or a combination of at least two of N, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide, toluene, methylene dichloride, dioxane, acetonitrile, N-pentane and N-hexane;
the second solvent is a solvent which is miscible with the first solvent and has a boiling point T 2 Surface tension of R 2 Any one or the combination of at least two of N-methyl pyrrolidone, sulfolane, ethylene glycol, triethyl phosphate, trimethyl phosphate, glycerol and dibutyl phthalate; t (T) 2 -T 1 ≥40℃，R 2 -R 1 ≥5dyne/cm；
The mass of the first solvent is 50% -90% based on 100% of the total mass of the first solvent and the second solvent;
dispersing hydrophilic inorganic particles in the polymer solution to obtain a casting solution; the mass ratio of the hydrophilic inorganic particles to the polymer is (3-7) 1;
coating the casting film liquid on a supporting net to obtain a liquid film containing the supporting net;
drying the liquid film at 30-120 ℃ for 0.1-1h, and removing the first solvent to obtain a primary film;
placing the primary membrane in a solvent bath, replacing the primary membrane with a solvent at 5-60 ℃ for 0.3-3h, and removing the second solvent to obtain a composite polymer porous membrane;
The solvent of the solvent bath comprises any one or a combination of at least two of water, ethanol, isopropanol, n-propanol and tert-butanol.
In a second aspect, the present invention provides a composite polymeric porous membrane prepared by the preparation method as described in the first aspect.
Preferably, the thickness of the composite polymeric porous membrane is 0.1 to 0.8mm, more preferably 0.3 to 0.7mm, still more preferably 0.4 to 0.6mm.
Preferably, the porosity of the composite polymeric porous membrane is > 60%, more preferably > 70%, even more preferably 80% -95%.
Preferably, the composite polymer porous membrane comprises a single-sided compact surface layer (upper-sided compact layer) and a single-sided open porous structure, wherein the upper surface is relatively compact and has smaller pore diameter, the lower surface is relatively porous and has larger pore diameter, and the composite polymer porous membrane is internally provided with a three-dimensional dendritic through hole structure.
Preferably, the pore diameter of the upper surface compact layer of the composite polymer porous membrane is less than or equal to 100nm, the thickness of the upper surface compact layer is 0.1-1 mu m, and the pore diameter of the lower surface porous layer is 0.5-2 mu m.
Preferably, the composite polymeric porous membrane has an area resistance of < 0.4 Ω/cm 2 More preferably 0.3. OMEGA/cm or less 2 More preferably not more than 0.28. OMEGA/cm 2 For example, it may be 0.19 to 0.28. Omega/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the The surface resistance was measured at 30℃in 30wt% KOH solution.
Preferably, the bubble point pressure of the composite polymeric porous membrane is > 1.5bar, more preferably > 2bar, for example, it may be 2-3bar.
Preferably, the tensile strength of the composite polymer porous membrane is not less than 25MPa, and more preferably 25-30MPa.
In a third aspect, the present invention provides the use of a composite polymeric porous membrane as described in the second aspect, applied to an electrolyser separator.
Preferably, the composite polymeric porous membrane is applied to an alkaline water electrolysis cell membrane.
In a fourth aspect, the present invention provides an alkaline water electrolysis cell comprising a cathode, an anode and a separator disposed between the cathode and the anode, the separator being a composite polymeric porous membrane according to the second aspect.
Compared with the prior art, the invention has the following beneficial effects:
(1) According to the preparation method provided by the invention, the casting solution is prepared by adopting specific first solvents and second solvents with different boiling points and surface tension, the first solvents and the second solvents are removed in a segmented way to obtain the composite polymer porous membrane, the composite polymer porous membrane with excellent comprehensive performance is obtained through the design and mutual cooperation of the solvents and the process, the inside of the composite polymer porous membrane is provided with a three-dimensional through hole structure with high porosity and large specific surface area, hydrophilic inorganic particles are uniformly loaded and are not easy to fall off, the upper surface of a compact small-aperture thin skin layer and the lower surface of an open large aperture are provided, and the composite polymer porous membrane is endowed with excellent hydrophilicity, electrolyte wettability and conductivity, and has the advantages of high mass transfer efficiency, good gas barrier effect, high mechanical property and low resistance.
(2) The composite polymer porous membrane can fully meet the performance requirement of an alkaline water electrolysis cell on a diaphragm, and the three-dimensional through hole structure with high internal porosity can promote the conduction of electrolyte in the anode and cathode so as to reduce the resistance of the diaphragm, and the surface resistance in 30wt% KOH solution at 30 ℃ is less than or equal to 0.28 ohm/cm 2 At a current density of 500mA/cm 2 The lower cell voltage is less than 1.9V, which has important significance for reducing the system energy consumption of the alkaline water electrolysis cell. Meanwhile, the upper surface of the composite polymer porous membrane is provided with a compact small-aperture thin skin layer, so that an excellent gas-isolation effect is provided for the composite polymer porous membrane, the bubble point pressure is more than or equal to 2bar, the crossover of hydrogen and oxygen is avoided, and the gas purity is high, and the composite polymer porous membrane is safe and reliable; and has excellent mechanical properties, and the tensile strength is more than or equal to 25MPa.
(3) The preparation method is simple and efficient, can conveniently and rapidly obtain the composite polymer porous membrane with excellent comprehensive performance, and has wide industrial application prospect.
Drawings
FIG. 1 is a cross-sectional SEM image of a composite polymeric porous membrane provided in example 1;
FIG. 2 is an SEM image of the upper surface of a composite polymeric porous membrane provided in example 1;
FIG. 3 is a SEM image of the lower surface of a composite polymeric porous membrane provided in example 1;
FIG. 4 is a cross-sectional SEM image of a composite polymeric porous membrane provided by comparative example 1;
FIG. 5 is a cross-sectional SEM image of a composite polymeric porous membrane provided by comparative example 2;
FIG. 6 is an SEM image of the upper surface of a composite polymeric porous membrane provided by comparative example 2;
fig. 7 is a lower surface SEM image of the composite polymer porous membrane provided in comparative example 2.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
The terms "comprising," "including," "having," "containing," or any other variation thereof, are intended to cover a non-exclusive inclusion. For example, a composition, step, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, step, method, article, or apparatus.
In the present invention, a feature defining "first" or "second" may explicitly or implicitly include one or more of such feature for distinguishing between the descriptive features, and not sequentially or lightly. In the description of the present invention, unless otherwise indicated, the meaning of "a plurality" is two or more.
The present invention will be described more specifically based on examples, but it cannot be said that the present invention is limited to these examples only. In the following examples of the invention, the polymers, support networks, solvents and hydrophilic inorganic particles used are all commercially available products. Specifically, polysulfone, available from Shanghai poplar New Material Co., ltd., model S3110; polyethersulfone, available from neode high plastics technologies, inc, model E2010; polyetheretherketone, available from Guangdong new materials technology Co., ltd., model A2000; polybenzimidazole, available from Shanghai Cheng Jun plastics technologies Inc. Polyphenylene sulfide support mesh, available from eastern japan; polypropylene support mesh, available from eastern lewis materials limited; polytetrafluoroethylene support mesh, available from shandong lekurd materials limited.
Example 1
A composite polymer porous membrane and a preparation method thereof, wherein the preparation method specifically comprises the following steps:
(1) Preparing a casting solution: dissolving polysulfone in a mixed solvent of N, N-dimethylformamide and N-methylpyrrolidone, and uniformly stirring to obtain a polymer solution; the mass percentage of polysulfone in the polymer solution is 12%, and the mass percentage of N, N-dimethylformamide and N-methylpyrrolidone in the mixed solvent are 50% respectively. Hydrophilic inorganic particles (ZrO 2 Primary particle diameter of 50 nm), wherein ZrO 2 The mass ratio of the polymer and polysulfone is 3:1, and after stirring for 24 hours, defoaming treatment is carried out for 2 hours, thus obtaining milky film casting liquid with uniform dispersion;
(2) Preparation of liquid film: pouring the casting solution obtained in the step (1) on a clean and ultra-flat substrate, regulating and controlling the distance between a scraper on a film scraping machine and a glass plate to scrape the casting solution to be flat, unreeling a polyphenylene sulfide supporting net roll on the casting solution, and standing to enable the casting solution to fully infiltrate between fibers of the polyphenylene sulfide supporting net to obtain a liquid film containing the supporting net;
(3) Removing the first solvent (N, N-dimethylformamide): drying the liquid film obtained in the step (2) at 80 ℃ for 0.2h, thereby removing the first solvent to obtain a primary film;
(4) Removing the second solvent (N-methylpyrrolidone): immersing the primary membrane obtained in the step (3) in deionized water at 20 ℃ for solvent replacement, stripping the primary membrane from the substrate after the primary membrane is completely solidified, continuously immersing the primary membrane in a new deionized water bath for repeated immersion until the water phase is clear and transparent, thereby completely removing the second solvent, and taking out and drying the primary membrane to obtain the composite polymer porous membrane.
The microscopic morphology of the composite polymer porous membrane was tested by using a scanning electron microscope (SEM, reglus 8100, hitachi corporation, japan), the cross-sectional SEM view of the composite polymer porous membrane provided in this example is shown in fig. 1, the upper SEM view is shown in fig. 2, and the lower SEM view is shown in fig. 3; as can be seen from the three SEM images, the pore size and porosity of the lower surface of the composite polymer porous membrane are generally greater than those of the upper surface.
Example 2
A composite polymer porous membrane and a preparation method thereof, which differ from example 1 only in the components of the casting solution, specifically as follows: dissolving polyether sulfone in a mixed solvent of N, N-dimethylacetamide and sulfolane, and uniformly stirring to obtain a polymer solution; the mass percentage of polyethersulfone in the polymer solution is 18%, the mass percentage of N, N-dimethylacetamide in the mixed solvent is 65%, and the mass percentage of sulfolane is 35%. Hydrophilic inorganic particles (magnesium hydroxide, the primary particle size of which is 80 nm) are added into the polymer solution, wherein the mass ratio of the magnesium hydroxide to the polyethersulfone is 4:1, and the mixture is uniformly dispersed to obtain casting solution; other steps and process parameters were the same as in example 1 to obtain a composite polymer porous membrane.
Example 3
A composite polymer porous membrane and a preparation method thereof, which differ from example 1 only in the components of the casting solution, specifically as follows: dissolving polyether-ether-ketone in a mixed solvent of acetonitrile and triethyl phosphate, and uniformly stirring to obtain a polymer solution; the mass percentage of polyether-ether-ketone in the polymer solution is 25%, the mass percentage of acetonitrile in the mixed solvent is 75%, and the mass percentage of triethyl phosphate is 25%. Hydrophilic inorganic particles (alumina, with the primary particle size of 100 nm) are added into the polymer solution, wherein the mass ratio of the alumina to the polyether-ether-ketone is 5:1, and the mixture is uniformly dispersed to obtain a casting solution; other steps and process parameters were the same as in example 1 to obtain a composite polymer porous membrane.
Example 4
A composite polymer porous membrane and a preparation method thereof, which differ from example 1 only in the components of the casting solution, specifically as follows: dissolving polybenzimidazole in a mixed solvent of dichloromethane and trimethyl phosphate, and uniformly stirring to obtain a polymer solution; the mass percentage of polybenzimidazole in the polymer solution is 30%, the mass percentage of methylene dichloride in the mixed solvent is 85%, and the mass percentage of trimethyl phosphate is 15%. Hydrophilic inorganic particles (zinc oxide, the primary particle size of which is 200 nm) are added into the polymer solution, wherein the mass ratio of the zinc oxide to the polybenzimidazole is 7:1, and the mixture is uniformly dispersed to obtain a casting solution; other steps and process parameters were the same as in example 1 to obtain a composite polymer porous membrane.
Example 5
A composite polymer porous membrane and a preparation method thereof, wherein the preparation method specifically comprises the following steps:
(1) Preparing a casting solution: a casting solution was prepared by the same composition and method as in example 1;
(2) Preparation of liquid film: uniformly coating the casting solution on two sides of a polypropylene supporting net by adopting a double-sided roll coating method to obtain a liquid film containing the supporting net;
(3) Removing the first solvent (N, N-dimethylformamide): drying the liquid film obtained in the step (2) at 30 ℃ for 1h, and removing the first solvent to obtain a primary film;
(4) Removing the second solvent (N-methylpyrrolidone): immersing the primary membrane obtained in the step (3) in deionized water at 20 ℃, immersing the primary membrane in a new deionized water bath for repeated immersion after the primary membrane is completely solidified, until the water phase is clear and transparent, thereby completely removing the second solvent, and taking out and drying the primary membrane to obtain the composite polymer porous membrane.
Example 6
A composite polymer porous membrane and a preparation method thereof, wherein the preparation method specifically comprises the following steps:
(1) Preparing a casting solution: a casting solution was prepared by the same composition and method as in example 1;
(2) Preparation of liquid film: uniformly coating the casting solution on two sides of a polytetrafluoroethylene support net by adopting a double-sided roll coating method to obtain a liquid film containing the support net;
(3) Removing the first solvent (N, N-dimethylformamide): drying the liquid film obtained in the step (2) for 0.1h at 120 ℃ to remove the first solvent, thereby obtaining a primary film;
(4) Removing the second solvent (N-methylpyrrolidone): immersing the primary membrane obtained in the step (3) in deionized water at 20 ℃, immersing the primary membrane in a new deionized water bath for repeated immersion after the primary membrane is completely solidified, until the water phase is clear and transparent, thereby completely removing the second solvent, and taking out and drying the primary membrane to obtain the composite polymer porous membrane.
Example 7
A composite polymer porous membrane and a preparation method thereof are different from example 1 only in that deionized water in the step (4) is replaced by absolute ethyl alcohol, and the temperature of solvent replacement is 5 ℃; other raw materials, steps and process parameters were the same as in example 1 to obtain a composite polymer porous membrane.
Example 8
A composite polymer porous membrane and a method for preparing the same, which are different from example 1 only in that deionized water in the step (4) is replaced by isopropanol, and the temperature of solvent replacement is 60 ℃; other raw materials, steps and process parameters were the same as in example 1 to obtain a composite polymer porous membrane.
Example 9
A composite polymer porous membrane and a preparation method thereof are different from example 1 only in that deionized water in the step (4) is replaced by a mixed solvent with the volume ratio of deionized water to isopropanol being 3:1, and the temperature of solvent replacement is 40 ℃; other raw materials, steps and process parameters were the same as in example 1 to obtain a composite polymer porous membrane.
Example 10
A composite polymer porous membrane and a preparation method thereof, which differ from example 1 only in the components of the casting solution, specifically as follows: dissolving polysulfone in a mixed solvent of N, N-dimethylformamide and N-methylpyrrolidone, and uniformly stirring to obtain a polymer solution; the mass percentage of polysulfone in the polymer solution is 12%, the mass percentage of N, N-dimethylformamide in the mixed solvent is 45%, and the mass percentage of N-methylpyrrolidone is 55%. Hydrophilic inorganic particles (ZrO 2 Primary particle diameter of50 nm), wherein ZrO 2 The mass ratio of the polymer and polysulfone is 3:1, and the polymer and polysulfone are uniformly dispersed to obtain a casting solution; other steps and process parameters were the same as in example 1 to obtain a composite polymer porous membrane.
Example 11
A composite polymer porous membrane and a preparation method thereof, which differ from example 1 only in the components of the casting solution, specifically as follows: dissolving polysulfone in a mixed solvent of N, N-dimethylformamide and N-methylpyrrolidone, and uniformly stirring to obtain a polymer solution; the mass percentage of polysulfone in the polymer solution is 12%, the mass percentage of N, N-dimethylformamide in the mixed solvent is 92%, and the mass percentage of N-methylpyrrolidone is 8%. Hydrophilic inorganic particles (ZrO 2 Primary particle diameter of 50 nm), wherein ZrO 2 The mass ratio of the polymer and polysulfone is 3:1, and the polymer and polysulfone are uniformly dispersed to obtain a casting solution; other steps and process parameters were the same as in example 1 to obtain a composite polymer porous membrane.
Example 12
A composite polymer porous membrane and a preparation method thereof, which differ from example 1 only in the components of the casting solution, specifically as follows: dissolving polysulfone in a mixed solvent of N, N-dimethylformamide and 1, 2-propylene glycol, and uniformly stirring to obtain a polymer solution; the mass percentage of polysulfone in the polymer solution is 12%, and the mass percentage of N, N-dimethylformamide and 1, 2-propanediol in the mixed solvent are respectively 50%. Hydrophilic inorganic particles (ZrO 2 Primary particle diameter of 50 nm), wherein ZrO 2 The mass ratio of the polymer and polysulfone is 3:1, and the polymer and polysulfone are uniformly dispersed to obtain a casting solution; other steps and process parameters were the same as in example 1 to obtain a composite polymer porous membrane.
Example 13
A composite polymer porous membrane and a preparation method thereof, wherein the preparation method specifically comprises the following steps:
(1) Preparing a casting solution: dissolving polysulfone in a mixed solvent of N, N-dimethylformamide and dodecyl mercaptan, and uniformly stirring to obtain a polymer solution; polymer solution polymerizationThe mass percentage of sulfone is 12%, and the mass percentage of N, N-dimethylformamide and dodecyl mercaptan in the mixed solvent is 50% respectively. Hydrophilic inorganic particles (ZrO 2 Primary particle diameter of 50 nm), wherein ZrO 2 The mass ratio of the polymer and polysulfone is 3:1, and after stirring for 24 hours, defoaming treatment is carried out for 2 hours, thus obtaining milky film casting liquid with uniform dispersion;
(2) Preparation of liquid film: pouring the casting solution obtained in the step (1) on a clean and ultra-flat substrate, regulating and controlling the distance between a scraper on a film scraping machine and a glass plate to scrape the casting solution to be flat, unreeling a polyphenylene sulfide supporting net roll on the casting solution, and standing to enable the casting solution to fully infiltrate between fibers of the polyphenylene sulfide supporting net to obtain a liquid film containing the supporting net;
(3) Removing the first solvent (N, N-dimethylformamide): drying the liquid film obtained in the step (2) at 80 ℃ for 0.2h, thereby removing the first solvent to obtain a primary film;
(4) Removal of the second solvent (dodecyl mercaptan): immersing the primary membrane obtained in the step (3) in methanol at 20 ℃ for solvent replacement, stripping the primary membrane from the substrate after the primary membrane is completely solidified, continuously immersing the primary membrane in a new deionized water bath for repeated immersion until the water phase is clear and transparent, thereby completely removing the second solvent, and taking out and drying the primary membrane to obtain the composite polymer porous membrane.
Comparative example 1
A composite polymer porous membrane and a preparation method thereof, wherein the preparation method specifically comprises the following steps:
(1) Dissolving polysulfone in N, N-dimethylformamide, and uniformly stirring to obtain a polymer solution; the mass percent of polysulfone in the polymer solution was 12%. Hydrophilic inorganic particles (ZrO 2 Primary particle diameter of 50 nm), wherein ZrO 2 The mass ratio of the polymer and polysulfone is 3:1, and after stirring for 24 hours, defoaming treatment is carried out for 2 hours, thus obtaining milky film casting liquid with uniform dispersion;
(2) Pouring the casting solution obtained in the step (1) on a clean and ultra-flat substrate, regulating and controlling the distance between a scraper on a film scraping machine and a glass plate to scrape the casting solution to be flat, unreeling a polyphenylene sulfide supporting net roll on the casting solution, and standing to enable the casting solution to fully infiltrate between fibers of the polyphenylene sulfide supporting net to obtain a liquid film containing the supporting net;
(3) And (3) drying the liquid film obtained in the step (2) for 0.2h at the temperature of 80 ℃ to remove the N, N-dimethylformamide, thereby obtaining the composite polymer porous film.
The composite polymeric porous membrane of comparative example 1 has a significantly reduced porosity compared to example 1 shown in fig. 3, as shown in fig. 4, which is a cross-sectional SEM image of the composite polymeric porous membrane provided in comparative example 1.
Comparative example 2
A composite polymer porous membrane and a preparation method thereof are different from example 1 only in that the drying step of step (3) is not performed, namely, the liquid membrane comprising the support net obtained in step (2) is directly immersed in deionized water at 20 ℃ for solvent replacement, and the composite polymer porous membrane is obtained.
The cross-sectional SEM image of the porous composite polymer membrane provided in comparative example 2 is shown in fig. 5, the upper surface SEM image is shown in fig. 6, and the lower surface SEM image is shown in fig. 7. Compared with example 1, the porous composite polymer membrane of comparative example 2 has a reduced porosity, and the upper and lower surfaces are both relatively dense and cracked structures, which are not conducive to the conduction of the electrolyte, and also cannot effectively insulate the gas.
Comparative example 3
A composite polymer porous membrane and a preparation method thereof, which differ from example 1 only in the components of the casting solution, specifically as follows: dissolving polysulfone in an N, N-dimethylformamide solvent, then adding a pore-forming agent polyvinylpyrrolidone into the solvent, and uniformly stirring to obtain a polymer solution; the mass percent of polysulfone in the polymer solution is 15%, the mass percent of N, N-dimethylformamide is 80%, and the mass percent of polyvinylpyrrolidone is 5%. Hydrophilic inorganic particles (ZrO 2 Primary particle diameter of 50 nm), wherein ZrO 2 The mass ratio of the polymer and polysulfone is 3:1, and the polymer and polysulfone are uniformly dispersed to obtain a casting solution; other steps and process parameters were the same as in comparative example 2, to obtain a composite polymer porous membrane.
The composite polymer porous membranes provided in examples 1 to 13 and comparative examples 1 to 3 were subjected to performance test by the following methods:
(1) Thickness: the test was carried out according to the method described in standard GB/T6672-2001.
(2) Porosity: porosity (%) = (wet film weight of bubble-dry film weight)/density of water/volume of wet film of bubble x 100%; the weight of the wet film is obtained by soaking a dry film to be tested in water for 24 hours and then testing.
(3) Surface resistance: the test was carried out according to the method in standard SJ/T10171.5-1991 under 30℃and 30% by weight KOH solution with a test area of 4cm 2 。
(4) Bubble point pressure: the test is carried out according to the method in the standard GB/T32361-2015, and the test instrument is Porolux TM 1000。
(5) Tensile strength: the test was carried out according to the method in standard GB/T1040-79.
(6) Cell voltage: a single-chamber electrolytic tank with a zero-gap structure is formed by adopting a foam nickel gas diffusion layer and a titanium bipolar plate, raney nickel is used as a cathode catalyst, and a direct current power supply is used for providing current under the conditions of the temperature of 80 ℃,30wt% of KOH solution and the flow rate of 50mL/min, and the current is 500mA/cm 2 Evaluating the cell voltage at current density;
the test results are shown in table 1:
TABLE 1
As can be seen from the data in table 1, the present invention can obtain a composite polymer porous membrane with excellent performance, which has a three-dimensional through-hole structure with high porosity inside, and has an upper surface of a dense small-pore-diameter thin skin layer and a lower surface with open large pore diameter, which has excellent hydrophilicity, electrolyte wettability and conductivity, and which has high bubble point pressure, low surface resistance and high tensile strength, and which can effectively reduce cell voltage as an alkaline water electrolyzer membrane, and has important significance for reducing system energy consumption of an alkaline water electrolyzer, through the combination and synergy of the specific types of first solvent and second solvent designs and the processes of respectively removing the first solvent and the second solvent by sections thereof. Further, by setting the types and the contents of the first solvent and the second solvent and controlling the parameters of the first solvent and the second solvent, the structure and the functional characteristics of the porous composite polymer membrane can be effectively regulated and controlled.
Specifically, comparing the preparation methods and test data of example 1 and comparative examples 1-2, it can be seen in conjunction with fig. 1, 4 and 5 that the composite polymeric porous membrane provided in comparative examples 1-2 has significantly lower porosity and significantly higher sheet resistance and cell voltage than in example 1, because the first solvent is easier to evaporate/volatilize than the second solvent under the same temperature conditions, and the second solvent can always be present in the primary membrane; phase separation of the casting solution occurs after a period of evaporation of the first solvent, forming a polymer-rich phase and a less polymeric lean phase, and pores are formed in the film when the second solvent is removed. The casting solution of comparative example 1 only contains the first solvent, and although the casting solution can undergo phase separation, most of the polymer phase separation occurs in the first solvent removal stage due to the lack of the second solvent, and pores cannot be formed in the membrane.
As can be seen from the data in table 1 and fig. 2, 3, 6 and 7, comparative example 2 adopts the conventional immersion precipitation method to prepare a porous film, which has a lower bubble point pressure and poor gas barrier property, compared with example 1, because the immersion precipitation method of comparative example 2 has a rapid replacement of a solvent with a coagulation bath, a rapid solvent-non-solvent exchange on the surface causes the surface layer to be broken through creep relaxation of the polymer, more polymer lean phase droplets are formed and combined, and cracks are easily generated on the surface, so that gas crossover easily occurs. The upper surface of the porous composite polymer membrane of example 1 is dense pores, and the lower surface is completely open, and the dense thin skin layer on the upper surface prevents the second solvent from diffusing further from the bottom layer to the solvent bath through the dense layer, and also prevents the solvent bath from penetrating into the casting solution; along with the gradual solidification of the upper layer of the membrane, the solvent in the membrane can diffuse into the solvent bath through the bottom surface, and the lean phase is gathered at the bottom to form macropores, so that electrolyte infiltration is facilitated, the membrane resistance is reduced, and the dense upper surface is favorable for isolating gas. The upper and lower surfaces of the porous film of comparative example 2 were both relatively dense and cracked structures, which both prevented the conduction of the electrolyte and failed to isolate the gas, and exhibited high sheet resistance and low bubble point pressure.
In combination with the preparation methods and test data of example 1 and comparative example 3, it is known that the membrane prepared by using two solvents having a boiling point difference and a surface tension difference and by removing the solvents in a sectional manner is more excellent in structure and performance than the conventional molding method of the NIPS+ pore-forming agent, and more meets the performance requirements of the water electrolysis membrane.
By combining the preparation methods and test data of examples 1-13 and comparative examples 1-2, the densification degree and the porosity of the upper and lower surfaces of the porous membrane can be changed by adjusting the ratio of the second solvent in the mixed solvent, the volatilization temperature of the first solvent, the solvent replacement condition and the like, so that the mechanical strength and the bubble point pressure of the porous membrane are higher, the cross mixing of hydrogen and oxygen can be effectively blocked in the electrolysis process, and the gas purity is effectively improved while the safety is ensured.
The applicant states that the present invention is illustrated by the above examples as well as methods of making and using the composite polymeric porous membrane of the present invention, but the present invention is not limited to, i.e., does not necessarily rely on, the above process steps to practice the present invention. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of selected raw materials, addition of auxiliary components, selection of specific modes, etc. fall within the scope of the present invention and the scope of disclosure.
Claims (10)
1. A method of preparing a composite polymeric porous membrane, the method comprising:
mixing a first solvent, a second solvent, a polymer and hydrophilic inorganic particles to obtain a casting solution;
the first solvent is a good solvent for the polymer, and the second solvent is miscible with the first solvent; the boiling point of the first solvent is less than the boiling point of the second solvent, and the surface tension of the first solvent is less than the surface tension of the second solvent;
coating the casting film liquid on a supporting net to obtain a liquid film containing the supporting net;
removing the first solvent in the liquid film to obtain a primary film;
and removing the second solvent in the primary membrane to obtain the composite polymer porous membrane.
2. The method of claim 1, wherein the polymer comprises one or a combination of at least two of polysulfone, polyethersulfone, polyetheretherketone, polytetrafluoroethylene, polyphenylsulfone, polybenzimidazole, and chitosan.
3. The preparation method according to claim 1 or 2, wherein the first solvent has a boiling point T 1 The boiling point of the second solvent is T 2 ，T 2 -T 1 ≥40℃；
Preferably, the first solvent has a surface tension R 1 The surface tension of the second solvent is R 2 ，R 2 -R 1 ≥5dyne/cm；
Preferably, the first solvent comprises any one or a combination of at least two of N, N-dimethylformamide, N-dimethylacetamide, dimethylsulfoxide, toluene, dichloromethane, dioxane, acetonitrile, N-pentane and N-hexane;
preferably, the second solvent comprises any one or a combination of at least two of N-methyl pyrrolidone, sulfolane, ethylene glycol, triethyl phosphate, trimethyl phosphate, glycerol and dibutyl phthalate;
preferably, the mass of the first solvent is 50% -90% based on 100% of the total mass of the first solvent and the second solvent;
preferably, the mass of the polymer is 12% to 30% based on 100% of the total mass of the first solvent, the second solvent and the polymer.
4. A method of preparing according to any one of claims 1 to 3, wherein the hydrophilic inorganic particles comprise any one or a combination of at least two of alumina, zirconia, silica, zinc oxide, ceria, barium sulfate, magnesium hydroxide;
preferably, the primary particle diameter of the hydrophilic inorganic particles is 30 to 200nm;
preferably, the mass ratio of the hydrophilic inorganic particles to the polymer is (3-7): 1;
Preferably, the preparation method of the casting film liquid specifically comprises the following steps: mixing a first solvent, a second solvent and a polymer to obtain a polymer solution; dispersing the hydrophilic inorganic particles in a polymer solution to obtain the casting solution.
5. The production method according to any one of claims 1 to 4, wherein the coating method comprises a roll coating method, a blade coating method, a dipping method, or a casting method;
preferably, the material of the support net comprises any one or a combination of at least two of polyphenylene sulfide, polypropylene, polyether-ether-ketone and polytetrafluoroethylene.
6. The method of any one of claims 1 to 5, wherein the method of removing the first solvent from the liquid film comprises drying;
preferably, the drying temperature is 30-120 ℃;
preferably, the drying time is 0.1-1h;
preferably, the method of removing the second solvent in the primary film comprises performing a solvent displacement in a solvent bath;
preferably, the solvent of the solvent bath comprises water and/or an alcoholic solvent, further preferably any one or a combination of at least two of water, ethanol, isopropanol, n-propanol, tert-butanol;
preferably, the temperature of the solvent displacement is 5-60 ℃;
Preferably, the solvent displacement time is 0.3 to 3 hours.
7. The preparation method according to any one of claims 1 to 6, characterized in that it comprises in particular:
mixing a first solvent, a second solvent and a polymer to obtain a polymer solution; the mass percentage of the polymer in the polymer solution is 12% -30%;
the first solvent is a good solvent of the polymer, and the boiling point of the first solvent is T 1 Surface tension of R 1 Including any one or a combination of at least two of N, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide, toluene, methylene dichloride, dioxane, acetonitrile, N-pentane and N-hexane;
the second solvent is miscible with the first solvent and has a boiling point T 2 Surface tension of R 2 Any one or the combination of at least two of N-methyl pyrrolidone, sulfolane, ethylene glycol, triethyl phosphate, trimethyl phosphate, glycerol and dibutyl phthalate; t (T) 2 -T 1 ≥40℃，R 2 -R 1 ≥5dyne/cm；
The mass of the first solvent is 50% -90% based on 100% of the total mass of the first solvent and the second solvent;
dispersing hydrophilic inorganic particles in the polymer solution to obtain a casting solution; the mass ratio of the hydrophilic inorganic particles to the polymer is (3-7) 1;
Coating the casting film liquid on a supporting net to obtain a liquid film containing the supporting net;
drying the liquid film at 30-120 ℃ for 0.1-1h, and removing the first solvent to obtain a primary film;
placing the primary membrane in a solvent bath, replacing the primary membrane with a solvent at 5-60 ℃ for 0.3-3h, and removing the second solvent to obtain a composite polymer porous membrane;
the solvent of the solvent bath comprises any one or a combination of at least two of water, ethanol, isopropanol, n-propanol and tert-butanol.
8. A composite polymer porous membrane prepared by the preparation method according to any one of claims 1 to 7;
preferably, the composite polymeric porous membrane has a thickness of 0.1 to 0.8mm;
preferably, the porosity of the composite polymer porous membrane is more than or equal to 70%;
preferably, the pore diameter of the upper surface compact layer of the composite polymer porous membrane is less than or equal to 100nm, the thickness of the upper surface compact layer is 0.1-1 mu m, and the pore diameter of the lower surface porous layer is 0.5-2 mu m;
preferably, the area resistance of the composite polymer porous membrane is less than or equal to 0.28 ohm/cm 2 ；
Preferably, the bubble point pressure of the composite polymer porous membrane is more than or equal to 2bar;
preferably, the tensile strength of the composite polymer porous membrane is more than or equal to 25MPa.
9. The use of a composite polymeric porous membrane according to claim 8, wherein the composite polymeric porous membrane is applied to an electrolyser membrane;
preferably, the composite polymeric porous membrane is applied to an alkaline water electrolysis cell membrane.
10. An alkaline water electrolyzer comprising a cathode, an anode, and a separator disposed between the cathode and the anode, the separator being the composite polymeric porous membrane of claim 8.
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