WO2020010660A1

WO2020010660A1 - Preparation method for ion-exchange membrane having ordered ionic conduction structure

Info

Publication number: WO2020010660A1
Application number: PCT/CN2018/099640
Authority: WO
Inventors: 尹燕; 张俊锋; 刘鑫; 盖费·迈克尔·多米尼克
Original assignee: 天津大学
Priority date: 2018-07-11
Filing date: 2018-08-09
Publication date: 2020-01-16
Also published as: CN109078501B; CN109078501A

Abstract

A preparation method for an ion-exchange membrane having an ordered ionic conduction structure, comprising: first, synthesizing a polymer A containing a metal ligand structure; and then individually formulating the polymer A, or the polymer A and a polymer B, the polymer A and a filler, or the polymer A, the polymer B, and the filler into the membrane preparation solution, fully dissolving same, and letting same stand for defoaming; pouring same into a culture dish, and forming a membrane by means of a solvent evaporation method, a spin coating method, a dip-coating method, a roll-to-roll silkscreen print method, or an inkjet method at conditions of a certain pressure, temperature, time, magnetic field intensity or electric field intensity; and after the membrane formation process ends, ionizing the membrane to obtain the ion-exchange membrane. When a magnetic field or an electric field is applied during membrane formation, the ionic conduction structure of the ion-exchange membrane can be orderly regulated, and a highly efficient and durable ion-exchange membrane having the ordered ionic conduction structure can be prepared.

Description

Preparation method of ion exchange membrane with ordered ion conduction structure

Technical field

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.

technical background

Ion exchange membranes are key materials in many fields such as adsorption, electrolysis, separation, batteries, supercapacitors and so on. As two important performance parameters of ion exchange membranes, ionic conductivity and water absorption always show a positive correlation, because only hydrophilic ionized groups can play an efficient ion conduction effect. However, 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.

In practical applications, 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. For example, 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. However, 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.

Summary of the invention

In order to solve the above technical problems, 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.

The present invention is achieved through the following technical solutions:

A method for preparing an ion-exchange membrane with an ordered ion-conducting structure. The method is performed according to the following steps:

(1) Synthesis of polymer A containing a metal coordination structure;

(2) Polymer A alone, or polymer A and polymer B, or polymer A and filler, or polymer A and polymer B and filler are dissolved in a solvent to a total concentration of 10 to 500 g / L The film-forming solution is fully dissolved and left standing to defoam;

(3) Under the conditions of a pressure of 1 atm, a magnetic field strength of 1 to 50 T, or an electric field strength of 1 to 100 kV / cm, the solvent evaporation method, spin coating method, dip coating method, roll-to-roll screen printing method or inkjet printing method are used. membrane;

(4) After the film formation process is completed, the membrane is ionized to obtain an ion exchange membrane having an ordered ion conduction structure.

Preferably, 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.

Preferably, 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. One.

Preferably, the proportion of the metal-containing coordination structure segment in the polymer A in the step (1) is 10% to 100%.

Preferably, 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.

Preferably, 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.

Preferably, 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.

Preferably, when the polymer A and the polymer B are dissolved in the solvent in the step (2), 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).

Preferably, 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;

Preferably, 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;

Preferably, 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;

Preferably, 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;

Preferably, 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. In the ink device, 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.

Preferably, the ionization treatment described in step (4) is direct ion replacement or ion replacement after oxidation.

The beneficial effects of the present invention are:

The method for preparing an ion exchange membrane with an ordered ion conduction structure provided by the invention has a wide range of applicable raw materials, a simple preparation process, and mild processing conditions. Compared with the general film formation method, 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.

BRIEF DESCRIPTION OF THE DRAWINGS

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;

4 is a comparison chart of the conductivity stability of the membrane 1 and the membrane 2;

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;

8 is a comparison diagram of the conductivity stability of the membrane 3 and the membrane 4;

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.

detailed description

The following further describes the present invention in detail through specific embodiments. The following embodiments may enable the person skilled in the art to more fully understand the present invention, but does not limit the present invention in any way.

Example 1:

(1) Preparation of polymers containing metal coordination structures

The proportion x of the segment containing the metal coordination structure is 50%. The specific steps are: dissolving 1.6 g of sodium pentacyanatoferrate and 3.8 g of 15-crown-5 in 10 ml of water, and 0.4 g of polyvinyl pyridine in 10 ml of methanol. The two solutions were mixed and reacted at 40 ° C for 36 hours. The reaction solution was poured into water, and the precipitate was washed 3 times with 1 mol / L dilute sulfuric acid, and then washed with ultrapure water to pH = 7, and then dried at 80 ° C for 12 hours. product;

(2) This polymer containing a metal coordination structure is dissolved in dimethylacetamide together with polysulfone and phosphotungstic acid at a ratio of 5:45:50 parts by mass, and the total solute concentration is 500 g / The film-forming solution of L, after being fully dissolved, stand still and defoam;

(3) Pour the film-forming solution into a petri dish, and evaporate the solvent at 80 ° C. for 12 h to form a film under the conditions of an air pressure of 1 atm and a magnetic field strength of 35 T;

(4) After the film formation process is completed, 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.

Example 2:

(1) Preparation of polymers containing metal coordination structures

The proportion x of the metal-containing coordination structure is 80%. The specific steps are as follows: 1 g of styrene, 5 g of dimethylsilicon bridged nickelocene, 0.1 g of tetramethylpiperidine oxide, and 0.3 g of azobisisobutyronitrile. In 100 ml of toluene, react at 130 ° C for 12h under the protection of nitrogen, pour the reaction solution into water, wash the precipitate with ultrapure water to pH = 7, and then dry at 80 ° C for 12h to obtain the product;

(2) This polymer containing a metal coordination structure and a magnesium-aluminum layered double hydroxide are dissolved together in a dimethylformamide at a ratio of 75:25 parts by mass, and the total solute concentration is 100 g / The film-forming solution of L, after being fully dissolved, stand still and defoam;

(3) Pour the film-forming solution into a petri dish, and evaporate the solvent at 20 ° C for 48h to form a film under the conditions of air pressure 1atm and magnetic field 1T;

(4) After the film formation process is completed, 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.

Example 3:

(1) Preparation of polymers containing metal coordination structures

The proportion x of the segment containing the metal coordination structure is 100%. The specific steps are: dissolve 3g of vinyl cobaltocene, 0.1g of tetramethylpiperidine oxide and 0.3g of azobisisobutyronitrile in 100ml of toluene, and protect under nitrogen. Reaction was performed at 130 ° C for 12 hours, and the temperature was lowered to room temperature. 1 g of tetracyanoethylene in 20 ml of toluene solution was added with a syringe. The reaction was continued for 12 hours. The reaction solution was poured into water, and the precipitate was soaked with 1 mol / L sodium hydroxide for 12 hours. The product was washed with pure water to pH = 7, and then dried at 80 ° C for 12h.

(2) dissolving such a polymer containing a metal coordination structure separately in azomethylpyrrolidone to prepare a film-forming solution having a total solute concentration of 10 g / L, and fully dissolving, and standing and defoaming;

(3) Pour the film-forming solution into a petri dish, and evaporate the solvent at 100 ° C for 15h to form a film under the conditions of an air pressure of 1 atm and an electric field of 50 kV / cm;

(4) After the film formation process is completed, 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.

Example 4

(1) Preparation of polymers containing metal coordination structures

The proportion of the segment containing the metal coordination structure x = 60%, the specific steps are: react 3g of polyetheretherketone with 300ml of 98% concentrated sulfuric acid at -15 ° C for 8h, add 3g of chloromethyloctyl ether to continue the reaction for 1h, add 3g p-hydroxypyridine was continued to react for 1h, the reaction solution was poured into water, the precipitate was washed to pH = 7, and dried at 80 ° C for 12h to obtain a precursor polymer; 1.6g of sodium pentacyanoferrate and 3.8g of 15-crown- 5 dissolved in 10 ml of water, 0.4 g of the precursor polymer was dissolved in 10 ml of methanol, the two solvents were mixed at a volume ratio of 3: 1, and the reaction was carried out at 50 ° C for 96 hours. The reaction solution was poured into water, and the precipitate was diluted with 1 mol / L of dilute sulfuric acid. Washed 3 times, then washed with ultrapure water to pH = 7, and then dried at 80 ° C for 12h as the product;

(2) 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;

(3) 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;

(4) After the film formation process is completed, 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. .

Example 5

(1) Preparation of polymers containing metal coordination structures

The proportion of the segment containing the metal coordination structure x = 70%. The specific steps are: react 3g of polysulfone with 300ml of 98% concentrated sulfuric acid at -15 ° C for 8h, add 3g of chloromethyloctyl ether to continue the reaction for 1h, and add 3g of stack. Sodium nitride was reacted at 70 ° C for 12 hours. The reaction solution was poured into water, and the precipitate was washed to pH = 7 and dried at 80 ° C for 12 hours to obtain a precursor polymer. 3 g of acetylene ferrocene and 3 g of the precursor polymer were dissolved. In 300ml of tetrahydrofuran, react at 30 ° C for 72h, add 5g of 100ml of tetrahydrofuran solution of nitros hexafluorophosphate, continue the reaction for 12h, pour the reaction solution into water, soak the precipitate with 1mol / L potassium chloride for 12h, and then use ultrapure The product was washed with water until pH = 7, and then dried at 80 ° C for 12h.

(2) This polymer containing a metal coordination structure is dissolved together with polyimide and graphene oxide in a mass ratio of 9: 90: 1 in m-cresol, and the total solute concentration is 50 g / The film-forming solution of L, after being fully dissolved, stand still and defoam;

(3) 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;

(4) After the film formation process is completed, 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. .

Example 6

(1) Preparation of polymers containing metal coordination structures

The proportion of the segment containing the metal coordination structure x = 10%, the specific steps are: 5 g of p-diphenyl ether sulfuryl chloride, 1 g of methyl quaternary silicon bridged cobaltocene, 0.1 g of tetramethylpiperidine oxide and 0.3 g Azobisisobutyronitrile was dissolved in 100ml of toluene and reacted at 130 ° C for 12h under the protection of nitrogen. The reaction solution was poured into water. The precipitate was soaked with 1mol / L potassium hydroxide for 12h, and then washed with ultrapure water to pH = 7. The product was dried at 80 ℃ for 12h;

(2) This polymer containing a metal coordination structure and polyethersulfone are dissolved together in dimethylformamide at a ratio of 90:10 parts by mass to prepare a film-forming solution having a total solute concentration of 200 g / L. , After fully dissolving, stand still and defoam;

(3) 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;

(4) After the film formation process is completed, 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. .

Example 7

(1) Preparation of polymers containing metal coordination structures

The proportion of the segment containing the metal coordination structure x = 75%. The specific steps are: dissolving 2 g of caprolactam, 5 g of methylphenylsilicon bridged cocenecene, 0.1 g of tetramethylpiperidine oxide and 0.3 g of azobisisobutyronitrile. In 100 ml of toluene, react at 130 ° C for 12h under the protection of nitrogen, pour the reaction solution into water, soak the precipitate with 1mol / L potassium hydroxide for 12h, then wash with ultrapure water to pH = 7, and then dry at 80 ° C for 12h. As a product

(2) 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;

(3) 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;

(4) After the film-forming process is completed, 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. .

Example 8

(1) Preparation of a polymer containing a metal coordination structure, the proportion of the segment containing the metal coordination structure x = 55%, the specific steps are: 2g pyromellitic anhydride, 2g diamine diphenyl ether, 5g diphenyl Silicone bridged nickelcene, 0.1g of tetramethylpiperidine oxide and 0.3g of azobisisobutyronitrile were dissolved in 100ml of toluene, and reacted at 130 ° C for 12h under the protection of nitrogen, and 3g of antimony pentachloride in 50ml of toluene solution was added, The reaction was continued for 12h. The reaction solution was poured into water, and the precipitate was soaked with 1mol / L sodium hydroxide for 12h, and then washed with ultrapure water to pH = 7, and then dried at 80 ° C for 12h as the product;

(2) This polymer containing metal coordination structure and polystyrene are dissolved together in dimethyl sulfoxide at a ratio of 70:30 parts by mass to prepare a film-forming solution having a total solute concentration of 400 g / L. , After fully dissolving, stand still and defoam;

(3) The film-forming solution is immersed in a polyethylene porous membrane, and the solvent is evaporated to form a film at 50 ° C. for 20 h under the conditions of an air pressure of 1 atm and an electric field strength of 45 kV / cm;

(4) After the film-forming process is completed, 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%. .

Example 9

(1) Preparation of polymers containing metal coordination structures

The proportion of the segment containing the metal coordination structure x = 85%, the specific steps are: 1g of diaminobenzidine, 1g of diphenyl isophthalate, 5g of methyl p-benzenesulfonic acid silicon bridge nickel dicene, 0.1 g of tetramethylpiperidine oxide and 0.3g of azobisisobutyronitrile were dissolved in 100ml of toluene, and reacted at 130 ° C for 12h under the protection of nitrogen, the reaction solution was poured into water, and the precipitate was soaked with 1mol / L of dilute sulfuric acid for 12h, and then used The product was washed with ultrapure water to pH = 7, and then dried at 80 ° C for 12h.

(2) dissolving such a polymer containing a metal coordination structure together with carbon nanotubes in a nitrogen methylpyrrolidone at a ratio of 99: 1 by mass, to prepare a film-forming solution having a total solute concentration of 25 g / L, After fully dissolving, let it stand and defoam;

(3) The film-forming solution is immersed in a porous nylon membrane, and the solvent is evaporated to form a film at 100 ° C. for 12 h under the conditions of an air pressure of 1 atm and an electric field strength of 1 kV / cm;

(4) After the film-forming process is completed, 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 ion conductivity of the ion exchange membrane prepared by the general dip coating method in all directions 0.102S / cm.

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%. .

Example 10

(1) Preparation of polymers containing metal coordination structures

The proportion of the segment containing the metal coordination structure x = 20%, the specific steps are: 5g of dichlorodimethylsilane, 0.5h of water, 3g of dimethylsilicon bridged nickelcene, 0.1g of tetramethylpiperidine oxide And 0.3g of azobisisobutyronitrile were dissolved in 100ml of toluene, and reacted at 130 ° C for 12h under the protection of nitrogen. The reaction solution was poured into water, and the precipitate was washed with ultrapure water to pH = 7, and then dried at 80 ° C for 12h to obtain the product;

(2) This polymer containing metal coordination structure and montmorillonite are dissolved together in dimethylformamide at a ratio of 50:50 parts by mass to prepare a film-forming solution with a total solute concentration of 100 g / L , After fully dissolving, stand still and defoam;

(3) 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;

(4) After the film formation process is completed, 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.

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%.

Example 11

(1) Preparation of polymers containing metal coordination structures

The proportion of the segment containing the metal coordination structure x = 30%. The specific steps are: reacting 3 g of polytetrafluoroethylene with 0.1 g of sodium hydride and 3 g of p-hydroxypyridine in a 300 ml dimethylformamide solution at 0 ° C for 36 hours. Pour into water, wash the precipitate to pH = 7, and dry at 80 ° C for 12h to obtain the precursor polymer; dissolve 1.6g of sodium pentacyanoferrate and 3.8g of 15-crown-5 in 10ml of water, 0.4g of precursor The polymer was dissolved in 10 ml of methanol, and the two solvents were mixed in a volume ratio of 3: 1, and the reaction was performed at 50 ° C for 96 hours. The reaction solution was poured into water, and the precipitate was washed 3 times with 1 mol / L diluted sulfuric acid, and then washed with ultrapure water to The product is pH = 7 and then dried at 80 ° C for 12h;

(2) This polymer containing a metal coordination structure is dissolved in xylene together with polypropylene and halloysite at a ratio of 20:70:10 parts by mass to prepare a system having a total solute concentration of 15 g / L. Membrane fluid, fully degassed after being fully dissolved;

(3) Inject the film-forming solution into a flexible screen substrate with a line width of 0.1mm and a line pitch, and perform continuous roll-to-roll under the conditions of an air pressure of 1 atm and an electric field strength of 100 kV / cm at a horizontal operating speed of 500 m / min at room temperature. Processed into a film;

(4) After the film formation process is completed, 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.

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%.

Example 12

(1) Preparation of polymers containing metal coordination structures

The proportion of the segment containing the metal coordination structure x = 40%, the specific steps are: reacting 3g polyethylene with 3g p-hydroxypyridine in 300ml dimethylformamide solution at 0 ° C and gamma rays for 8h, and pouring the reaction solution into In water, the precipitate was washed to pH = 7, and dried at 80 ° C for 12 h to obtain a precursor polymer; 1.6 g of sodium pentacyanoferrate and 3.8 g of 15-crown-5 were dissolved in 10 ml of water, and 0.4 g of the precursor polymer Dissolve in 10ml of methanol, mix the two solvents at a volume ratio of 3: 1, and react at 50 ° C for 96h. Pour the reaction solution into water, wash the precipitate 3 times with 1mol / L dilute sulfuric acid, and then wash with ultrapure water to pH = 7, and then dried at 80 ℃ for 12h is the product;

(2) 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;

(3) Inject the film-forming solution into a 0.06mm line width and line pitch on a flexible screen substrate. Under the conditions of an air pressure of 1 atm and an electric field strength of 65 kV / cm, continuous rewinding is performed at a room temperature and a horizontal running speed of 0.1 m / min. Roll processing into film;

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.

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%.

Example 13

(1) Preparation of polymers containing metal coordination structures

The proportion of the segment containing the metal coordination structure x = 65%. The specific steps are as follows: 3 g of polyphenylene ether, 3 g of bromosuccinimide and 0.1 g of azobisisobutyronitrile are dissolved in 300 ml of nitrogen methylpyrrolidone, and the temperature is 30 ° C. After 48 hours of reaction, 3g of sodium azide was added and reacted at 70 ° C for 12h. The reaction solution was poured into water, the precipitate was washed to pH = 7, and dried at 80 ° C for 12h to obtain a precursor polymer; 3g of ethynyl nickellocene and 3g of the precursor polymer was dissolved in 300ml of tetrahydrofuran, reacted at 30 ° C for 72h, the reaction solution was poured into water, the precipitate was washed with ultrapure water to pH = 7, and then dried at 80 ° C for 12h to obtain the product;

(2) 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;

(3) 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;

(4) After the film formation process is completed, 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. .

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 %.

Example 14

(1) Preparation of a polymer containing a metal coordination structure, the proportion of the segment containing the metal coordination structure x = 15%, the specific steps are: 1g vinylcyclohexane, 5g dimethylsilicon bridged ferrocene, 0.1 g of tetramethylpiperidine oxide and 0.3g of azobisisobutyronitrile were dissolved in 100ml of toluene, and reacted at 130 ° C for 12h under the protection of nitrogen. 3g of antimony pentachloride in 50ml of toluene solution was added with a syringe, and the reaction was continued for 12h. The reaction solution was poured into In water, the precipitate was soaked with 1 mol / L sodium hydroxide for 12 h, and then washed with ultrapure water to pH = 7, and then dried at 80 ° C. for 12 h to obtain the product;

(2) 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;

(3) The mixed liquid of the film-forming liquid and the ultraviolet curable foaming ink with a mass ratio of 10:90 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 50 T Sprayed onto the substrate, and then formed into a film by UV curing for 1min;

(4) After the film formation process is completed, 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 %.

Example 15

(1) preparing a polymer containing a metal coordination structure, the proportion of the segment containing the metal coordination structure x = 95%, and the specific steps are: dissolving 3 g of polyvinyl chloride and 3 g of sodium azide in 300 ml of nitrogen methylpyrrolidone, The reaction was carried out at 70 ° C for 12 hours. The reaction solution was poured into water, and the precipitate was washed to pH = 7 and dried at 80 ° C for 12 hours to obtain a precursor polymer. 3 g of ethynylferrocene and 3 g of the precursor polymer were dissolved in 300 ml of tetrahydrofuran. , React at 30 ° C for 72h, pour the reaction solution into water, wash the precipitate with ultrapure water to pH = 7, and then dry at 80 ° C for 12h to be the product;

(2) 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;

(3) The mixed solution of the film-forming liquid and the UV-curable foaming ink with a mass ratio of 60:40 is charged into the inkjet device, and the pressure is 1 atm and the electric field strength is 300 kV / cm. The mixed solution is sprayed onto the substrate, and then formed into a film by UV curing for 7 minutes;

(4) After the film formation process is completed, 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 %.

Although the preferred embodiments of the present invention have been described above with reference to the accompanying drawings, the present invention is not limited to the specific embodiments described above, and the specific embodiments described above are merely schematic and are not restrictive, and are common techniques in the art. Under the enlightenment of the present invention, a person can also make many specific changes without departing from the scope of the invention and the scope of protection of the claims, which all fall within the protection scope of the present invention.

Claims

A method for preparing an ion-exchange membrane having an ordered ion-conducting structure is characterized in that the method is performed according to the following steps:

(1) Synthesis of polymer A containing a metal coordination structure;

(2) Polymer A alone, or polymer A and polymer B, or polymer A and filler, or polymer A and polymer B and filler are dissolved in a solvent to a total concentration of 10 to 500 g / L The film-forming solution is fully dissolved and left standing to defoam;

(3) Under the conditions of a pressure of 1 atm, a magnetic field strength of 1 to 50 T, or an electric field strength of 1 to 100 kV / cm, the solvent evaporation method, spin coating method, dip coating method, roll-to-roll screen printing method or inkjet printing method are used. membrane;

(4) After the film formation process is completed, the membrane is ionized to obtain an ion exchange membrane having an ordered ion conduction structure.
The method for preparing an ion exchange membrane with an ordered ion conduction structure according to claim 1, wherein the polymer matrix in the polymer A in step (1) is polyimide or polyamide , Polyetheretherketone, polysulfone, polyethersulfone, polytetrafluoroethylene, polydimethylsiloxane, polystyrene, polybenzimidazole, polyphenylene ether, polyethylene, polyvinyl chloride, polyvinylpyridine Or one or more of polyvinylcyclohexane.
The method for preparing an ion exchange membrane with an ordered ion conduction structure according to claim 1, wherein the metal coordination structure in step (1) is iron pentacyanopyridine, ferrocene, One of ferrocene oxide, cobaltocene, cobaltocene oxide, nickelcene, or nickelcene oxide.
The method for preparing an ion-exchange membrane with an ordered ion-conducting structure according to claim 1, wherein the proportion of the metal-containing coordination structure in the polymer A in the step (1) is 10 % To 100%.
The method for preparing an ion exchange membrane with an ordered ion conduction structure according to claim 1, wherein the polymer B in step (2) is polyimide, polysulfone, polyethersulfone , Polystyrene, polyphenylene sulfide, polyvinylpyridine, polypropylene, polyacrylonitrile, polyphosphazene, polyvinylidene fluoride, or polymethyl methacrylate.
The method for preparing an ion-exchange membrane having an ordered ion-conducting structure according to claim 1, wherein the filler in step (2) is a layered double layer of phosphotungstic acid, phosphomolybdic acid, and magnesium-aluminum One of hydroxide, carbon nanotube, halloysite, rectorite, montmorillonite, silicon dioxide, graphene oxide, boron nitride, or nitrogen carbide.
The method for preparing an ion exchange membrane having an ordered ion conduction structure according to claim 1, wherein the solvent in step (2) is dimethylformamide, dimethylacetamide, nitrogen One of methylpyrrolidone, dimethyl sulfoxide, m-cresol, chloronaphthalene, tetrahydrofuran or xylene.
The method for preparing an ion-exchange membrane having an ordered ion-conducting structure according to claim 1, characterized in that, when the polymer A and the polymer B are dissolved in the solvent in step (2) The ratio by mass of the polymer A to the polymer B is (10-90): (10-90); when the polymer A and the filler are dissolved in the solvent, the polymerization The mass ratio of the substance 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, the polymerization The mass ratio of the substance A, the polymer B, and the filler is (5 to 90): (5 to 90): (1 to 50).
The method for preparing an ion-exchange membrane having an ordered ion-conducting structure according to claim 1, wherein the solvent evaporation method in step (3) is pouring a film-forming solution into a petri dish, and Film formation at ～ 100oC for 12 ～ 48h;

The spin coating method described in step (3) is to form a film on a horizontal turntable, and rotate the film at a room temperature of 1 to 1000 r / s for 1 to 100 s to form a film;

The dipping 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 hours 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 perform the operation at a horizontal running speed of 0.1 to 500 m / min at room temperature. Continuous roll-to-roll processing into film;

In the inkjet printing method described in step (3), 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) is charged into an inkjet device. The mixed solution is sprayed to the substrate through a nozzle at room temperature, and then UV-cured to form a film after 1 to 10 minutes.
The method for preparing an ion exchange membrane with an ordered ion conduction structure according to claim 1, wherein the ionization treatment in step (4) is direct ion replacement or ion replacement after oxidation.