WO2020010660A1 - Procédé de préparation d'une membrane échangeuse d'ions ayant une structure de conduction ionique ordonnée - Google Patents

Procédé de préparation d'une membrane échangeuse d'ions ayant une structure de conduction ionique ordonnée Download PDF

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WO2020010660A1
WO2020010660A1 PCT/CN2018/099640 CN2018099640W WO2020010660A1 WO 2020010660 A1 WO2020010660 A1 WO 2020010660A1 CN 2018099640 W CN2018099640 W CN 2018099640W WO 2020010660 A1 WO2020010660 A1 WO 2020010660A1
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ion
polymer
exchange membrane
film
membrane
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Chinese (zh)
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尹燕
张俊锋
刘鑫
盖费·迈克尔·多米尼克
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天津大学
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0079—Manufacture of membranes comprising organic and inorganic components
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0002—Organic membrane manufacture
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0002—Organic membrane manufacture
    • B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
    • B01D67/0011—Casting solutions therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/26—Polyalkenes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/30—Polyalkenyl halides
    • B01D71/32—Polyalkenyl halides containing fluorine atoms
    • B01D71/34—Polyvinylidene fluoride
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/38—Polyalkenylalcohols; Polyalkenylesters; Polyalkenylethers; Polyalkenylaldehydes; Polyalkenylketones; Polyalkenylacetals; Polyalkenylketals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/56—Polyamides, e.g. polyester-amides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/66—Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
    • B01D71/68—Polysulfones; Polyethersulfones
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
    • H01M8/1086—After-treatment of the membrane other than by polymerisation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/42—Ion-exchange membranes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Definitions

  • the invention belongs to the technical field of preparation of ion conductive polymer materials, and particularly relates to a method for preparing an ion exchange membrane.
  • Ion exchange membranes are key materials in many fields such as adsorption, electrolysis, separation, batteries, supercapacitors and so on.
  • ionic conductivity and water absorption always show a positive correlation, because only hydrophilic ionized groups can play an efficient ion conduction effect.
  • an excessively high water absorption rate will cause obvious swelling of the ion exchange membrane, resulting in a decrease in the performance stability and durability of the membrane.
  • Related studies have shown that increasing the degree of separation of the hydrophilic and hydrophobic phases of an ion exchange membrane can help to increase the ionic conductivity of the membrane and reduce the water absorption of the membrane.
  • the most closely related to the demand for energy efficiency is often the conduction of ions in a specific direction within the ion exchange membrane.
  • the power output of an ion exchange membrane fuel cell is mainly obtained by the conduction of ions in the direction of the transmission surface of the ion exchange membrane.
  • an ion exchange membrane prepared by a general film-forming method has an isotropic structure and ion conduction characteristics. Without changing the composition of the ion exchange membrane, the ideal ion exchange membrane should have an anisotropic structure, so that the ion conductivity in a specific direction can be optimized and enhanced, so as to obtain higher demand energy efficiency in practical applications.
  • the present invention provides a method for preparing an ion exchange membrane with an ordered ion conduction structure.
  • the method adopts a processing technique of applying a magnetic field or an electric field when a solution is cast into a film, which can ionize the ions of the ion exchange membrane.
  • the conductive structure is regulated in an orderly manner, and an ion-exchange membrane with high-efficiency and durable ion-conducting capacity is prepared.
  • a method for preparing an ion-exchange membrane with an ordered ion-conducting structure is performed according to the following steps:
  • the membrane is ionized to obtain an ion exchange membrane having an ordered ion conduction structure.
  • the polymer matrix in the polymer A in step (1) is polyimide, polyamide, polyetheretherketone, polysulfone, polyethersulfone, polytetrafluoroethylene, polydimethylsiloxane One or more of alkane, polystyrene, polybenzimidazole, polyphenylene ether, polyethylene, polyvinyl chloride, polyvinylpyridine, or polyvinylcyclohexane.
  • the metal coordination structure described in step (1) is selected from the group consisting of iron pentacyanopyridine, ferrocene, ferrocene oxide, cobaltocene, cobaltocene oxide, nickelocene, or nickelocene oxide.
  • iron pentacyanopyridine ferrocene
  • ferrocene oxide cobaltocene
  • cobaltocene oxide nickelocene oxide
  • nickelocene nickelocene oxide
  • the proportion of the metal-containing coordination structure segment in the polymer A in the step (1) is 10% to 100%.
  • the polymer B described in step (2) is polyimide, polysulfone, polyethersulfone, polystyrene, polyphenylene sulfide, polyvinylpyridine, polypropylene, polyacrylonitrile, polyphosphorus One of nitrile, polyvinylidene fluoride, or polymethyl methacrylate; its purpose is that when polymer A alone or polymer A and filler have weak mechanical properties, the addition of polymer B can make the membrane mechanical The strength is increased to a level that meets practical applications, and all polymers that can play this role can be used here as polymer B.
  • the filler described in step (2) is phosphotungstic acid, phosphomolybdic acid, magnesium-aluminum layered double hydroxide, carbon nanotubes, halloysite, rectorite, montmorillonite, silica, One of graphene oxide, boron nitride, or nitrogen carbide; its purpose is that when the polymer A or polymer A and polymer B are not significantly affected by the magnetic or electric field, the addition of filler can make the film The ordered structure is strengthened, and all materials that can play this role can be used as fillers here.
  • the solvent described in step (2) is one of dimethylformamide, dimethylacetamide, nitrogen methylpyrrolidone, dimethylsulfoxide, m-cresol, chloronaphthalene, tetrahydrofuran or xylene.
  • Species; its purpose is to make polymer A or polymer A and polymer B or polymer A and filler or polymer A and polymer B and filler fully dissolve and disperse, all solvents that can play this role can be here use.
  • the ratio by mass of the polymer A to the polymer B is (10 to 90): (10 to 90); when the polymer A and the filler are dissolved in the solvent, the ratio by mass of the polymer A to the filler is (50 to 99): (1 to 50); When the polymer A, the polymer B, and the filler are dissolved in the solvent, a ratio by mass of the polymer A, the polymer B, and the filler is (5 to 90): (5 to 90): (1 to 50).
  • the solvent evaporation method described in step (3) is to pour the film-forming solution into a petri dish, and volatilize the solvent at 20 to 100 ° C. for 12 to 48 hours to form a film;
  • the spin coating method described in step (3) is to form the film-forming liquid droplets on a horizontal turntable, and rotate the film at 1 to 100 r / s at room temperature for 1 to 100 s to form a film;
  • the dip coating method described in step (3) is to immerse the film-forming solution into the porous membrane and volatilize the solvent at 20 to 100 ° C. for 12 to 48 h to form a film;
  • the roll-to-roll screen printing method described in step (3) is to inject a film-forming liquid into a flexible screen substrate having a line width and a line pitch of 0.01 to 0.1 mm, and a level of 0.1 to 500 m / min at room temperature. Continuous roll-to-roll filming at running speed;
  • the inkjet printing method described in step (3) is to charge a mixed solution of a film-forming liquid and an ultraviolet-curable foaming ink with a mass ratio of (10 to 90): (10 to 90) into a spray.
  • the mixed solution is sprayed onto the substrate through a nozzle at room temperature, and then UV-cured to form a film in 1 to 10 minutes.
  • the ionization treatment described in step (4) is direct ion replacement or ion replacement after oxidation.
  • the method for preparing an ion exchange membrane with an ordered ion conduction structure has a wide range of applicable raw materials, a simple preparation process, and mild processing conditions.
  • the present invention applies a magnetic field or an electric field during the film formation process, so that the ion exchange membrane obtains an ordered ion conduction structure, and significantly improves the ion conduction efficiency of the membrane in a specific direction; at the same time, this height
  • the orderly ion-conducting structure improves the degree of separation of the hydrophilic and hydrophobic phases in the ion exchange membrane, thereby reducing the water absorption of the membrane and greatly improving the stability of the ion conductivity. Therefore, the ion exchange membrane prepared by the method of the present invention has wide application prospects in many fields such as adsorption, electrolysis, separation, batteries, supercapacitors and the like.
  • Fig. 1 is a comparison view of the microscopic morphology of the ion exchange membrane (membrane 1) prepared in Example 1 and an ion exchange membrane (membrane 2) with the same formula prepared by a general solvent evaporation method (observed by a transmission electron microscope, left picture) B represents the magnetic field, and the direction of the arrow is the direction of the magnetic field);
  • FIG. 2 is a comparison diagram of the ionic conductivity of the membrane 1 and the membrane 2;
  • FIG. 3 is a comparison diagram of water absorption of the film 1 and the film 2;
  • FIG. 5 is a comparison diagram of energy output of a fuel cell assembled with a membrane 1 and a membrane 2;
  • FIG. 6 is a comparison diagram of durability of a fuel cell assembled with a membrane 1 and a membrane 2;
  • FIG. 7 is a comparison diagram of the ion conductivity of the ion exchange membrane (membrane 3) prepared in Example 2 and an ion exchange membrane (membrane 4) with the same formula prepared by a general solvent evaporation method;
  • FIG. 9 is a comparison diagram of the ion conductivity of the ion exchange membrane (film 5) prepared in Example 3 and an ion exchange membrane (film 6) with the same formula prepared by a general solvent evaporation method;
  • FIG. 10 is a comparison chart of the conductivity stability of the films 5 and 6.
  • the membrane is removed from the petri dish, and immersed in 1 mol / L of dilute sulfuric acid for ion replacement to obtain an ion exchange membrane with an ordered ion conduction structure.
  • the left image of FIG. 1 is a transmission electron microscope image of the ion exchange membrane (film 1) prepared in Example 1.
  • B in the figure represents a magnetic field, and the direction of the arrow is the direction of the magnetic field.
  • the right image of FIG. 1 is a transmission electron microscope image of an ion exchange membrane (film 2) with the same formulation prepared by a general solvent evaporation method.
  • the difference between the general solvent evaporation method and the preparation method of Example 1 is that no magnetic field is applied during the solvent evaporation process. Comparing the left and right diagrams in Figure 1, it can be found that the membrane 1 prepared under magnetic field conditions has a continuous hydrophilic phase arranged in the direction of the magnetic field, which is an orderly channel that can achieve efficient ion conduction.
  • the membrane 2 prepared by the general solvent evaporation method does not have an ordered structure inside, and its hydrophilic ion-conducting region exhibits an isotropic random distribution and has poor connectivity.
  • Figure 2 is a comparison diagram of the ionic conductivity of membrane 1 and membrane 2 (20-95 ° C water). It can be found that the membrane 1 prepared under magnetic field conditions has anisotropic ionic conductivity, and the ionic conductivity in the direction of the parallel magnetic field is significantly higher than the ionic conductivity in the direction of the vertical magnetic field.
  • the membrane 2 prepared by a general solvent evaporation method has an isotropic ionic conductivity, which is significantly lower than that of the membrane 1 in the direction of a parallel magnetic field.
  • the ion-conducting characteristics of these two membranes are determined by the distribution of the hydrophilic ion-conducting groups in both of them.
  • Figure 3 is a comparison diagram of the water absorption of film 1 and film 2 (20-95 ° C water). It can be found that the water absorption of the film 1 prepared under the magnetic field condition is significantly lower than that of the film 2 prepared by the general solvent evaporation method, and the difference between the two is more obvious at higher temperatures.
  • the ordered arrangement of ion conduction regions in the left figure of Figure 1 has a higher degree of affinity and water phase separation than the random distribution in the right figure, which reduces the water absorption of the membrane.
  • Figure 4 is a comparison chart of the conductivity stability of membrane 1 and membrane 2 (in water at 95 ° C). It can be found that the conductivity stability of the membrane 1 prepared under the magnetic field condition is obviously better than that of the membrane 2 prepared by the general solvent evaporation method, and the lower water absorption is an important reason for the improvement of the membrane stability.
  • FIG. 5 is a comparison diagram of the power output of a fuel cell assembled with membrane 1 and membrane 2 when the magnetic field direction is the transmission direction of the membrane (95 ° C, 95% relative humidity). It can be found that the ultimate power density of a fuel cell assembled from membrane 1 prepared under magnetic field conditions is significantly higher than that of a fuel cell assembled from membrane 2 prepared by a general solvent evaporation method, which is closely related to the significantly improved transmission surface conductivity of membrane 1. Related.
  • Fig. 6 is a comparison of the durability of a fuel cell assembled with membrane 1 and membrane 2 when the magnetic field direction is the transmission direction of the membrane (95 ° C, 95% relative humidity, constant voltage 0.6V). It can be found that the durability of the fuel cell assembled from the membrane 1 prepared under magnetic field conditions is significantly better than that of the fuel cell assembled from the membrane 2 prepared by the general solvent evaporation method, which is closely related to the significantly improved conductivity stability of the membrane 1.
  • the film is removed from the petri dish, reacted with nitros hexafluorophosphate to carry out nickel site oxidation, and then immersed in a 1 mol / L potassium bicarbonate aqueous solution for ion replacement to obtain Ion exchange membrane with an ordered ion conducting structure.
  • FIG. 7 is a comparison diagram of the ionic conductivity (20-95 ° C. water) of the ion exchange membrane (membrane 3) prepared in Example 2 and an ion exchange membrane (membrane 4) with the same formula prepared by a general solvent evaporation method.
  • the difference between the general solvent evaporation method and the preparation method of Example 2 is that no magnetic field is applied during the solvent evaporation process. It can be found that the film 3 prepared under magnetic field conditions has anisotropic ionic conductivity, and the ionic conductivity in the direction of the parallel magnetic field is significantly higher than that in the direction of the vertical magnetic field.
  • the membrane 4 prepared by a general solvent evaporation method has an isotropic ionic conductivity, and is significantly lower than that of the membrane 3 prepared in Example 2 under a magnetic field condition in the direction of parallel magnetic fields.
  • FIG. 8 is a comparison chart of the conductivity stability of membrane 3 and membrane 4 (in water at 95 ° C.). It can be found that the conductivity stability of the film 3 prepared under the magnetic field condition is obviously better than that of the film 4 prepared by the general solvent evaporation method.
  • the membrane is removed from the petri dish and immersed in 1 mol / L sodium hydroxide for ion replacement to obtain an ion exchange membrane having an ordered ion conduction structure.
  • FIG. 9 is a comparison diagram of ion conductivity (20-95 ° C. water) of the ion exchange membrane (membrane 5) prepared in Example 3 and an ion exchange membrane (membrane 6) with the same formula prepared by a general solvent evaporation method.
  • the difference between the general solvent evaporation method and the preparation method of Example 3 is that no electric field is applied during the solvent evaporation process. It can be found that the membrane 5 prepared under the electric field condition has anisotropic ionic conductivity, and the ionic conductivity in the direction of the parallel electric field is significantly higher than the ionic conductivity in the direction of the vertical electric field.
  • the membrane 6 prepared by a general solvent evaporation method has an isotropic ionic conductivity, which is significantly lower than that of the membrane 5 prepared in Example 3 under an electric field condition in a direction of parallel electric fields.
  • FIG. 10 is a comparison chart of the conductivity stability of membrane 5 and membrane 6 (in water at 95 ° C.). It can be found that the conductivity stability of the film 5 prepared under the electric field condition is obviously better than that of the film 6 prepared by a general solvent evaporation method.
  • This polymer containing a metal coordination structure is dissolved in nitrogen methylpyrrolidone together with polyvinylpyridine and phosphomolybdic acid at a mass ratio of 90: 5: 5, and the total solute concentration is 300 g. / L of the film-forming solution, after fully dissolved, stand still and defoam;
  • the film-forming liquid droplets are rotated on a horizontal turntable under the conditions of an air pressure of 1 atm and a magnetic field of 40 T, and the film is rotated at 1000 r / s for 1 s at room temperature;
  • the membrane is removed from the horizontal turntable and immersed in 1 mol / L of dilute sulfuric acid for ion replacement to obtain an ion exchange membrane with an ordered ion conduction structure.
  • the ion conductivity of the ion-exchange membrane prepared in Example 4 was compared with that of the ion-exchange membrane with the same formula prepared in a general spin-coating method (in water at 95 ° C.). The difference between the general spin-coating method and the preparation method in Example 4 was the spin-coating process. No magnetic field is applied.
  • the results were as follows: the ion conductivity of the ion exchange membrane prepared in Example 4 was 0.228 S / cm in the direction of the parallel magnetic field, and the ion conductivity was 0.097 S / cm in the direction of the vertical magnetic field; 0.132S / cm.
  • the conductivity stability comparison between the ion exchange membrane prepared in Example 4 and an ion exchange membrane with the same formula prepared by a general spin coating method was performed, and the ionic conductivity attenuation rates of the two were measured in 95 ° C water for 30 days.
  • the results were as follows:
  • the ion conductivity membrane prepared in Example 4 has an ion conductivity decay rate of 10.1% in the direction of the parallel magnetic field and an ion conductivity decay rate of 11.4% in the direction of the vertical magnetic field.
  • the ion conductivity decay rate of the ion exchange membrane prepared by the general spin coating method is 49% in each direction. .
  • the film-forming droplets are formed on a horizontal turntable under the conditions of an air pressure of 1 atm and an electric field of 20 kV / cm, and the film is formed by rotating at a rotation speed of 200 r / s for 30 s at room temperature;
  • the membrane is removed from the horizontal turntable and immersed in 1 mol / L sodium chloride for ion replacement to obtain an ion exchange membrane with an ordered ion conduction structure.
  • the ion conductivity of the ion exchange membrane prepared in Example 5 is compared with that of the ion exchange membrane with the same formula (95 ° C. water) prepared by the general spin coating method. No electric field is applied in.
  • the results were as follows: the ion conductivity of the ion exchange membrane prepared in Example 5 was 0.045 S / cm in the direction of the parallel electric field, and the ion conductivity was 0.011 S / cm in the direction of the vertical electric field; 0.019S / cm.
  • the conductivity stability comparison between the ion exchange membrane prepared in Example 5 and an ion exchange membrane with the same formula prepared by a general spin coating method was performed, and the ionic conductivity attenuation rates of the two were measured in 95 ° C water for 30 days.
  • the results were as follows:
  • the ion conductivity membrane prepared in Example 5 has an ion conductivity decay rate of 1.5% in the parallel electric field direction and an ion conductivity decay rate of 1.2% in the vertical electric field direction.
  • the ion conductivity membrane has a 17.8% decay rate of ion conductivity in each direction prepared by a general spin coating method. .
  • the film-forming droplets are formed on a horizontal turntable under the conditions of a pressure of 1 atm and an electric field of 20 kV / cm, and the film is formed by rotating the film for 100 s at a speed of 1 r / s at room temperature;
  • the film is removed from the horizontal turntable, and immersed in 1 mol / L potassium hydroxide for ion replacement to obtain an ion exchange membrane having an ordered ion conduction structure.
  • the ion conductivity of the ion exchange membrane prepared in Example 6 was compared with an ion exchange membrane with the same formula prepared in a general spin coating method (95 ° C water). The difference between the general spin coating method and the preparation method in Example 6 is that the solvent evaporates. No electric field was applied during the process.
  • the results were as follows: the ion conductivity of the ion exchange membrane prepared in Example 6 was 0.109 S / cm in the direction of the parallel electric field, and the ion conductivity was 0.041 S / cm in the direction of the vertical electric field; 0.076S / cm.
  • the conductivity stability comparison between the ion exchange membrane prepared in Example 6 and an ion exchange membrane with the same formula prepared by a general spin coating method was performed, and the ion conductivity attenuation rates of the two in the 95 ° C water for 30 days were measured, and the results were as follows:
  • the ion exchange membrane prepared in Example 6 had an ionic conductivity decay rate of 3.9% in the parallel electric field direction and an ionic conductivity decay rate of 4.7% in the vertical electric field direction.
  • the ion conductivity decay rate of the ion exchange membrane prepared by the general spin coating method was 22.8% in each direction. .
  • This polymer containing a metal coordination structure is dissolved together with polyphenylene sulfide in a ratio of 10:90 parts by mass in chloronaphthalene, and a film-forming solution having a total solute concentration of 20 g / L is sufficiently prepared. Leave to defoam after dissolution;
  • the film-forming solution is immersed in a polytetrafluoroethylene porous membrane, and the film is formed by evaporating the solvent at 20 ° C. for 48 h under the conditions of an air pressure of 1 atm and a magnetic field intensity of 15 T;
  • the dip-coated film is reacted with nitrosyl tetrafluoroborate to undergo cobalt-site oxidation, and then immersed in 1 mol / L sodium bicarbonate for ion replacement to obtain ordered ion conduction. Structure of an ion exchange membrane.
  • the ion conductivity of the ion exchange membrane prepared in Example 7 was compared with the ion exchange membrane of the same formula prepared in the general dip coating method (in water at 95 ° C). The difference between the general dip coating method and the preparation method in Example 7 is that the solvent evaporates. No magnetic field was applied during the process.
  • the results were as follows: the ion conductivity of the ion exchange membrane prepared in Example 7 was 0.076 S / cm in the direction of the parallel magnetic field and the ion conductivity was 0.025 S / cm in the direction of the vertical magnetic field; the ion conductivity of the ion exchange membrane prepared by the general dip coating method in all directions 0.044S / cm.
  • the conductivity stability comparison between the ion exchange membrane prepared in Example 7 and an ion exchange membrane with the same formula prepared by a general dip coating method was performed, and the ionic conductivity decay rates of the two in the 95 ° C water for 30 days were measured.
  • the results are as follows:
  • the ion conductivity membrane prepared in Example 7 had an ion conductivity attenuation rate of 1.1% in the parallel magnetic field direction and an ion conductivity attenuation rate of 1.0% in the vertical magnetic field direction.
  • the ion conductivity membrane prepared by the general dip coating method had an ion conductivity attenuation rate of 9.9% in each direction. .
  • an ion-exchange membrane having an ordered ion-conducting structure can be obtained by immersing the dip-coated membrane in 1 mol / L potassium hydroxide for ion replacement.
  • the ion conductivity of the ion exchange membrane prepared in Example 8 is compared with that of the ion exchange membrane with the same formula (95 ° C. water) prepared by the general dip coating method.
  • the difference between the general dip coating method and the preparation method of Example 8 is that the solvent evaporates. No electric field was applied during the process.
  • the results were as follows: the ion conductivity of the ion exchange membrane prepared in Example 8 was 0.170 S / cm in the direction of the parallel electric field and the ion conductivity was 0.069 S / cm in the direction of the vertical electric field.
  • the ion conductivity of the ion exchange membrane prepared by the general dip coating method in all directions 0.091S / cm.
  • the conductivity stability comparison between the ion exchange membrane prepared in Example 8 and an ion exchange membrane with the same formula prepared by a general dip coating method was performed, and the ionic conductivity attenuation rates of the two were measured in 95 ° C water for 30 days.
  • the results were as follows:
  • the ion conductivity membrane prepared in Example 8 has an ion conductivity decay rate of 0.4% in the parallel electric field direction and an ion conductivity decay rate of 1.8% in the vertical electric field direction.
  • the ion conductivity membrane decay rate in each direction of the ion exchange membrane prepared by the general dip coating method is 21.9%. .
  • an ion-exchange membrane having an ordered ion-conducting structure can be obtained by immersing the dip-coated membrane in 1 mol / L of dilute sulfuric acid for ion replacement.
  • the ion conductivity of the ion exchange membrane prepared in Example 9 was compared with an ion exchange membrane with the same formulation prepared in a general dip coating method (in water at 95 ° C).
  • the difference between the general dip coating method and the preparation method in Example 9 is that the solvent evaporates. No electric field was applied during the process.
  • the results were as follows: the ion conductivity of the ion exchange membrane prepared in Example 9 was 0.188 S / cm in the parallel electric field direction, and the ion conductivity was 0.075 S / cm in the vertical electric field direction.
  • the conductivity stability comparison between the ion exchange membrane prepared in Example 9 and an ion exchange membrane with the same formula prepared by a general dip coating method was performed, and the ionic conductivity attenuation rates of the two in the 95 ° C water for 30 days were measured.
  • the results are as follows:
  • the ion exchange membrane prepared in Example 9 had an ion conductivity decay rate of 2.1% in the parallel electric field direction and an ionic conductivity decay rate of 1.9% in the vertical electric field direction.
  • the ion conductivity decay rate of the ion exchange membrane prepared by the general dip coating method was 13.5%. .
  • the film-forming solution is injected into a flexible screen substrate with a line width of 0.01 mm and a line pitch, and continuous roll-to-roll processing is performed at a horizontal operating speed of 100 m / min under the conditions of an air pressure of 1 atm and a magnetic field strength of 18 T. membrane;
  • the membrane is reacted with antimony pentachloride for nickel site oxidation, and then immersed in 1mol / L sodium hydroxide for ion replacement to obtain an ion exchange membrane with an ordered ion conduction structure. .
  • the ion conductivity of the ion exchange membrane prepared in Example 10 was compared with that of an ion exchange membrane with the same formula prepared by a general roll-to-roll screen printing method (in water at 95 ° C).
  • the general roll-to-roll screen printing method was the same as in Example 10.
  • the difference in the preparation method is that no magnetic field is applied during roll-to-roll processing.
  • the results were as follows:
  • the ion conductivity of the ion exchange membrane prepared in Example 10 was 0.079 S / cm in the parallel magnetic field direction and the ion conductivity was 0.025 S / cm in the vertical magnetic field direction.
  • the ion exchange membrane prepared by the general roll-to-roll screen printing method was in all directions.
  • the ionic conductivity is 0.045S / cm.
  • the conductivity stability of the ion-exchange membrane prepared in Example 10 Compare the conductivity stability of the ion-exchange membrane prepared in Example 10 with an ion-exchange membrane of the same formula prepared by a general roll-to-roll screen printing method, and measure the ionic conductivity attenuation rates of the two in 95 ° C water for 30 days.
  • the results are as follows: the ion exchange membrane prepared in Example 10 has an ion conductivity attenuation rate of 1.5% in the parallel magnetic field direction and an ion conductivity decay rate of 1.8% in the vertical magnetic field direction.
  • the ion exchange membrane prepared by the general roll-to-roll screen printing method has various directions. The ionic conductivity decay rate was 16.0%.
  • the membrane is immersed in 1 mol / L of dilute sulfuric acid for ion replacement to obtain an ion exchange membrane with an ordered ion conduction structure.
  • the ion conductivity of the ion-exchange membrane prepared in Example 11 was compared with that of an ion-exchange membrane with the same formula prepared by a general roll-to-roll screen printing method (in water at 95 ° C).
  • the general roll-to-roll screen printing method was the same as in Example 11.
  • the difference in the preparation method is that no electric field is applied during the roll-to-roll process.
  • the results were as follows: the ion conductivity of the ion exchange membrane prepared in Example 11 was 0.143 S / cm in the parallel electric field direction and the ion conductivity was 0.086 S / cm in the vertical electric field direction.
  • the ion exchange membrane prepared by the general roll-to-roll screen printing method was in all directions.
  • the ionic conductivity is 0.103S / cm.
  • the conductivity stability of the ion exchange membrane prepared in Example 11 with an ion exchange membrane with the same formula prepared by a general roll-to-roll screen printing method Compare the conductivity stability of the ion exchange membrane prepared in Example 11 with an ion exchange membrane with the same formula prepared by a general roll-to-roll screen printing method, and measure the ionic conductivity decay rate of the two in 95 ° C water for 30 days.
  • the results are: the ion exchange membrane prepared in Example 11 has an ion conductivity attenuation rate of 0.5% in the parallel electric field direction and an ion conductivity attenuation rate of 0.3% in the vertical electric field direction.
  • the ion exchange membrane prepared by the general roll-to-roll screen printing method has various directions.
  • the ionic conductivity decay rate was 7.9%.
  • This polymer containing a metal coordination structure is dissolved in dimethyl sulfoxide together with polyacrylonitrile and rectorite in a mass ratio of 50:20:30, and the total solute concentration is 200 g. / L of the film-forming solution, after fully dissolved, stand still and defoam;
  • the membrane is immersed in 1 mol / L of dilute sulfuric acid for ion replacement to obtain an ion exchange membrane with an ordered ion conduction structure.
  • the ion conductivity of the ion-exchange membrane prepared in Example 12 was compared with that of an ion-exchange membrane with the same formula prepared in a general roll-to-roll screen printing method (in water at 95 ° C.).
  • the general roll-to-roll screen printing method was the same as in Example 12.
  • the difference in the preparation method is that no electric field is applied during the roll-to-roll process.
  • the results are as follows:
  • the ion conductivity of the ion exchange membrane prepared in Example 12 is 0.139 S / cm in the parallel electric field direction and the ion conductivity is 0.065 S / cm in the vertical electric field direction.
  • the ion exchange membrane prepared by the general roll-to-roll screen printing method has various directions.
  • the ionic conductivity is 0.088S / cm.
  • the conductivity stability of the ion-exchange membrane prepared in Example 12 with an ion-exchange membrane of the same formula prepared by a general roll-to-roll screen printing method Compare the conductivity stability of the ion-exchange membrane prepared in Example 12 with an ion-exchange membrane of the same formula prepared by a general roll-to-roll screen printing method, and measure the ionic conductivity decay rates of the two in 95 ° C water for 30 days.
  • the results are as follows: the ion exchange membrane prepared in Example 12 has an ion conductivity attenuation rate of 3.1% in the parallel electric field direction and an ion conductivity attenuation rate of 2.6% in the vertical electric field direction.
  • the ion exchange membrane prepared by the general roll-to-roll screen printing method has various directions.
  • the ionic conductivity decay rate was 21.4%.
  • This polymer containing a metal coordination structure is dissolved in dimethylacetamide together with polyphosphazene and silica in a mass ratio of 45:45:10, and the total solute concentration is 20 g / L of the film-forming solution, after fully dissolved, stand still and defoam;
  • the mixed liquid of the film-forming liquid and the ultraviolet curable foaming ink with a mass ratio of 90:10 is charged into the inkjet device, and the mixed liquid is sprayed at room temperature through a nozzle under the conditions of an air pressure of 1 atm and a magnetic field strength of 25 T. Sprayed to the substrate, and then formed into a film after 10min UV curing;
  • the membrane is reacted with tetracyanoethylene to carry out nickel site oxidation, and then immersed in 1 mol / L sodium chloride for ion replacement to obtain an ion exchange membrane with an ordered ion conduction structure. .
  • Example 13 Compare the ion conductivity of the ion exchange membrane prepared in Example 13 with the ion exchange membrane of the same formula prepared in the general inkjet printing method (95 ° C water).
  • the difference between the general inkjet printing method and the preparation method in Example 13 is that No magnetic field is applied during ink printing and UV curing.
  • the results were as follows: the ion conductivity of the ion exchange membrane prepared in Example 13 was 0.084 S / cm in the direction of the parallel magnetic field, and the ion conductivity was 0.030 S / cm in the direction of the vertical magnetic field.
  • the ion conductivity of the ion exchange membrane prepared by the general inkjet printing method in all directions 0.049S / cm.
  • the conductivity stability comparison between the ion exchange membrane prepared in Example 13 and the ion exchange membrane with the same formula prepared by the inkjet printing method was performed, and the ionic conductivity attenuation rates of the two in the 95 ° C water for 30 days were measured, and the results were as follows:
  • the ion conductivity attenuation rate of the ion exchange membrane prepared in Example 13 in the parallel magnetic field direction was 1.2%, and the ion conductivity attenuation rate in the vertical magnetic field direction was 1.1%.
  • the ion conductivity attenuation rate of the ion exchange membrane prepared by the general inkjet printing method was 12.5 %.
  • This polymer containing metal coordination structure is dissolved in dimethyl sulfoxide together with polyvinylidene fluoride and boron nitride in a mass ratio of 44: 55: 1, and the total solute concentration is formulated as 200g / L film-forming solution, fully dissolved and left to defoam;
  • the membrane is immersed in 1 mol / L potassium hydroxide for ion replacement to obtain an ion exchange membrane with an ordered ion conduction structure.
  • the ion conductivity of the ion exchange membrane prepared in Example 14 was compared with an ion exchange membrane with the same formulation prepared in a general inkjet printing method (95 ° C water).
  • the difference between the general inkjet printing method and the preparation method of Example 14 is that No magnetic field is applied during ink printing and UV curing.
  • the results were as follows:
  • the ion conductivity of the ion exchange membrane prepared in Example 14 was 0.139 S / cm in the direction of the parallel magnetic field, and the ion conductivity was 0.068 S / cm in the direction of the vertical magnetic field.
  • the ion conductivity of the ion exchange membrane prepared by the general inkjet printing method in all directions 0.092S / cm.
  • the conductivity stability comparison between the ion exchange membrane prepared in Example 14 and the ion exchange membrane with the same formula prepared by the inkjet printing method was performed, and the ionic conductivity attenuation rates of the two were measured in 95 ° C water for 30 days.
  • the results were as follows:
  • the ion conductivity membrane prepared in Example 14 has an ion conductivity decay rate of 0.5% in the direction of the parallel magnetic field and an ion conductivity decay rate of 1.2% in the direction of the vertical magnetic field.
  • the ion conductivity decay rate of the ion exchange membrane prepared by the general inkjet printing method is 13.1 %.
  • This polymer containing a metal coordination structure is dissolved in tetrahydrofuran together with polymethyl methacrylate and nitrogen carbide at a mass ratio of 33: 66: 1, and the total solute concentration is 350g / L.
  • the film-forming solution is fully dissolved and left standing to defoam;
  • the membrane is reacted with tetracyanoethylene to undergo iron site oxidation, and then immersed in 1 mol / L sodium hydroxide for ion replacement to obtain an ion exchange membrane with an ordered ion conduction structure. .
  • the ion conductivity of the ion exchange membrane prepared in Example 15 is compared with that of an ion exchange membrane with the same formula prepared in a general inkjet printing method (in water at 95 ° C.).
  • the difference between the general inkjet printing method and the preparation method in Example 15 is that No electric field is applied during ink printing and UV curing.
  • the results were as follows: the ion conductivity of the ion exchange membrane prepared in Example 15 was 0.099 S / cm in the parallel electric field direction, and the ion conductivity was 0.035 S / cm in the vertical electric field direction.
  • the ion conductivity of the ion exchange membrane prepared by the general inkjet printing method in all directions It was 0.057 S / cm.
  • the conductivity stability comparison between the ion exchange membrane prepared in Example 15 and the ion exchange membrane with the same formula prepared by the inkjet printing method was performed, and the ionic conductivity attenuation rates of the two were measured in 95 ° C water for 30 days.
  • the results were as follows:
  • the ion conductivity membrane prepared in Example 15 had an ion conductivity decay rate of 2.5% in the parallel electric field direction and an ion conductivity decay rate of 2.6% in the vertical electric field direction.
  • the ion conductivity decay rate of the ion exchange membrane prepared by the general inkjet printing method was 19.1 %.

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Abstract

Un procédé de préparation d'une membrane échangeuse d'ions ayant une structure de conduction ionique ordonnée, comprenant : premièrement, la synthèse d'un polymère a contenant une structure de ligand métallique; puis la formulation individuelle du polymère A, ou le polymère A et un polymère B, le polymère A et une charge, ou le polymère A, le polymère B, et la charge dans la solution de préparation de membrane, dissolution complète de celui-ci, et laisser le même support pour démoussage; le versement de celui-ci dans un récipient de culture, et la formation d'une membrane au moyen d'un procédé d'évaporation de solvant, un procédé d'enrobage par centrifugation, un procédé d'enrobage par immersion, un procédé d'impression à écran à soie rouleau à rouleau, ou un procédé à jet d'encre dans des conditions d'une certaine pression, température, temps, intensité de champ magnétique ou intensité de champ électrique; et après les extrémités du processus de formation de membrane, ionisation de la membrane pour obtenir la membrane échangeuse d'ions. Lorsqu'un champ magnétique ou un champ électrique est appliqué pendant la formation de la membrane, la structure de conduction ionique de la membrane échangeuse d'ions peut être régulée de manière ordonnée, et une membrane échangeuse d'ions hautement efficace et durable ayant la structure de conduction ionique ordonnée peut être préparée.
PCT/CN2018/099640 2018-07-11 2018-08-09 Procédé de préparation d'une membrane échangeuse d'ions ayant une structure de conduction ionique ordonnée WO2020010660A1 (fr)

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CN109880078A (zh) * 2018-12-29 2019-06-14 福建师范大学泉港石化研究院 一种薄壁耐高温耐辐射阻燃电缆料聚醚醚酮及其制备方法
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CN110137550A (zh) * 2019-05-28 2019-08-16 西北工业大学 一种碱性阴离子交换膜及制备方法和甲酸盐燃料电池制备方法
CN110620253B (zh) * 2019-09-25 2022-09-02 东北大学 一种利用旋涂技术基于磺化氧化石墨烯制备非水质子交换膜的方法
CN111013669B (zh) * 2019-12-04 2022-09-06 大连融科储能技术发展有限公司 阳离子交换膜及其制备方法和应用
CN111342096B (zh) * 2020-03-09 2022-10-04 长春工业大学 燃料电池用吡啶化交联型阴离子交换膜及其制备方法
CN112751067B (zh) * 2021-01-04 2021-11-16 西北工业大学 一种交联型阴离子交换膜及其制备方法和应用
CN115353657B (zh) * 2022-08-15 2023-07-04 湖北工程学院 一种磁场诱导的有机-无机复合交联阴离子交换膜的制备方法

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