CN112221357B - Sulfonated polyether-ether-ketone composite membrane of attapulgite and metal organic framework composite material and preparation method and application thereof - Google Patents
Sulfonated polyether-ether-ketone composite membrane of attapulgite and metal organic framework composite material and preparation method and application thereof Download PDFInfo
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- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
- H01M8/1025—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having only carbon and oxygen, e.g. polyethers, sulfonated polyetheretherketones [S-PEEK], sulfonated polysaccharides, sulfonated celluloses or sulfonated polyesters
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- 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
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Abstract
The invention belongs to the technical field of fuel cells, and particularly relates to a sulfonated polyether ether ketone composite membrane made of attapulgite and a metal organic framework composite material, and a preparation method and application thereof. The method comprises the following steps: 1) preparing a composite material of attapulgite and a metal organic framework; 2) preparing the sulfonated polyether-ether-ketone composite exchange membrane of the attapulgite and metal organic framework composite material. According to the invention, firstly, a certain amount of attapulgite is added in the preparation process of the metal organic framework, the attapulgite-metal organic framework hybrid composite material is prepared in situ, and the effective combination of the attapulgite and the metal organic framework material is realized on the basis of keeping the structure of the metal organic framework material. And then compounding the prepared attapulgite-metal organic framework material with sulfonated polyether ether ketone to prepare the proton exchange membrane, thereby improving the comprehensive performance of the composite membrane.
Description
Technical Field
The invention belongs to the technical field of fuel cells, and particularly relates to a sulfonated polyether-ether-ketone composite membrane made of attapulgite and a metal organic framework composite material, and a preparation method and application thereof.
Background
Metal Organic Frameworks (MOFs) are a class of Metal ions and organic ligandsThe novel material with a highly ordered porous network structure is formed and widely applied to the aspects of gas adsorption and separation, catalysis and the like. In addition, as a porous material, the metal organic framework has the characteristics of structural diversity and controllability, and particularly easy functional modification, so that the metal organic framework has a very good application potential in proton conduction [ adv. matrix. interfaces,2019,6,1801146 ], such as the classical MIL (matrix institute Lavoisier) material, the ZIFs (zeolite-inert frameworks) material, and the uo-66 (universal i Oslo) material, which are widely researched as proton conductors. In contrast, UiO-66 is a framework structure made from terephthalic acid and ZrCl 4 The metal organic framework material has good thermal and chemical stability, large pore-size structure and specific surface area, and easy realization of preparation process, and has good application potential in the field of proton conduction. Li research group prepared a series of-SO-containing 3 H、-COOH、-NH 2 a-Br functional group of UiO-66 material [ Crystal. grown Des.,2015,15,5827 ], with a maximum proton conductivity of 0.34X 10 -2 S cm -1 (40 ℃, 97% RH). The Hong group obtained UiO-66- (SO 5142-) 5146 by functionalizing sulfonic acid with the skeleton structure of UiO-66 [ Angew. chem. int. Ed.,2015,54, 5142-) 3 H) 2 The conductivity of the material reaches 8.4 x 10 -2 S cm -1 (80℃,90％RH)。
However, how to apply metal organic framework materials with better conductivity to the field of Proton Exchange Membranes (PEMs) still faces many challenges. The difficulty of film formation and the difficulty of long-distance proton transmission caused by the brittleness of the metal organic framework material bulk phase can be realized, and the strategy of compounding and preparing the metal organic framework and the polymer matrix can realize the practical application of the metal organic framework material in the field of proton exchange membranes by combining the stability characteristic of the polymer matrix on the basis of fully utilizing the proton conduction capability of the metal organic framework. The metal organic framework materials are reported in polymer modification researches such as Nafion polymers, sulfonated polyaryl ether, polyethylene, polybenzimidazole and chitosan. However, the research on the application of the metal organic framework material in the proton exchange membrane still fails to meet the practical application requirements. On the one hand, in the strategy of compounding a single metal organic framework material with a polymer matrix, the metal organic framework can only realize lower filling amount due to the difference between the interface property of the metal organic framework matrix and the polymer matrix, and the improvement of the conductivity is limited. On the other hand, the single metal organic framework material does not have an obvious effect of improving the mechanical property of the composite system, and the mechanical property cannot be effectively improved. The hybrid preparation method of the metal organic framework and the material with special structure and performance is helpful for solving the problems. Attapulgite (ATP) is a water-containing magnesium-aluminum-rich silicate mineral with porous chain layers, and has abundant reserves and low price. As a natural nano material, the material has the characteristics of high thermal stability and mechanical strength, one-dimensional crystal morphology, abundant surface hydroxyl groups and the like, and is an ideal choice for preparing composite hybrid materials. The strategy of hybrid preparation of the attapulgite and the metal organic framework material can realize the improvement of the mechanical property of the composite system on the basis of utilizing the high strength and the thermal stability of the attapulgite. Attapulgite is applied to the research of chitosan composite modification, so that the mechanical properties of a composite system are effectively improved [ Polymer composites.2020,41, 2254-; J.appl.Polym.Sci.,2020,137,49079 ]. Meanwhile, the structural characteristics of the surface of the attapulgite can effectively regulate and control the surface interface property and the micro morphology of the metal organic framework material, improve the compatibility and the dispersibility between a metal organic framework material hybrid system and a polymer, and realize effective improvement of comprehensive performance.
Therefore, the invention designs that a metal organic framework and attapulgite are hybridized to prepare a novel attapulgite-metal organic framework material, and then the novel attapulgite-metal organic framework material is compounded with a sulfonated polyether ether ketone (SPEEK) matrix to prepare a proton exchange membrane, so that the main performance of the composite membrane is researched. The selection of the sulfonated polyether ether ketone has the advantages of low price, low fuel permeation, better mechanical property and the like. The surface hydroxyl-rich characteristics of the attapulgite are utilized to realize the regulation and control of the surface interface properties of the crystal structure of the metal organic framework material and exert the performance characteristics of the proton conductor; and the mechanical property is effectively improved by utilizing the high mechanical strength characteristic of the attapulgite. Meanwhile, the morphological characteristics of the attapulgite one-dimensional crystal are more beneficial to the construction of a proton transmission channel and the improvement of the conductivity. In addition, the attapulgite has the advantages of abundant reserves and low price, so that the application and research of the attapulgite have better economic benefits.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a sulfonated polyether ether ketone composite membrane made of attapulgite and a metal organic framework composite material, and a preparation method and application thereof.
The technical scheme provided by the invention is as follows:
a preparation method of a sulfonated polyether ether ketone composite membrane of attapulgite and metal organic framework composite material comprises the following steps:
1) preparing a composite material of attapulgite and a metal organic framework;
2) preparing the sulfonated polyether-ether-ketone composite membrane of the attapulgite and the metal organic framework composite material.
Based on the technical scheme, firstly, a certain amount of attapulgite is added in the preparation process of the metal organic framework, the attapulgite-metal organic framework hybrid material is prepared in situ, and the effective combination of the attapulgite and the metal organic framework material is realized on the basis of keeping the structure of the metal organic framework material. And then compounding the prepared attapulgite-metal organic framework material with sulfonated polyether ether ketone to prepare the proton exchange membrane.
Specifically, the step 1) comprises the following steps:
1a) 1.0-1.5 parts by mass of ZrCl 4 Adding the mixture into 50-75 parts by mass of N, N-dimethylformamide solution, carrying out ultrasonic treatment to fully dissolve the mixture, then adding 0.08-0.13 part by mass of attapulgite into the solution, and stirring at room temperature after ultrasonic treatment to obtain uniformly dispersed first solution; carrying out ultrasonic treatment on 1.0 part by mass of 2, 5-dimercapto-terephthalic acid and 50-75 parts by mass of N, N-dimethylformamide solution to completely dissolve the 2, 5-dimercapto-terephthalic acid and the N, N-dimethylformamide solution to obtain a second solution;
1b) mixing the first solution and the second solution, stirring at room temperature to uniformly disperse, then transferring into a reaction kettle for reaction, naturally cooling to room temperature after reaction, carrying out centrifugal separation, washing and drying the obtained solid to obtain an intermediate material;
1c) adding 1.0 part by mass of the intermediate material obtained in the step 1b) into 60-85 parts by mass of H 2 O 2 And heating and stirring the solution for reaction, naturally cooling the solution to room temperature, performing centrifugal separation on the reaction solution, washing and drying the obtained solid to obtain the attapulgite and metal organic framework composite material.
Specifically, in the step 1b), the reaction temperature is 115-125 ℃; the reaction time is 20-28 h; washing the obtained solid with N, N-dimethylformamide and absolute ethyl alcohol respectively for 3-4 times, and drying the solid; the drying temperature is 75-85 ℃; the drying time is 20-28 h.
Specifically, in step 1 c):
H 2 O 2 the mass percentage of the solution is 25-35%; the temperature of the heating and stirring reaction is 75-85 ℃; the heating and stirring reaction time is 5-8 h; washing the obtained solid respectively with deionized water and absolute ethyl alcohol for 3-4 times, and finally drying the solid; the drying temperature is 75-85 ℃; the drying time is 20-28 h;
in the attapulgite and metal organic framework composite material, the mass ratio of the attapulgite to the metal organic framework is 100/5-100/15;
the metal organic framework is UiO-66- (SO) 3 H) 2 。
Specifically, the step 2) comprises the following steps: adding the attapulgite and metal organic framework composite material obtained in the step 1) into a third organic solvent, then performing ultrasonic dispersion uniformly, adding the mixture into a solution of a fourth organic solvent of sulfonated polyether ether ketone, stirring at room temperature to mix uniformly, then performing tape casting on the mixed solution to prepare a membrane, and then heating and drying to obtain the sulfonated polyether ether ketone composite membrane of the attapulgite and metal organic framework composite material.
Specifically, in the step 2):
the mass ratio of the attapulgite, the metal organic framework composite material and the third organic solvent is (0.04-0.06): 10;
the mass ratio of the sulfonated polyether ether ketone to the fourth organic solvent is (0.9-1.1): 30;
the third organic solvent is N, N-dimethylacetamide or N, N-dimethylformamide;
the fourth organic solvent is N, N-dimethylacetamide or N, N-dimethylformamide;
the mass ratio of the sulfonated polyether ether ketone to the attapulgite to the metal organic framework composite material is 100/5-100/15;
the sulfonation degree of the sulfonated polyether-ether-ketone is 30-50 percent;
the heating and drying temperature is 55-65 ℃; the drying time is 2-6 h.
The invention also provides a sulfonated polyether ether ketone composite membrane of the attapulgite and the metal organic framework composite material.
The composite membrane provided by the invention combines a natural attapulgite material with high thermal stability and mechanical strength, one-dimensional crystal morphology, abundant surface hydroxyl groups and other characteristics with a metal organic framework material with better proton conductivity, thereby realizing the comprehensive improvement of the conductivity and mechanical properties.
The invention also provides application of the sulfonated polyether-ether-ketone composite membrane prepared from the attapulgite and the metal organic framework composite material as a composite proton exchange membrane.
The technical scheme of the invention mainly solves the following problems:
1. the attapulgite nano material is introduced into a metal organic framework structure, so that the characteristics of the attapulgite as a material reinforcement are exerted, and the mechanical property of a polymer composite system is improved.
2. By controlling the mass ratio of the attapulgite to the metal organic framework raw material, the micro-morphology and the surface properties are regulated, the problem of difference of the interface properties of the metal organic framework material and a polymer matrix is solved, the conductivity characteristics of the metal organic framework are brought into play, and the comprehensive performance of a polymer composite system is improved.
Detailed Description
The principles and features of the present invention are described below, and the examples are provided for illustration only and are not intended to limit the scope of the present invention.
In examples 1-3 below: the preparation process of the sulfonated polyether ether ketone comprises the following steps:
polyetheretherketone (raw polyetheretherketone from Victrex, UK, M w 36000). The preparation process of the sulfonated polyether-ether-ketone comprises the following steps: dissolving the dried polyether-ether-ketone powder in 98 wt% concentrated sulfuric acid, wherein the reaction temperature is 60 ℃, and the reaction time is 4 h. And then pouring the solution into an ice-water mixture, stirring, washing the solid with deionized water until the filtrate is neutral, filtering and collecting the solid, and then drying at 80 ℃ for 24 hours to obtain the product of sulfonated polyether ether ketone.
The preparation process of the pure sulfonated polyether ether ketone membrane comprises the following steps:
1.0g of sulfonated polyether ether ketone was weighed, dissolved sufficiently in 30ml of an organic solvent, and stirred at room temperature for 2 hours to form a uniform solution. And then uniformly distributing the mixed solution on a clean glass plate for casting film making, drying at 60 ℃, cooling to room temperature, and demoulding to obtain the pure sulfonated polyether-ether-ketone film.
The above-mentioned N, N-dimethylformamide and ZrCl 4 All of them were analytical grade (purchased from national institute of medicine), 2, 5-dimercapto-terephthalic acid analytical grade (purchased from Zhengzhou Junke Biotechnology Co., Ltd.)
30% H as described above 2 O 2 Absolute ethanol was analytically pure (purchased from the national pharmaceutical group) and deionized water was prepared from the laboratory. The metal organic framework material is UiO-66- (SO) 3 H) 2 。
Example 1
A preparation method of a sulfonated polyether ether ketone composite proton exchange membrane made of attapulgite and a metal organic framework composite material comprises the following steps:
(1) in a dry, clean 50ml beaker, 0.6g ZrCl was accurately weighed in 4 Then, 30ml of N, N-dimethylformamide solution was added and the mixture was sonicated for 30min to dissolve it sufficiently. Then, 0.05g of attapulgite powder was added, and after 30min of ultrasonic treatment, the mixture was stirred at room temperature for 50min to obtain a uniformly dispersed solution. Another dry and clean 50ml beaker was weighed accurately and added with 0.46g of 2, 5-dimercapto-terephthalic acid, 30ml of N, N-dimethylformamide was added, and the mixture was subjected to ultrasonic treatment for 30min to complete the dissolution.
Mixing the two solutions, stirring at room temperature for 30min, and transferring into a reaction kettle to react at 120 deg.C for 24 h. After 24h, the reaction kettle is naturally cooled to room temperature, centrifugal separation is carried out, the obtained solid is respectively washed for 4 times by using N, N-dimethylformamide and absolute ethyl alcohol, and the solid is dried for 24h at 80 ℃.
The above-mentioned N, N-dimethylformamide and ZrCl 4 All were analytically pure (purchased from the national pharmaceutical group), 2, 5-dimercapto-terephthalic acid analytically pure (purchased from zheng zhou co.
(2) 1.0g of the solid from step (1) was added to 40ml of 30% H 2 O 2 The solution was heated to 80 ℃ and stirred for 6 hours, and then cooled to room temperature. And (3) carrying out centrifugal separation on the reaction liquid, washing the solid for 4 times by using deionized water and absolute ethyl alcohol respectively, and finally drying the solid for 24 hours at 80 ℃ to obtain the attapulgite and metal organic framework composite material.
30% H as described above 2 O 2 Absolute ethanol was analytically pure (purchased from the national pharmaceutical group) and deionized water was prepared from the laboratory. The metal organic framework material is UiO-66- (SO) 3 H) 2 -5。
(3) Taking 0.05g of the sample in the step (2), adding 10ml of N, N-dimethylformamide solution, performing ultrasonic treatment for 30min to uniformly disperse the sample, then adding the sample into 1.0g of N, N-dimethylformamide solution of sulfonated polyether ether ketone, stirring at room temperature for 2-3 h, uniformly dispersing the mixed solution on a clean glass plate, casting to prepare a membrane, and drying at 60 ℃ to obtain the sulfonated polyether ether ketone composite proton exchange membrane made of the attapulgite and the metal organic framework composite material.
In the sulfonated polyether ether ketone composite proton exchange membrane made of the attapulgite and the metal organic framework composite material, the mass ratio of the attapulgite to the metal organic framework material is 5/100, and the mass ratio of the attapulgite to the metal organic framework composite material to the sulfonated polyether ether ketone is 5/100.
Example 2
A preparation method of a sulfonated polyether ether ketone composite proton exchange membrane of attapulgite and metal organic framework composite material comprises the following steps:
(1) in a dry, clean 50ml beaker, 0.6g ZrCl was accurately weighed in 4 Then, 30ml of N, N-dimethylformamide solution was added, and ultrasonic treatment was carried out for 30min to sufficiently dissolve the compound. Then 0.1g of attapulgite powder was added, and after 30min of ultrasonic treatment, the mixture was stirred at room temperature for 50min to obtain a uniformly dispersed solution. Another dry and clean 50ml beaker was accurately weighed and added with 0.46g of 2, 5-dimercapto-terephthalic acid, 30ml of N, N-dimethylformamide, and the mixture was sonicated for 30min to dissolve completely.
Mixing the two solutions, stirring at room temperature for 30min, and transferring into a reaction kettle to react at 120 deg.C for 24 h. After 24h, the reaction kettle is naturally cooled to room temperature, centrifugal separation is carried out, the obtained solid is respectively washed for 4 times by using N, N-dimethylformamide and absolute ethyl alcohol, and the solid is dried for 24h at 80 ℃. The above-mentioned N, N-dimethylformamide, dehydrated alcohol, ZrCl 4 All were analytically pure (purchased from the national pharmaceutical group), 2, 5-dimercapto-terephthalic acid analytically pure (purchased from zheng zhou co.
(2) 1.0g of the solid from step (1) was added to 40ml of 30% H 2 O 2 The solution was heated to 80 ℃ and stirred for 6 hours, and then cooled to room temperature. And (3) carrying out centrifugal separation on the reaction liquid, washing the solid for 4 times by using deionized water and absolute ethyl alcohol respectively, and finally drying the solid for 24 hours at 80 ℃ to obtain the attapulgite and metal organic framework composite material.
30% H as described above 2 O 2 Absolute ethanol was analytically pure (purchased from the national pharmaceutical group) and deionized water was prepared from the laboratory. The metal organic framework material is UiO-66- (SO) 3 H) 2 -10。
(3) And (3) taking 0.05g of the sample in the step (2), adding 10ml of N, N-dimethylformamide solution, carrying out ultrasonic treatment for 30min to uniformly disperse the sample, then adding the sample into 1.0g of N, N-dimethylformamide solution of sulfonated polyether ether ketone, stirring at room temperature for 2-3 h to uniformly mix the sample, then uniformly dispersing the mixture on a clean glass plate for casting membrane preparation, and drying at 60 ℃ to obtain the sulfonated polyether ether ketone composite proton exchange membrane of the attapulgite and metal organic framework composite material.
In the sulfonated polyether ether ketone composite proton exchange membrane made of the attapulgite and the metal organic framework composite material, the mass ratio of the attapulgite to the metal organic framework material is 10/100, and the mass ratio of the attapulgite to the metal organic framework material to the sulfonated polyether ether ketone is 5/100.
Example 3
A preparation method of a sulfonated polyether ether ketone composite proton exchange membrane made of attapulgite and a metal organic framework composite material comprises the following steps:
(1) in a dry, clean 50ml beaker, 0.6g ZrCl was accurately weighed in 4 Then, 30ml of N, N-dimethylformamide solution was added, and ultrasonic treatment was carried out for 30min to sufficiently dissolve the compound. Then, 0.15g of attapulgite powder was added, and after 30min of ultrasonic treatment, the mixture was stirred at room temperature for 50min to obtain a uniformly dispersed solution. Another dry and clean 50ml beaker was weighed accurately and 0.46g of 2, 5-dimercapto-terephthalic acid was added, 30ml of N, N-dimethylformamide was added and the solution was dissolved completely by ultrasound for 30 min. Mixing the two solutions, stirring at room temperature for 30min, and transferring into a reaction kettle to react at 120 deg.C for 24 h. After 24h, the reaction kettle is naturally cooled to room temperature, centrifugal separation is carried out, the obtained solid is respectively washed for 4 times by using N, N-dimethylformamide and absolute ethyl alcohol, and the solid is dried for 24h at 80 ℃.
(2) 1.0g of the solid from step (1) was added to 40ml of 30% H 2 O 2 The solution was heated to 80 ℃ and stirred for 6 hours, and then cooled to room temperature. And (3) carrying out centrifugal separation on the reaction liquid, washing the solid for 4 times by using deionized water and absolute ethyl alcohol respectively, and finally drying the solid for 24 hours at 80 ℃ to obtain the attapulgite-metal organic framework material. 30% H as described above 2 O 2 Absolute ethanol was analytically pure (purchased from the national pharmaceutical group) and deionized water was prepared from the laboratory. The metal organic framework material is UiO-66- (SO) 3 H) 2 -15。
(3) And (3) taking 0.05g of the sample in the step (2), adding 10ml of N, N-dimethylformamide solution, performing ultrasonic treatment for 30min to uniformly disperse the sample, then adding the sample into 1.0g of N, N-dimethylformamide solution of sulfonated polyether ether ketone, stirring at room temperature for 2-3 h to uniformly mix the sample, then uniformly dispersing the mixture on a clean glass plate for casting to prepare a membrane, and drying at 60 ℃ to obtain the sulfonated polyether ether ketone composite proton exchange membrane of the attapulgite and metal organic framework composite material.
In the sulfonated polyether ether ketone composite proton exchange membrane made of the attapulgite and the metal organic framework composite material, the mass ratio of the attapulgite to the metal organic framework material is 15/100, and the mass ratio of the attapulgite to the metal organic framework material to the sulfonated polyether ether ketone is 5/100.
The following table 1 lists the main performance index data of the sulfonated polyetheretherketone proton exchange membrane of the attapulgite and metal organic framework composite material prepared in examples 1-3.
TABLE 1
The film performance test conditions prepared in each example were as follows:
(1) proton conductivity test: testing the resistance of the film on a frequency response analyzer by AC impedance method, cutting the film into 1.5cm × 2.5cm sample strips, with the frequency scanning range of the tester being 1-10 6 Hz. The proton conductivity σ (S/cm) of the membrane is calculated by the following formula:
wherein L and A are the distance (cm) between the two electrodes and the effective cross-sectional area (cm) of the film to be measured between the two electrodes -2 ) And R is the resistance (omega) of the film, and is obtained by calculating data obtained by an alternating current impedance test.
(2) And (3) testing tensile strength: the film samples were cut into rectangular strips of 40mm length and 15mm width and tested on an electronic tensile machine using a tensile speed of 2 mm/min.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (8)
1. A preparation method of a sulfonated polyether ether ketone composite membrane of attapulgite and metal organic framework composite material is characterized by comprising the following steps:
1) the preparation method of the attapulgite and metal organic framework composite material comprises the following specific steps:
1a) preparation of a composition containing ZrCl 4 A first solution of attapulgite and N, N-dimethylformamide; preparing a second solution comprising 2, 5-dimercapto-terephthalic acid and N, N-dimethylformamide;
1b) mixing the first solution and the second solution, stirring at room temperature to uniformly disperse, then transferring into a reaction kettle for reaction, naturally cooling to room temperature after reaction, carrying out centrifugal separation, washing and drying the obtained solid to obtain an intermediate material;
1c) adding the intermediate material obtained in step 1b) to H 2 O 2 In the solution, heating, stirring and reacting, then naturally cooling to room temperature, carrying out centrifugal separation on the reaction solution, washing and drying the obtained solid to obtain the attapulgite and metal organic framework composite material;
2) preparing the sulfonated polyether-ether-ketone composite membrane of the attapulgite and the metal organic framework composite material.
2. The method for preparing the sulfonated polyether ether ketone composite membrane of the attapulgite and the metal organic framework composite material according to claim 1, which is characterized in that: in the step 1a), 1.0-1.5 parts by mass of ZrCl 4 Adding the mixture into 50-75 parts by mass of N, N-dimethylformamide solution, carrying out ultrasonic treatment to fully dissolve the mixture, then adding 0.08-0.13 part by mass of attapulgite into the solution, and stirring at room temperature after ultrasonic treatment to obtain uniformly dispersed first solution; and (2) carrying out ultrasonic treatment on 1.0 part by mass of 2, 5-dimercapto-terephthalic acid and 50-75 parts by mass of N, N-dimethylformamide solution to completely dissolve the 2, 5-dimercapto-terephthalic acid and the N, N-dimethylformamide solution to obtain a second solution.
3. The method for preparing the sulfonated polyetheretherketone composite membrane of the attapulgite and metal organic framework composite material according to claim 1, wherein the method comprises the following steps: in the step 1b), the reaction temperature is 115-125 ℃; the reaction time is 20-28 h; washing the obtained solid with N, N-dimethylformamide and absolute ethyl alcohol respectively for 3-4 times, wherein the drying temperature is 75-85 ℃; the drying time is 20-28 h.
4. The method for preparing the sulfonated polyether ether ketone composite membrane of attapulgite and metal-organic framework composite material according to claim 1, wherein in the step 1 c):
H 2 O 2 the mass percentage of the solution is 25-35%, 1.0 mass part of the intermediate material obtained in the step 1b) is added into 60-85 mass parts of H 2 O 2 In solution;
the temperature of the heating and stirring reaction is 75-85 ℃; the heating and stirring reaction time is 5-8 h; washing the obtained solid respectively with deionized water and absolute ethyl alcohol for 3-4 times, wherein the drying temperature is 75-85 ℃; the drying time is 20-28 h;
in the attapulgite and metal organic framework composite material, the mass ratio of the attapulgite to the metal organic framework is 100/5-100/15;
the metal organic framework is UiO-66- (SO) 3 H) 2 。
5. The method for preparing the sulfonated polyether ether ketone composite membrane of attapulgite and metal organic framework composite material according to claim 1, wherein the step 2) comprises the following steps: adding the attapulgite and metal organic framework composite material obtained in the step 1) into a third organic solvent, then performing ultrasonic dispersion uniformly, adding the mixture into a solution containing a fourth organic solvent of sulfonated polyether ether ketone, stirring at room temperature to uniformly mix, then performing tape casting on the mixed solution to prepare a membrane, and then heating and drying to obtain the sulfonated polyether ether ketone composite membrane of the attapulgite and metal organic framework composite material.
6. The method for preparing the sulfonated polyether ether ketone composite membrane of attapulgite and metal-organic framework composite material according to claim 5, wherein in the step 2):
the mass ratio of the attapulgite to the metal organic framework composite material to the third organic solvent is (0.04-0.06): 10;
the mass ratio of the sulfonated polyether-ether-ketone to the fourth organic solvent is (0.9-1.1): 30;
the third organic solvent is N, N-dimethylacetamide or N, N-dimethylformamide;
the fourth organic solvent is N, N-dimethylacetamide or N, N-dimethylformamide;
the mass ratio of the sulfonated polyether ether ketone in the fourth organic solvent to the attapulgite and metal organic framework composite material in the third organic solvent is 100/5-100/15;
the sulfonation degree of the sulfonated polyether-ether-ketone is 30-50 percent;
the heating and drying temperature is 55-65 ℃; the drying time is 2-6 h.
7. A sulfonated polyether ether ketone composite membrane of attapulgite and a metal organic framework composite material prepared according to the preparation method of any one of claims 1 to 6.
8. The use of the sulfonated polyether ether ketone composite membrane of attapulgite and metal organic framework composite material according to claim 7, wherein: as a composite proton exchange membrane.
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