CN115528283A - Proton exchange membrane suitable for low-humidity environment and preparation method thereof - Google Patents

Proton exchange membrane suitable for low-humidity environment and preparation method thereof Download PDF

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CN115528283A
CN115528283A CN202210872652.9A CN202210872652A CN115528283A CN 115528283 A CN115528283 A CN 115528283A CN 202210872652 A CN202210872652 A CN 202210872652A CN 115528283 A CN115528283 A CN 115528283A
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imidazolium salt
proton exchange
exchange membrane
polybenzimidazole
phosphoric acid
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郝金凯
张洪杰
邵志刚
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Dalian Institute of Chemical Physics of CAS
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/1041—Polymer electrolyte composites, mixtures or blends
    • H01M8/1046—Mixtures of at least one polymer and at least one additive
    • H01M8/1048—Ion-conducting additives, e.g. ion-conducting particles, heteropolyacids, metal phosphate or polybenzimidazole with phosphoric acid
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    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/1039—Polymeric electrolyte materials halogenated, e.g. sulfonated polyvinylidene fluorides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
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    • H—ELECTRICITY
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    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract

The invention belongs to the field of fuel cell membrane materials, and relates to a proton exchange membrane suitable for a low-humidity environment and a preparation method thereof. The proton exchange membrane is compounded by taking imidazolium salt crystals, polybenzimidazole, polyvinyl benzyl chloride and phosphoric acid as raw materials, wherein the imidazolium salt crystals are substances formed by taking 4, 5-disubstituted imidazolium salts as the raw materials and are fixed in a metal organic framework crystal material. The preparation of the proton exchange membrane comprises the steps of forming a casting solution by polybenzimidazole, polyethylene derivatives and imidazolium salt crystals, pouring the casting solution into a glass mold, fully drying to obtain a membrane, immersing the membrane into a phosphoric acid solution, and drying to obtain the proton exchange membrane; the proton exchange membrane has high proton conductivity and mechanical strength, the addition of the free radical quencher in the preparation process slows down the oxidative degradation of HT-PEM, and the mechanical strength of the membrane is effectively improved by crosslinking, adding a nano material, blending with another stable polymer, improving the membrane structure and the like.

Description

Proton exchange membrane suitable for low-humidity environment and preparation method thereof
Technical Field
The invention relates to a proton exchange membrane suitable for a low-humidity environment and a preparation method thereof, belonging to the field of fuel cell membrane materials.
Background
Proton Exchange Membrane Fuel Cells (PEMFCs) are high-efficiency clean energy systems that convert chemical energy into electrical energy using low-carbon renewable fuels such as hydrogen, and exhibit great potential in the fields of vehicle-mounted power supplies, portable power supplies, stationary power supplies, micro cogeneration systems, and the like, as an important part of the hydrogen energy industry chain in the global energy structure adjustment process. Since the byproducts are mainly discharged into the environment in the form of water, the method has wide application space in the field of automobile fuel cells. However, the popularization of the current pem fuel cell is still limited by the problems of cost and service life, wherein the pem is used as a key material of the fuel cell and accounts for about 20% of the total cost of the stack, and the breakthrough of the performance of the pem fuel cell will have a profound influence on the development of the fuel cell.
Proton exchange membranes are a core component of PEMFCs, and PEMs are distinguished from membranes used in general chemical power sources. Proton exchange membrane fuel cells have become the most competitive clean alternative power source for gasoline internal combustion engines. The material used as PEM should satisfy the following conditions: (1) good proton conductivity; (2) the electroosmosis of water molecules in the membrane is small; (3) permeability of gas in the membrane is as small as possible; (4) the electrochemical stability is good; (5) the dry-wet conversion performance is good; (6) has certain mechanical strength; (7) the processability is good, and the price is proper.
Compared with the traditional Proton Exchange Membrane Fuel Cell (PEMFC), the high-temperature low-humidity proton exchange membrane fuel cell (HT-PEMFC) has the advantages that the operation temperature is favorable for improving the reaction activity of the catalyst and accelerating the reaction speed, the carbon monoxide poisoning resistance of the catalyst is improved, and the simple hydrothermal management is facilitated. As a core component of HT-PEMFC, the main function of a high temperature proton exchange membrane (HT-PEM) is to transport protons from the anode to the cathode, separate the reactants and isolate the electrons to avoid short circuits. The phosphoric acid doped proton exchange membrane has the advantages of high proton conductivity, good chemical stability and the like under the conditions of high temperature, low humidity or no water, so that the phosphoric acid doped proton exchange membrane becomes a research hotspot of a high-temperature proton exchange membrane material. However, some of the deficiencies of current HT-PEM preparations made in a serial manner have limited their further commercialization. For example, while phosphoric acid in the membrane increases proton conductivity, the mechanical strength of the membrane is sacrificed. Furthermore, the loss of phosphoric acid is particularly severe after long runs, especially when oxidation and mechanical degradation of the polymer chains occur. Therefore, how to solve the three main challenges of HT-PEM (phosphoric acid loss, membrane oxidative degradation and membrane mechanical degradation) is of great importance for the commercialization of HT-PEMFCs.
Disclosure of Invention
The invention aims to provide a proton exchange membrane suitable for a low-humidity environment and a preparation method thereof, and aims to solve the problems of phosphoric acid loss, membrane oxidative degradation, membrane mechanical degradation and the like of the proton exchange membrane in the low-humidity environment.
The technical purpose of the invention is realized by the following technical scheme:
the invention provides a proton exchange membrane which is compounded by taking an imidazolium salt crystal, polybenzimidazole, polyvinyl benzyl chloride and phosphoric acid as raw materials, wherein the imidazolium salt crystal is prepared by the following steps: the preparation method comprises the following steps of (1) fixing 4, 5-disubstituted imidazolium salt serving as a raw material in a metal organic framework crystal material to prepare the material; the 4, 5-disubstituted imidazolium salt is a 1-butyl C4, C5-disubstituted imidazolium salt or a 1-hexyl C4, C5-disubstituted imidazolium salt.
In the above technical solution, further, the raw materials of the imidazolium salt crystal further include chloromethyl styrene, polybenzimidazole and a radical quencher.
In the above technical solution, further, the metal organic framework crystal material is a cubic structure with micropores, and the pore diameter of the metal organic framework crystal material is 100-1000nm; the metal organic framework crystal material is one or more than two of MIL-101 (Fe), MIL-101 (Cr), MIL-53 (Fe), ZIF-6, ZIF-8 and ZIF-10; the phosphoric acid is polypeptide organic phosphoric acid or inorganic phosphoric acid.
In the above technical solution, further, the imidazolium salt crystal is synthesized by a low-temperature vacuum method, and C4 and C5 substituted imidazolium salts are "fixed" in a crystal material of a metal-organic framework material having a microporous cubic structure, including the following steps:
(1) Placing the metal organic framework crystal material with the micropore cubic structure into a Schlenk tube with a constant pressure funnel, and continuously vacuumizing to keep the metal organic framework crystal material in a vacuum state;
(2) Mixing the mixed solution of the 4, 5-disubstituted imidazolium salt and the p-chloromethyl styrene with the metal organic framework crystal material in the step (1) in a low-temperature environment, stirring for reaction, and adding the polybenzimidazole and the free radical quencher for mixing;
(3) After the reaction is finished, centrifugal treatment is carried out, and the precipitate is dried to carry out self-crosslinking on vinyl in the chloromethyl styrene to obtain the imidazolium salt crystal.
In the technical scheme, further, the vacuum degree of the vacuum state in the step (1) is-0.6 to-1.0 MPa; the low-temperature reaction temperature in the step (2) is-20 to-10 ℃, and the stirring time is 48 to 96 hours; in the step (3), the drying temperature of the precipitate is 60-100 ℃, and the drying time is 4-8h; the steps (1) and (2) are in the same vacuum state.
In the above technical solution, further, the substituents of C4 and C5 in the 4, 5-disubstituted imidazolium salt are R respectively 1 And R 2 Said R is 1 And R 2 All of methyl, ethyl, propyl, butyl, isopropyl and tert-butyl, and the structures of the 1-butyl C4, C5 disubstituted imidazolium salt or the 1-hexyl C4, C5 disubstituted imidazolium salt are respectively as follows:
Figure RE-GDA0003898705740000031
the free radical quencher is any one of phosphorylated cerium dioxide, sulfonated manganese dioxide, cerium dioxide and manganese dioxide;
the mass ratio of the metal organic framework material to the 4, 5-disubstituted imidazolium salt to the p-chloromethyl styrene, the polybenzimidazole and the free radical quencher is that the metal organic framework material to the 4, 5-disubstituted imidazolium salt to the p-chloromethyl styrene to the polybenzimidazole to the free radical quencher = 0.3-1.5.
The invention also provides a preparation method of the proton exchange membrane, which comprises the following steps:
A. preparing a polybenzimidazole high-boiling-point solution, adding polyvinyl benzyl chloride at room temperature, and stirring to obtain a mixed solution of polybenzimidazole and polyvinyl benzyl chloride;
B. adding an imidazolium salt crystal into the mixed solution of the polybenzimidazole and the polyvinyl benzyl chloride obtained in the step A, and stirring at room temperature to obtain a functionalized membrane casting solution;
C. pouring the membrane casting solution prepared in the step B into a glass mold, and after the membrane casting solution is fully dried, stripping the obtained membrane from the glass mold;
D. weighing phosphoric acid, adding the phosphoric acid into deionized water to prepare a phosphoric acid aqueous solution, soaking the membrane obtained in the step C in the phosphoric acid aqueous solution, and fishing out the membrane;
E. and D, washing the membrane fished out in the step D for more than 5 times by using deionized water, and drying to obtain the proton exchange membrane suitable for the low-humidity environment.
In the above technical solution, further, in the step a, the mass concentration of the polybenzimidazole high boiling point solution is 0.5-2wt%, and the high boiling point solvent used for preparing the polybenzimidazole high boiling point solution is one of N-methylpyrrolidone, N-dimethylformamide, tetrahydrofuran, and dimethyl sulfoxide.
In the above technical scheme, further, the stirring time in step a is 24-48h, and the stirring time in step B is 24-48h.
In the above technical scheme, further, the mass ratio of each component in steps a and B is 1-1.5.
In the above technical solution, further, the phosphoric acid aqueous solution has a mass concentration of 5 to 15wt%. In the above technical scheme, further, in the step C, the drying temperature of the casting solution is 60-80 ℃, and the drying time is 24-48h; the soaking time in the step D is 24-48h; and in the step E, the drying temperature is 40-60 ℃, and the drying time is 24-48h.
Advantageous effects
1. The low-humidity proton exchange membrane prepared by the invention comprises a skeleton polymer material prepared by blending polybenzimidazole polyethylene benzyl chloride, and the phosphate compound and an imidazolium salt crystal material play an ion transmission function, and have excellent mechanical properties and low cost under low-humidity operating conditions, on one hand, the polybenzimidazole material has good stability and good adsorptivity to phosphoric acid, on the other hand, the addition of the polyethylene benzyl chloride can improve the toughness of the skeleton material, and the alkane end group of the polyethylene benzyl chloride can further carry out chemical combination reaction with the polybenzimidazole to form a more stable network structure, so that the stability of the composite membrane is improved;
an ordered proton transmission channel is constructed by adding an imidazolium salt crystal structure formed by imidazolium salts and a metal organic framework, so that phosphoric acid can be uniformly and orderly locked in the channel of the crystal structure, the ion transfer resistance is reduced, the ion transmission efficiency is improved, the electrochemical performance is further improved, the metal organic framework in the imidazolium salt crystal material provides a containing place for vinyl compounds in imidazolium salts and chloromethyl styrene, and the prepared anion exchange membrane cannot cause the chemical degradation of an ionic membrane and the loss of functional ion groups due to the change of a reaction environment;
the imidazolium salt crystal material is added into the framework polymer material, so that the active sites of proton conduction are increased, the effective compatibility of the membrane framework polymer material, the crystal material and the phosphoric acid molecules is realized, the imidazolium salt crystal material can be uniformly dispersed in the polymer material, the problems of agglomeration, loss and the like are avoided, and the proton conduction uniformity and efficiency of the proton exchange membrane are improved.
2. According to the invention, a metal organic framework crystal material and an imidazolium salt are used as a functional material of a proton exchange membrane, and the imidazolium salt crystal can adsorb phosphoric acid compounds in imidazole MOFs structure and pores of the crystal structure, so that phosphoric acid adsorption sites are increased, and proton conductivity is improved; in addition, when the prepared composite membrane is soaked in a phosphoric acid solution, phosphoric acid molecules can enter an imidazolium salt crystal structure and are fixed in an imidazole microporous structure in the crystal structure to form a structure of a 'boat in bottle', the structure has a large internal space, a macromolecular structure and a small pore structure, so that internal compounds such as phosphoric acid and the like can not flow out, the loss of the phosphoric acid along with water flow in the operation process of a fuel cell is effectively avoided, and a sulfonated free radical quencher is filled in a polymer framework to improve the proton conductivity, so that the conductivity stability and the mechanical strength of a finished proton membrane are improved;
3. the invention slows down the phosphoric acid loss by preparing the capture sites of the phosphoric acid molecules or increasing the interaction between the polymer and the phosphoric acid molecules, synthesizes the polymer with cross-linking and branched structures to protect the polymer skeleton from the attack of free radicals, adds the free radical quencher to slow down the oxidative degradation of HT-PEM in the preparation process, and effectively improves the mechanical strength of the outer membrane by cross-linking, adding nano materials, blending with another stable polymer, improving the membrane structure and the like.
4. According to the invention, through special molecular structure design and different functional particles added in the membrane, phosphoric acid is used as a high-temperature proton exchange membrane of a proton conductor, the filling amount of the proton conductor is large, so that higher proton conductivity is obtained, the adsorption force of the phosphoric acid and a polymer membrane is increased, and the chemical stability of the membrane is improved.
Detailed Description
The present invention will be described in further detail below.
Example 1:
(1) Weighing 10g of MIL-101 (Fe) and placing the MIL-101 (Fe) into a Schlenk tube provided with a constant pressure funnel, continuously vacuumizing to keep the vacuum degree at-1.0 MPa, and reducing the temperature of the Schlenk tube to-10 ℃;
(2) A mixed solution of 20g of 1-hexyl-4, 5-dimethylimidazolium salt and 6g of p-chloromethyl styrene was weighed and injected into the Schlenk tube of the step (1), and stirring was continued for 96 hours to allow the 1-hexyl-4, 5-dimethylimidazolium salt and the p-chloromethyl styrene to react sufficiently, and then 40g of polybenzimidazole and 0.2g of 3nm phosphorylated ceria were weighed and added thereto to mix;
(3) After the reaction is finished, centrifuging the precipitate, and drying at 60 ℃ for 8h to enable vinyl to be self-crosslinked to form an imidazolium salt crystal;
(4) Weighing 12g of polybenzimidazole at 25 ℃, dissolving the polybenzimidazole in 2388g of N-methylpyrrolidone, stirring and dissolving to obtain a polymer solution with the concentration of 0.5%, then weighing 4g of polyvinyl benzyl chloride, adding the mixture, and stirring for 24 hours;
(5) Weighing 4g of imidazolium salt crystals, adding into the step (4), and stirring for 24 hours until the mixture is uniform to obtain a casting solution for later use;
(6) Filling the casting solution obtained in the step (5) into a glass mold, drying at 60 ℃ for 48h, and stripping the dried film from a glass plate for later use;
(7) Weighing 5g of polypeptide phosphoric acid, and adding the polypeptide phosphoric acid into 95g of deionized water to obtain a polypeptide phosphoric acid solution with the concentration of 5%;
(8) And (3) placing the membrane obtained in the step (6) in the solution prepared in the step (7), soaking for 24h, taking out, repeatedly washing for 5 times by using deionized water, and completely drying for 48h at 40 ℃ to obtain the proton exchange membrane suitable for the low-humidity environment.
Example 2:
(1) Weighing 5g of MIL-101 (Cr) and placing the MIL-101 (Cr) into a Schlenk tube provided with a constant-pressure funnel, continuously vacuumizing to keep the vacuum degree at-0.8 MPa, and reducing the temperature of the Schlenk tube to-15 ℃;
(2) Weighing a mixed solution of 7.5g of 1-hexyl-4, 5-diethylimidazole and 7.5g of p-chloromethyl styrene, injecting the mixed solution into the Schlenk tube in the step (1), continuously stirring the mixed solution for 36 hours to ensure that the 1-hexyl-4, 5-ethylmethylimidazolium salt and the p-chloromethyl styrene fully react, and then weighing 15g of polybenzimidazole and 0.15g of sulfonated manganese dioxide with the particle size of 10nm, adding the polybenzimidazole and the sulfonated manganese dioxide into the mixed solution, and mixing the polybenzimidazole and the sulfonated manganese dioxide;
(3) After the reaction is finished, centrifuging the precipitate, and drying at 70 ℃ for 7h to enable vinyl to be self-crosslinked to form an imidazolium salt crystal;
(4) Weighing 4g of polybenzimidazole at 25 ℃, dissolving in 396g of N, N-diformylamide, stirring and dissolving to obtain a polymer solution with the concentration of 1%, then weighing 2.4g of polyvinyl benzyl chloride, and stirring for 48 hours;
(5) Weighing 2g of imidazolium salt crystals, adding into the step (4), and stirring for 48 hours until the mixture is uniform to obtain a casting solution for later use;
(6) Filling the casting solution obtained in the step (5) into a glass mold, drying at 70 ℃ for 36h, and stripping the dried film from a glass plate for later use;
(7) Weighing 10g of polypeptide phosphoric acid, and adding the polypeptide phosphoric acid into 90g of deionized water to obtain a phosphoric acid solution with the concentration of 10%;
(8) And (3) placing the membrane obtained in the step (6) in the solution prepared in the step (7), soaking for 36h, taking out, repeatedly washing for 5 times by using deionized water, and completely drying for 36h at 50 ℃ to obtain the proton exchange membrane suitable for the low-humidity environment.
Example 3:
(1) Weighing 4g of ZIF-8, placing the ZIF-8 in a Schlenk tube with a constant-pressure funnel, continuously vacuumizing to keep the vacuum degree at-0.6 MPa, and reducing the temperature of the Schlenk tube to-20 ℃;
(2) Weighing a mixed solution of 8g of 1-hexyl-4, 5-dimethylimidazolium salt and 12g of p-chloromethyl styrene, injecting the mixed solution into the Schlenk tube in the step (1), continuously stirring for 48 hours to ensure that the 1-hexyl-4, 5-dimethylimidazolium salt and the p-chloromethyl styrene fully react, and then weighing 8g of polybenzimidazole and 0.4g of 5nm sulfonated cerium dioxide to be added for mixing;
(3) After the reaction is finished, centrifuging the precipitate, and drying at 60 ℃ for 8h to enable vinyl to be self-crosslinked to form an imidazolium salt crystal;
(4) Weighing 4g of polybenzimidazole at 25 ℃, dissolving the polybenzimidazole in 196g of N, N-dimethylamide, stirring and dissolving to obtain a polymer solution with the concentration of 2%, then weighing 6g of polyvinyl benzyl chloride, and stirring for 48 hours;
(5) Weighing 4g of imidazolium salt crystals, adding into the step (4), and stirring for 36h until the mixture is uniform to obtain a casting solution for later use;
(6) Filling the casting solution obtained in the step (5) into a glass mold, drying at 80 ℃ for 24h, and stripping the dried film from a glass plate for later use;
(7) Weighing 15g of phosphoric acid, and adding the phosphoric acid into 85g of deionized water to obtain a phosphoric acid solution with the concentration of 15%;
(8) And (4) placing the membrane obtained in the step (6) in the solution prepared in the step (7), soaking for 48h, taking out, repeatedly washing for 5 times by using deionized water, and completely drying for 24h at 60 ℃ to obtain the proton exchange membrane suitable for the low-humidity environment.
Comparative example 1:
(1) Weighing 12g of polybenzimidazole at 25 ℃, dissolving the polybenzimidazole in 2388g of N-methylpyrrolidone, stirring and dissolving to obtain a polymer solution with the concentration of 0.5%, then weighing 4g of polyvinyl benzyl chloride, adding, and stirring for 24 hours to obtain a membrane casting solution;
(2) Filling the casting solution obtained in the step (1) into a glass mold, drying at 60 ℃ for 48h, and stripping the dried film from a glass plate for later use;
(3) Weighing 5g of polypeptide phosphoric acid, and adding the polypeptide phosphoric acid into 95g of deionized water to obtain a polypeptide phosphoric acid solution with the concentration of 5%;
(4) And (4) placing the membrane obtained in the step (3) in the solution prepared in the step (7), soaking for 24h, taking out, repeatedly washing for 5 times by using deionized water, and completely drying for 48h at 40 ℃ to obtain the proton exchange membrane suitable for the low-humidity environment.
Comparative example 2:
(1) Weighing 10g of MIL-101 (Fe) and placing the MIL-101 (Fe) into a Schlenk tube provided with a constant pressure funnel, continuously vacuumizing to keep the vacuum degree at-1.0 MPa, and reducing the temperature of the Schlenk tube to-10 ℃;
(2) Weighing a mixed solution of 20g of 1-hexyl-4, 5-dimethylimidazolium salt and 6g of p-chloromethyl styrene, injecting the mixed solution into the Schlenk tube in the step (1), continuously stirring for 96 hours to ensure that the 1-hexyl-4, 5-dimethylimidazolium salt and the p-chloromethyl styrene fully react, then weighing 40g of polybenzimidazole and 0.2g of phosphorylated cerium dioxide, adding the polybenzimidazole and the phosphorylated cerium dioxide, and continuously stirring;
(3) After the reaction is finished, centrifuging the precipitate, and drying at 60 ℃ for 8h to enable vinyl to be self-crosslinked to form an imidazolium salt crystal;
(4) Weighing 12g of polybenzimidazole at 25 ℃, dissolving in 2388g of N-methylpyrrolidone, and stirring for dissolving to obtain a polymer solution with the concentration of 0.5%;
(5) Weighing 4g of imidazolium salt crystals, adding into the step (4), and uniformly stirring to obtain a membrane casting solution for later use;
(6) Filling the casting solution obtained in the step (5) into a glass mold, drying at 60 ℃ for 48h, and stripping the dried film from a glass plate for later use;
(7) Weighing 5g of polypeptide phosphoric acid, and adding the polypeptide phosphoric acid into 95g of deionized water to obtain a polypeptide phosphoric acid solution with the concentration of 5%;
(8) And (3) placing the membrane obtained in the step (6) in the solution prepared in the step (7), soaking for 24h, taking out, repeatedly washing for 5 times by using deionized water, and completely drying for 48h at 40 ℃ to obtain the proton exchange membrane suitable for the low-humidity environment.
Comparative example 3:
(1) Weighing 10g of MIL-101 (Fe) and placing the MIL-101 (Fe) into a Schlenk tube provided with a constant pressure funnel, continuously vacuumizing to keep the vacuum degree at-1.0 MPa, and reducing the temperature of the Schlenk tube to-10 ℃;
(2) Weighing 20g of 1-hexyl-4, 5-dimethyl imidazolium salt, injecting into the Schlenk tube in the step (1), continuously stirring for 96h to ensure that the 1-hexyl-4, 5-dimethyl imidazolium salt enters the metal organic framework crystal material, then weighing 40g of polybenzimidazole and 0.2g of phosphorylated cerium dioxide, and continuously stirring;
(3) After the reaction is finished, centrifuging the precipitate, and drying at 60 ℃ for 8h to enable vinyl to be self-crosslinked to form an imidazolium salt crystal;
(4) Weighing 12g of polybenzimidazole at 25 ℃, dissolving in 2388g of N-methylpyrrolidone, stirring and dissolving to obtain a polymer solution with the concentration of 0.5%, then weighing 4g of polyvinyl benzyl chloride, and stirring for 24 hours;
(5) Weighing 4g of imidazolium salt crystals, adding into the step (4), and stirring for 24 hours until the mixture is uniform to obtain a membrane casting solution for later use;
(6) Filling the casting solution obtained in the step (5) into a glass mold, drying at 60 ℃ for 48h, and stripping the dried film from a glass plate for later use;
(7) Weighing 5g of polypeptide phosphoric acid, and adding the polypeptide phosphoric acid into 95g of deionized water to obtain a polypeptide phosphoric acid solution with the concentration of 5%;
(8) And (3) placing the membrane obtained in the step (6) in the solution prepared in the step (7), soaking for 24h, taking out, repeatedly washing for 5 times by using deionized water, and completely drying for 48h at 40 ℃ to obtain the proton exchange membrane suitable for the low-humidity environment.
Comparative example 4:
(1) Weighing 10g of MIL-101 (Fe) and placing the MIL-101 (Fe) into a Schlenk tube provided with a constant pressure funnel, continuously vacuumizing to keep the vacuum degree at-1.0 MPa, and reducing the temperature of the Schlenk tube to-10 ℃;
(2) Weighing a mixed solution of 20g of 1-hexyl-4, 5-dimethylimidazolium salt and 2g of p-chloromethyl styrene, injecting the mixed solution into the Schlenk tube in the step (1), continuously stirring for 96 hours to ensure that the 1-hexyl-4, 5-dimethylimidazolium salt and the p-chloromethyl styrene fully react, then weighing 40g of polybenzimidazole and 0.2g of phosphorylated cerium dioxide, adding the polybenzimidazole and the phosphorylated cerium dioxide, and continuously stirring;
(3) After the reaction is finished, centrifuging the precipitate, and drying at 60 ℃ for 8h to enable vinyl to be self-crosslinked to form an imidazolium salt crystal;
(4) Weighing 12g of polybenzimidazole at 25 ℃, dissolving the polybenzimidazole in 2388g of N-methylpyrrolidone, stirring and dissolving to obtain a polymer solution with the concentration of 0.5%, then weighing 4g of polyvinyl benzyl chloride, adding the mixture, and stirring for 24 hours;
(5) Weighing 4g of imidazolium salt crystals, adding into the step (4), and stirring for 24 hours until the mixture is uniform to obtain a casting solution for later use;
(6) Filling the casting solution obtained in the step (5) into a glass mold, drying at 60 ℃ for 48h, and stripping the dried film from a glass plate for later use;
(7) Weighing 5g of polypeptide phosphoric acid, and adding the polypeptide phosphoric acid into 95g of deionized water to obtain a 5% polypeptide phosphoric acid solution;
(8) And (3) placing the membrane obtained in the step (6) in the solution prepared in the step (7), soaking for 24h, taking out, repeatedly washing for 5 times by using deionized water, and completely drying for 48h at 40 ℃ to obtain the proton exchange membrane suitable for the low-humidity environment.
Comparative example 5:
(1) Weighing 10g of MIL-101 (Fe) and placing the MIL-101 (Fe) into a Schlenk tube provided with a constant pressure funnel, continuously vacuumizing to keep the vacuum degree at-1.0 MPa, and reducing the temperature of the Schlenk tube to-10 ℃;
(2) Weighing a mixed solution of 20g of 1-hexyl-4, 5-dimethylimidazolium salt and 40g of p-chloromethyl styrene, injecting the mixed solution into the Schlenk tube in the step (1), continuously stirring for 96 hours to ensure that the 1-hexyl-4, 5-dimethylimidazolium salt and the p-chloromethyl styrene fully react, then weighing 40g of polybenzimidazole and 0.2g of phosphorylated cerium dioxide, adding the polybenzimidazole and the phosphorylated cerium dioxide, and continuously stirring;
(3) After the reaction is finished, centrifuging the precipitate, and drying at 60 ℃ for 8 hours to enable the vinyl to be self-crosslinked to form an imidazolium salt crystal;
(4) Weighing 12g of polybenzimidazole at 25 ℃, dissolving in 2388g of N-methylpyrrolidone, stirring and dissolving to obtain a polymer solution with the concentration of 0.5%, then weighing 4g of polyvinyl benzyl chloride, and stirring for 24 hours;
(5) Weighing 4g of imidazolium salt crystals, adding into the step (4), and stirring for 24 hours until the mixture is uniform to obtain a casting solution for later use;
(6) Filling the casting solution obtained in the step (5) into a glass mold, drying at 60 ℃ for 48h, and stripping the dried film from a glass plate for later use;
(7) Weighing 5g of polypeptide phosphoric acid, and adding the polypeptide phosphoric acid into 95g of deionized water to obtain a 5% polypeptide phosphoric acid solution;
(8) And (3) placing the membrane obtained in the step (6) in the solution prepared in the step (7), soaking for 24h, taking out, repeatedly washing for 5 times by using deionized water, and completely drying for 48h at 40 ℃ to obtain the proton exchange membrane suitable for the low-humidity environment.
Comparative example 6:
(1) Weighing 10g of MIL-101 (Fe) and placing the MIL-101 (Fe) into a Schlenk tube provided with a constant pressure funnel, continuously vacuumizing to keep the vacuum degree at-1.0 MPa, and reducing the temperature of the Schlenk tube to-10 ℃;
(2) Weighing 20g of mixed solution of 1-hexyl-4, 5-dimethylimidazolium salt and 6g of p-chloromethyl styrene, injecting the mixed solution into the Schlenk tube in the step (1), continuously stirring for 96h to ensure that the 1-hexyl-4, 5-dimethylimidazolium salt and the p-chloromethyl styrene fully react, then weighing 80g of polybenzimidazole and 0.2g of phosphorylated cerium dioxide, and continuously stirring;
(3) After the reaction is finished, centrifuging the precipitate, and drying at 60 ℃ for 8 hours to enable the vinyl to be self-crosslinked to form an imidazolium salt crystal;
(4) Weighing 12g of polybenzimidazole at 25 ℃, dissolving the polybenzimidazole in 2388g of N-methylpyrrolidone, stirring and dissolving to obtain a polymer solution with the concentration of 0.5%, then weighing 4g of polyvinyl benzyl chloride, adding the mixture, and stirring for 24 hours;
(5) Weighing 4g of imidazolium salt crystals, adding into the step (4), and stirring for 24 hours until the mixture is uniform to obtain a casting solution for later use;
(6) Filling the casting solution obtained in the step (5) into a glass mold, drying at 60 ℃ for 48h, and stripping the dried film from a glass plate for later use;
(7) Weighing 5g of polypeptide phosphoric acid, and adding the polypeptide phosphoric acid into 95g of deionized water to obtain a 5% polypeptide phosphoric acid solution;
(8) And (5) placing the membrane obtained in the step (6) in the solution prepared in the step (7), soaking for 24h, taking out, repeatedly washing for 5 times by using deionized water, and completely drying for 48h at 40 ℃ to obtain the proton exchange membrane suitable for the low-humidity environment.
Comparative example 7:
(1) Weighing 10g of MIL-101 (Fe) and placing the MIL-101 (Fe) into a Schlenk tube provided with a constant pressure funnel, continuously vacuumizing to keep the vacuum degree at-1.0 MPa, and reducing the temperature of the Schlenk tube to-10 ℃;
(2) Weighing 20g of mixed solution of 1-hexyl-4, 5-dimethylimidazolium salt and 6g of p-chloromethyl styrene, injecting the mixed solution into the Schlenk tube in the step (1), continuously stirring for 96h to ensure that the 1-hexyl-4, 5-dimethylimidazolium salt and the p-chloromethyl styrene fully react, then weighing 10g of polybenzimidazole and 0.2g of phosphorylated cerium dioxide, and continuously stirring;
(3) After the reaction is finished, centrifuging the precipitate, and drying at 60 ℃ for 8 hours to enable the vinyl to be self-crosslinked to form an imidazolium salt crystal;
(4) Weighing 12g of polybenzimidazole at 25 ℃, dissolving in 2388g of N-methylpyrrolidone, stirring and dissolving to obtain a polymer solution with the concentration of 0.5%, then weighing 4g of polyvinyl benzyl chloride, and stirring for 24 hours;
(5) Weighing 4g of imidazolium salt crystals, adding into the step (4), and stirring for 24 hours until the mixture is uniform to obtain a membrane casting solution for later use;
(6) Filling the casting solution obtained in the step (5) into a glass mold, drying at 60 ℃ for 48h, and stripping the dried film from a glass plate for later use;
(7) Weighing 5g of polypeptide phosphoric acid, and adding the polypeptide phosphoric acid into 95g of deionized water to obtain a polypeptide phosphoric acid solution with the concentration of 5%;
(8) And (3) placing the membrane obtained in the step (6) in the solution prepared in the step (7), soaking for 24h, taking out, repeatedly washing for 5 times by using deionized water, and completely drying for 48h at 40 ℃ to obtain the proton exchange membrane suitable for the low-humidity environment.
Compared with comparative examples 1-7, comparative example 1 without adding imidazolium salt crystal material and comparative example 2 without adding polyethylene derivative, the proton exchange membranes of the examples and the comparative examples were subjected to the test of conductivity and tensile strength, and the results are shown in table 1. Table 1 shows that the membrane prepared by the present invention has high conductivity and tensile strength, and the effect is superior to that of the comparative example. The imidazolium salt is respectively introduced into the proton exchange membrane in two forms of covalent crosslinking and metal organic framework solid fixation, so that the number of functional groups in the membrane is increased, a regular ordered ion transfer channel is constructed by virtue of a regular lattice structure, and the ion transfer resistance is reduced; meanwhile, polyvinyl benzyl chloride and a cross-linking agent are adopted to carry out cross-linking reaction to prepare a skeleton structure, so that the stability and the mechanical strength of the ion exchange membrane are improved.
In comparative example 1, no imidazolium salt crystal material is added, polybenzimidazole is adopted to lock phosphoric acid molecules in the preparation of a proton exchange membrane, and the performance of the proton exchange membrane is reduced due to serious phosphoric acid loss along with the side length of running time;
in the process of preparing the proton exchange membrane in the comparative example 2, the polyethylene derivative is not added into the framework material, and the framework material does not form a cross-linked network structure, so that on one hand, the imidazolium salt crystal is not firmly fixed in the framework material and is easy to lose to cause performance damage, and on the other hand, the prepared membrane has poor chemical stability and is easy to degrade.
In comparative example 3, p-chloromethyl styrene was not added, the imidazolium salt could not form a macromolecule with p-chloromethyl styrene and was immobilized in the metal organic framework crystal material, and the electrochemical performance was high just after the membrane was prepared, but the imidazolium salt gradually lost with the time, and the performance of the membrane was sharply decreased.
In comparative example 4, the addition amount of p-chloromethyl styrene is small, part of imidazolium salt can not form macromolecules with p-chloromethyl styrene and is fixed in the metal organic framework crystal material, and the prepared proton exchange membrane can gradually lose imidazolium salt in the running process, so that the performance of the proton exchange membrane is also reduced.
In comparative example 5, the addition amount of p-chloromethyl styrene was too large, the polymer structure formed after the self-crosslinking of p-chloromethyl styrene covered the imidazolium salt crystal structure, and the proton exchange membrane prepared was poor in performance but strong in mechanical strength.
In comparative example 6, the amount of polybenzimidazole added was large, and the prepared proton exchange membrane was excellent in performance because polybenzimidazole has strong adsorbability to phosphoric acid compounds, but the proton exchange membrane prepared from polybenzimidazole was insufficient in toughness and was liable to cause defects such as cracks and brittle fracture.
In comparative example 7, the amount of polybenzimidazole added was small, and the proton exchange membrane prepared was poor in performance, high in mechanical tensile strength, and easily degradable.
TABLE 1 conductivity and tensile Strength of the proton exchange Membrane
Figure RE-GDA0003898705740000121
Figure RE-GDA0003898705740000131
The proton exchange membranes prepared in the examples and comparative examples of the present invention were immersed in the Fenton reagent for durability test, and the results are shown in table 2. Proton exchange membranes in which no covalent cross-linking is performed and no radical quencher is added have significantly poor chemical resistance.
TABLE 2 proton exchange membrane Mass residual Rate testing
Case(s) Mass residual ratio of 100h exchange Membrane%
Example 1 99.2
Example 2 99.1
Example 3 98.9
Comparative example 1 72
Comparative example 2 81
Comparative example 3 67
Comparative example 4 87.3
Comparative example 5 77.2
Comparative example 6 89.9
Comparative example 7 67
The present embodiment is only for explaining the present invention, and it is not limited to the present invention, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present invention.

Claims (10)

1. A proton exchange membrane, comprising: the proton exchange membrane is formed by compounding imidazolium salt crystals, polybenzimidazole, polyethylene benzyl chloride and phosphoric acid which serve as raw materials, wherein the imidazolium salt crystals are as follows: a substance formed by taking 4, 5-disubstituted imidazolium salt as a raw material is fixed in the metal organic framework crystal material; the 4, 5-disubstituted imidazolium salt is 1-butyl C4, C5 disubstituted imidazolium salt or 1-hexyl C4, C5 disubstituted imidazolium salt.
2. The proton exchange membrane according to claim 1, wherein the raw material of the imidazolium salt crystal further comprises chloromethyl styrene, polybenzimidazole, and a radical quencher.
3. The proton exchange membrane according to claim 1 wherein: the metal organic framework crystal material is of a cubic structure with micropores, and the pore diameter of each micropore is 100-1000nm; the metal organic framework crystal material is one or more than two of MIL-101 (Fe), MIL-101 (Cr), MIL-53 (Fe), ZIF-6, ZIF-8 and ZIF-10; the phosphoric acid is polypeptide organic phosphoric acid or inorganic phosphoric acid.
4. The proton exchange membrane according to claim 2 wherein: the imidazolium salt crystal is synthesized by adopting a low-temperature vacuum method, and comprises the following steps:
(1) Making the metal organic framework crystal material in a vacuum state;
(2) Mixing the mixed solution of the 4, 5-disubstituted imidazolium salt and the p-chloromethyl styrene with the metal organic framework crystal material obtained in the step (1) under a low-temperature environment, stirring, adding the polybenzimidazole and the free radical quencher, and mixing;
(3) Centrifuging and drying to obtain the imidazolium salt crystal.
5. The proton exchange membrane of claim 4 wherein: the vacuum degree of the vacuum state in the step (1) is-0.6 to-1.0 MPa; the low-temperature reaction temperature in the step (2) is-20 to-10 ℃, the stirring time is 48 to 96 hours, the drying temperature of the precipitate in the step (3) is 60 to 100 ℃, and the drying time is 4 to 8 hours; the steps (1) and (2) are in the same vacuum state.
6. The proton exchange membrane of claim 3 wherein: the C4 and C5 substituents in the 4, 5-disubstituted imidazolium salt are respectively R 1 And R 2 Said R is 1 And R 2 All of methyl, ethyl, propyl, butyl, isopropyl and tert-butyl, and the structures of the 1-butyl C4, C5 disubstituted imidazolium salt or the 1-hexyl C4, C5 disubstituted imidazolium salt are respectively as follows:
Figure FDA0003755944350000011
the free radical quencher is any one of phosphorylated cerium dioxide, sulfonated manganese dioxide, cerium dioxide and manganese dioxide;
the addition mass ratio of the metal organic framework material, the 4, 5-disubstituted imidazolium salt, the p-chloromethyl styrene, the polybenzimidazole and the free radical quencher is (1-0.5).
7. The process for the preparation of a proton exchange membrane according to any one of claims 1 to 6, wherein: the method comprises the following steps:
A. preparing a polybenzimidazole high-boiling-point solution, adding polyvinyl benzyl chloride at room temperature, and stirring to obtain a mixed solution;
B. adding the imidazolium salt crystal into the mixed solution obtained in the step A, and stirring at room temperature to obtain a membrane casting solution;
C. pouring the casting solution prepared in the step B into a glass mold, and after drying, stripping the obtained film from the glass mold;
D. c, soaking the film obtained in the step C in a phosphoric acid aqueous solution;
E. and D, washing the membrane obtained in the step D for more than 5 times by using deionized water, and drying to obtain the proton exchange membrane.
8. The method of claim 7, wherein: in the step A, the mass concentration of the polybenzimidazole high-boiling-point solution is 0.5-2wt%, and the high-boiling-point solvent for preparing the polybenzimidazole high-boiling-point solution is one of N-methylpyrrolidone, N-dimethylformamide, tetrahydrofuran and dimethyl sulfoxide; and D, the mass concentration of the phosphoric acid aqueous solution in the step D is 5-15wt%.
9. The method for producing according to claim 7, characterized in that: the mass ratio of each component in the steps A and B is that the imidazolium salt crystal is polybenzimidazole-polyvinyl benzyl chloride = 1-1.5.
10. The method of claim 7, wherein: the stirring time in the step A is 24-48h, and the stirring time in the step B is as follows: 24-48h; in the step C, drying the casting solution at the temperature of 60-80 ℃ for 24-48h; the soaking time in the step D is 24-48h; in the step E, the drying temperature is 40-60 ℃, and the drying time is 24-48h.
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