CN117069921B - High-performance membrane material and preparation method and application thereof - Google Patents

High-performance membrane material and preparation method and application thereof Download PDF

Info

Publication number
CN117069921B
CN117069921B CN202311330778.4A CN202311330778A CN117069921B CN 117069921 B CN117069921 B CN 117069921B CN 202311330778 A CN202311330778 A CN 202311330778A CN 117069921 B CN117069921 B CN 117069921B
Authority
CN
China
Prior art keywords
membrane
polymer
membrane material
film
acid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202311330778.4A
Other languages
Chinese (zh)
Other versions
CN117069921A (en
Inventor
徐立
房平磊
黄冲
刘凯
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Yantai Jiumu Chemical Co ltd
Original Assignee
Yantai Jiumu Chemical Co ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Yantai Jiumu Chemical Co ltd filed Critical Yantai Jiumu Chemical Co ltd
Priority to CN202311330778.4A priority Critical patent/CN117069921B/en
Publication of CN117069921A publication Critical patent/CN117069921A/en
Application granted granted Critical
Publication of CN117069921B publication Critical patent/CN117069921B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
    • C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
    • C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/10—Definition of the polymer structure
    • C08G2261/11—Homopolymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
    • C08G2261/324—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed
    • C08G2261/3241—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed containing one or more nitrogen atoms as the only heteroatom, e.g. carbazole
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Fuel Cell (AREA)

Abstract

The invention relates to the technical field of membrane materials, in particular to a high-performance membrane material, a preparation method and application thereof, wherein the membrane material comprises the following polymer structures:Y 1 、Y 2 、Y 3 、Y 4 each independently selected from aryl, aralkyl, heteroalkyl, alkyl, perfluoroalkyl, or absent, ar 2 Selected from the group consisting of substituted or unsubstituted arylene, aralkylene, heteroalkylene, alkylene, perfluoroalkylene, heteroarylene, or absent or oxygen, sulfur, nitrogen, ar 1 、Ar 3 Independently selected from substituted or unsubstituted arylene, aralkylene, heteroalkylene, alkylene, perfluoroalkylene, heteroarylene, or absent, R 1 ‑R 14 Each independently selected from the group consisting of hydrogen, alkyl, aryl, aralkyl, heteroalkyl, heteroaryl, and perfluoroalkyl. The high-performance membrane material prepared from the polymer has good ionic conductivity and stable physical and chemical properties, and has great application potential in fuel cell ionic membranes.

Description

High-performance membrane material and preparation method and application thereof
Technical Field
The invention relates to a high-performance membrane material, a preparation method and application thereof, and belongs to the technical field of membrane materials.
Background
The fuel cell is a device for directly converting chemical energy of hydrogen-rich fuel such as hydrogen, methanol, hydrocarbon and the like and oxygen in air into electric energy, and has the characteristics of cleanness, high efficiency, environmental friendliness and the like. Fuel cells are classified according to the electrolyte, and can be classified into Alkaline Anion Exchange Membrane Fuel Cells (AAEMFC), proton Exchange Membrane Fuel Cells (PEMFC), phosphoric Acid Fuel Cells (PAFC), solid Oxide Fuel Cells (SOFC), and the like. Among them, proton membrane fuel cells are the most developed and most used type of fuel cells, and have a mature commercial chain. However, the electrode reaction of the proton membrane fuel cell requires noble metals such as platinum as a catalyst, which significantly increases the cost of the proton exchange membrane fuel cell. And trace sulfur dioxide, carbon monoxide and the like existing in the fuel and the oxidant can reduce or even deactivate the activity of the catalyst, so that the catalyst is poisoned. These drawbacks have prevented the practical application and commercialization of proton exchange membrane fuel cell technology. However, the alkaline anion exchange membrane fuel cell has more advantages such as higher reaction efficiency, allowing the use of non-noble metals such as silver, nickel, etc. as catalysts, better tolerance to carbon monoxide, etc. in the gas raw material, etc. than other kinds of fuel cells, and has been receiving attention.
The function of the anion exchange membrane in a basic anion exchange membrane fuel cell is to conduct ions and to isolate gases from electrons (electronic insulators). How to provide an anion exchange membrane with both high ionic conductivity and excellent alkali resistance is an important challenge in preparing an effective anion exchange membrane. When the polymer structure is designed, the Ion Exchange Capacity (IEC) can be improved by adding a functional group with charges in the molecular structure, so that the ion conductivity is further improved; however, a high Ion Exchange Capacity (IEC) means a high water absorption, which affects the mechanical stability. In general, mechanical properties are in opposition to electrochemical properties, and to obtain a suitable anion exchange membrane for alkaline fuel cells, the ion exchange capacity and mechanical strength must be balanced. And secondly, the alkali resistance of the anion exchange membrane prevents the membrane material from being slowly decomposed in an alkaline environment, so that the efficiency of the fuel cell is greatly reduced. The alkali resistance of the membrane material can be improved by designing the functional group structure of the polymer. In general, the main requirements for ion exchange membranes of alkaline fuel cells are: low cost, good mechanical property, high ionic conductivity and excellent alkali resistance, and can conduct hydroxyl ions.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention provides a high-performance membrane material, a preparation method and application thereof, wherein the membrane material has good ion conductivity, stable physical and chemical properties and excellent alkali resistance, and the preparation method is simple and easy to implement and has great potential in the aspect of application of fuel cell ion membranes.
The technical scheme for solving the technical problems is as follows: a high performance film material comprising a polymer having the formula:
；
Y 1 、Y 2 each independently selected from aryl, aralkyl, heteroalkyl, alkyl, perfluoroalkyl, or absent and Y 1 And Y 2 At least one of which is selected from aryl, aralkyl, heteroalkyl, alkyl or perfluoroalkyl, when Y 1 And Y 2 In the absence of one of the, absent Y 1 Or Y 2 The attached imidazolyl group is neutral;
Y 3 、Y 4 each independently selected from aryl, aralkyl, heteroalkyl, alkyl, perfluoroalkyl, or absent and Y 3 And Y 4 At least one of which is selected from aryl, aralkyl, heteroalkyl, alkyl or perfluoroalkyl, when Y 3 And Y 4 In the absence of one of the, absent Y 3 Or Y 4 The attached imidazolyl group is neutral;
Ar 2 selected from substituted or unsubstituted arylene, aralkylene, heteroalkylene, alkylene, perfluoroalkylene, heteroarylene, O, S, N, or absent; when Ar is 2 When the substituent is contained in the compound, ar 2 In which groups are substituted with 1,2, 3 or 4 substituents independently selected from alkyl, aryl, aralkyl, perfluoroalkyl, heteroalkyl, heteroaryl and halogen; when Ar is 2 When the benzene ring does not exist, the bond end is directly connected to any position of the benzene ring;
Ar 1 、Ar 3 independently selected from substituted or unsubstituted arylene, aralkylene, heteroalkylene, alkylene, perfluoroalkylene, heteroarylene, or absent; when Ar is 1 Or Ar 3 When the substituent is contained in the compound, ar 1 Or Ar 3 In which groups are substituted with 1,2, 3 or 4 substituents independently selected from alkyl, aryl, aralkyl, perfluoroalkyl, heteroalkyl, heteroaryl and halogen; when Ar is 1 Or Ar 3 In the absence, the imidazole bond end is directly connected with any benzene ringAn intentional position;
R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 8 、R 9 、R 10 、R 11 、R 12 、R 13 、R 14 each independently selected from hydrogen, alkyl, aryl, aralkyl, heteroalkyl, heteroaryl, or perfluoroalkyl;
M - selected from fluoride, chloride, bromide, iodide, hydroxide, carbonate, bicarbonate, cyanide, sulfate, phosphate, triflate, and any combination thereof;
n is an integer greater than 1; the heteroatoms in the heteroalkyl, heteroalkylene, heteroarylene, and heteroaryl groups are selected from O, S or N.
Further, the polymer comprises one or more anions M - Wherein the one or more anions M - Counteracting one or more positive charges in the polymer.
Further, the polymer comprises the following structural formula:
。
further, the polymer is selected from any one of the following structural formulas:
。
the invention also discloses a preparation method of the high-performance film material, which comprises the following steps:
s1, synthesis of polymer
Dissolving a monomer in a solvent, adding a catalyst and a ligand under the protection of inert gas, heating and preserving heat for polymerization reaction, pouring a reaction system into a precipitator after the reaction is finished, and filtering, cleaning and drying to obtain the polymer;
the monomer is as follows:；
s2, functionalization treatment
And (2) dissolving the polymer obtained in the step (S1) into a solvent, then adding a functionalization reagent, sealing, preserving heat and stirring under a heating condition, and finally pouring the reaction solution into a precipitator, and filtering, washing and drying to obtain the membrane material.
Further, the monomer is selected from any one of the following structures:
。
further, the solvent is one or a combination of a plurality of N-methyl pyrrolidone, N-dimethylformamide, dimethyl sulfoxide and N, N-dimethylacetamide;
the precipitant is one or a combination of more of purified water, phosphoric acid, hydrobromic acid, hydrofluoric acid, dilute sulfuric acid, hydroiodic acid, industrial hydrochloric acid, cyanic acid and trifluoromethanesulfonic acid;
the catalyst is any one of trans-1, 5, 9-cyclododecatriene nickel (0), nickel chloride and nickel chloride glycol dimethyl ether complex, and the ligand is 2,2' -bipyridine.
Further, the functionalizing agent is any one of methyl iodide, ethyl iodide, propyl iodide, butyl iodide, pentane iodide, hexane iodide, heptane iodide, octane iodide, nonane iodide and decane iodide.
Further, in the step S1, the dissolution temperature of the monomer dissolved in the solvent is 30.0-50.0 ℃, the heat preservation reaction temperature is 130.0-135.0 ℃, and the heat preservation reaction time is 10-20 h;
in the step S2, the heating temperature is 75-85 ℃, and the airtight stirring time is 12-24 hours;
in the step S1 and the step S2, the filtering and washing temperature is 20.0-30.0 ℃; the drying temperature is 90.0-120.0 ℃, and the drying time is more than 24 hours.
The invention also discloses application of the high-performance membrane material, and the membrane material is applied to an ion exchange membrane of a fuel cell.
The method for preparing the ion exchange membrane of the fuel cell by using the membrane material comprises the following steps: and (3) dissolving the dried membrane material polymer with a solvent A to obtain a uniform solution with the mass fraction of 5% -10%, coating a film on a clean glass plate, drying, carefully stripping to obtain a high-performance ion exchange membrane, immersing the ion membrane into a 1M potassium hydroxide solution, immersing for 24-48 h, washing with purified water until the aqueous solution is neutral, and drying to obtain the high-performance ion exchange membrane.
The beneficial effects of the invention are as follows:
the membrane material of the invention fully utilizes the structural characteristics of polymer functional groups, such as: the imidazolium salt has the characteristics of large pi bond of ring conjugation and large steric hindrance, so that positive charges are delocalized and uniformly dispersed in an imidazole ring, the aggressivity of hydroxide ions is weakened, and the like, and the alkali resistance of the membrane material is enhanced. Meanwhile, the high-performance membrane material not only has higher ion transmission efficiency, but also can effectively control the water absorption swelling rate of the membrane material, and well balances the relationship between the Ion Exchange Capacity (IEC) and the mechanical strength.
The membrane material provided by the invention has high alkali resistance, good mechanical property, good ionic conductivity and proper swelling degree, so that the membrane material has great potential in the application of an anion membrane of an alkaline fuel cell.
Drawings
FIG. 1 is a graph showing the relationship between the swelling degree and the temperature of the films A, B, C, D and E;
FIG. 2 is a graph showing the comparison of mechanical properties of films A, B, C, D and E;
FIG. 3 is a graph of ionic conductivity versus temperature for films A, B, C, D, E;
FIG. 4 is a graph comparing the stability of films A, B, C, D, E immersed in 1M sodium hydroxide solution at 60.0deg.C;
fig. 5 is a performance test of oxyhydrogen type single cells of a film.
Detailed Description
The following describes the present invention in detail. The present invention may be embodied in many other forms than described herein and similarly modified by those skilled in the art without departing from the spirit of the invention, so that the invention is not limited to the specific embodiments disclosed.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
Example 1:
an anion exchange membrane material for use in a fuel cell, said membrane material comprising a polymer a having the structure:
；
the specific synthetic route for polymer a is:
；
preparation of A-1: weighing p-chlorobenzaldehyde (CAS No. 104-88-1) and sodium bisulphite (CAS No. 7631-90-5) according to a molar ratio of 1:1.5, wherein the sodium bisulphite is prepared into a 30% aqueous solution, then preserving heat for 2 hours at 80 ℃, filtering the reaction solution after heat preservation to obtain white solid salt, and then drying. Weighing [1,1' -biphenyl group according to a molar ratio of 1:2.1]-3,3', 4' -tetramino (CAS No.: 91-95-2) and an off-white solid salt, the solvent being ethanol, the solvent amount being [1,1' -biphenyl ]]10.0 times of 3,3', 4' -tetramino, heat preservation for 5h at 75 ℃, HPLC detection, no raw material remained, and reaction purity of 80.5%. The A-1 is obtained through desolventizing, water boiling and pulping, and the yield is: 72.5% HPLC purity was 98.4%. 1 H NMR (500 MHz，Chloroform-d): 12.56 (s, 2H), 8.10-8.05 (m, 4H), 8.04-8.01 (d, 1H), 7.95-7.85 (m, 3H), 7.76 (d, 1H), 7.68 (d, 1H), 7.49-7.43 (m, 4H). Detection by LC-MS: the theoretical molecular weight is 455.34, and the actual detection result molecular weight is 455.0.
Preparation of A-2: weighing A-1 and potassium hydroxide according to a molar ratio of 1.0:3.0, wherein the solvent is dimethyl sulfoxide, the solvent amount is 25.0 times of the weight of the A-1, then weighing methyl iodide and the A-1 according to a molar ratio of 3:1, dropwise adding methyl iodide at 30 ℃, carrying out heat preservation reaction for 2h, and detecting by HPLC, wherein the reaction purity is 97.4%. The A-2 is obtained through hydrolysis, filtration, water boiling and pulping, and the yield is: 85.1% HPLC purity was 99.5%.
1 H NMR (500 MHz, chlorine-d): 7.94-7.83 (m, 3H), 7.82-7.74 (m, 5H), 7.66 (d, 1H), 7.51 (d, 1H), 7.47-7.42 (m, 4H), 4.00 (s, 3H), 3.94 (s, 3H). LC-MS: the theoretical molecular weight is 483.39, and the actual detection result molecular weight is 483.1.
Preparation of A-3: weighing A-2 and N, N-dimethylformamide according to a weight ratio of 1.0:40.0, dissolving the A-2 in the N, N-dimethylformamide, and adding trans-1, 5, 9-cyclododecatriene nickel (0) and 2,2' -bipyridine under the protection of inert gas at low temperature, wherein the molar ratio of the A-2 to the catalyst to the ligand is 1.0:3.0:3.0. Then the reaction is kept at 135 ℃ for 15 hours, and when the system is a viscous liquid, the reaction is stopped. The reaction liquid is slowly hydrolyzed into hydrochloric acid for precipitation under the temperature of 30.0 ℃ and then is filtered, washed and dried to obtain A-3.
Preparation of Polymer A: dissolving A-3 in N, N-dimethylformamide 40.0 times, weighing A-2 and iodobutane according to a molar ratio of 1.0:6.0, hermetically stirring and reacting for 20 hours at 30 ℃, hydrolyzing the reaction solution into deionized water, filtering, washing and drying to obtain a polymer A.
Example 2:
an anion exchange membrane material for use in a fuel cell, said membrane material comprising a polymer B having the structure:
；
the specific synthetic route of the polymer B is as follows:
；
preparation of B-1: weighing p-chlorobenzaldehyde (CAS No. 104-88-1) and sodium bisulphite (CAS No. 7631-90-5) according to a molar ratio of 1:1.5, wherein the sodium bisulphite is prepared into a 30% aqueous solution, then preserving heat for 2 hours at 80 ℃, filtering the reaction solution after heat preservation to obtain white solid salt, and then drying. Weighing 4-bromo-1, 2-phenylenediamine (CAS No. 1575-37-7) and off-white solid salt according to a molar ratio of 1:2.1, wherein the solvent is ethanol, the solvent amount is 10.0 times of that of the 4-bromo-1, 2-phenylenediamine, and the temperature is kept for 5h at 75 ℃, and the raw materials are not remained and have a reaction purity of 91.5% by GC detection. The B-1 is obtained through desolventizing, water boiling and pulping, and the yield is: 82.2% and GC purity 97.4%.
1 H NMR (500 MHz, chlorine-d): 12.56 (s, 1H), 8.17-8.11 (m, 2H), 7.69 (d, 1H), 7.6-7.52 (m, 2H), 7.52-7.46 (m, 2H). Detection by GC-MS: the theoretical molecular weight is 307.57, and the actual detection result molecular weight is 307.1.
Preparation of B-2: weighing (2, 3,5, 6-tetramethyl-1, 4-phenyl) bisboric acid (CASNo.: 1222008-16-3) and B-1 according to a molar ratio of 1:2.1, adding catalysts of palladium acetate and xanthene, wherein the molar ratio of the catalyst to the ligand is 1.0:0.01:0.02, the solvent is dioxane, the solvent amount is 10.0 times that of the B-1, the potassium carbonate is prepared into 30% aqueous solution by mass percent, the aqueous solution is preserved for 6 hours at 75 ℃, the HPLC detection is carried out, the raw materials are free from residue, and the reaction purity is 85.3%. The B-2 is obtained through extraction, water washing, column passing, solvent removal and recrystallization, and the yield is: 74.5% and HPLC purity of 98.4%.
1 H NMR (500 MHz, chlorine-d): 12.56 (s, 2H), 8.14-8.08 (m, 4H), 7.88 (t, 2H), 7.65-7.57 (m, 3H), 7.51 (d, 1H), 7.47-7.41 (m, 4H), 2.44 (d, 12H). Detection by LC-MS: the theoretical molecular weight is 587.54, and the molecular weight of the actual detection result is 587.2.
The preparation process of the B-3, the B-4 and the polymer B is the same as that of the A-2, the A-3 and the polymer A.
Example 3:
an anion exchange membrane material for use in a fuel cell, said membrane material comprising a polymer C having the structure:
；
the specific synthetic route for polymer C is:
；
the preparation of polymer C differs from that of polymer B in that: the (2, 3,5, 6-tetramethyl-1, 4-phenyl) bisboronic acid (CAS No.: 1222008-16-3) in preparation B-1 was replaced with 2,2' - (2, 6-naphthalenediyl) bis [4, 5-tetramethyl ] -1,3, 2-dioxapentaborane (CAS No.: 849543-98-2) and then polymer C was prepared according to the procedure for preparation of polymer B.
Example 4:
an anion exchange membrane material for use in a fuel cell, said membrane material comprising a polymer D having the structure:
the specific synthetic route for polymer D is:
；
preparation of D-1: 4-hydroxy-1, 2-phenylenediamine (CAS No. 367-31-7), 4-fluoro-1, 2-phenylenediamine (CAS No. 615-72-5) and potassium carbonate are weighed in sequence according to a molar ratio of 1.0:1.2:3.0, the solvent is N, N-dimethylformamide, the solvent amount is 10.0 times of the weight of the 4-fluoro-1, 2-phenylenediamine, the reaction is carried out at 140 ℃ for 28h in a heat preservation mode, no residual 4-hydroxy-1, 2-phenylenediamine exists through HPLC detection, and the reaction purity is 75.7%. Washing with water, desolventizing and recrystallizing to obtain D-1, wherein the yield is as follows: 65.8% HPLC purity 95.4%.
1 H NMR (500 MHz, chlorine-d): 6.41 (d, 2H), 6.22 (t, 2H), 6.08 (d, 2H), 5.07 (d, 2H), 4.89 (d, 2H), 4.66 (d, 2H), 4.51 (d, 2H). LC-MS: the theoretical molecular weight is 230.27, and the molecular weight of the actual detection result is 230.1.
The preparation process of D-2, D-3, D-4 and polymer D is the same as that of A-1, A-2, A-3 and polymer A.
Comparative example 1:
the fuel cell anion exchange membrane polymer E disclosed many times in the literature and patents has the structural formula:
；
the specific synthetic route for polymer E is:
；
the preparation of polymer E differs from that of polymer B in that: the (2, 3,5, 6-tetramethyl-1, 4-phenyl) bisboronic acid (CAS No.: 1222008-16-3) in preparation B-2 was replaced with p-chlorobenzoic acid (CAS No.: 1679-18-1), and then polymer E was prepared according to the process for preparing polymer B.
Polymer application: coating film and related test thereof
And (3) coating: the polymer a, polymer B, polymer C, polymer D, and polymer E synthesized in example 1, example 2, example 3, example 4, and comparative example 1 were prepared into casting solutions with a mass fraction of 15% using dimethyl sulfoxide, respectively. Coating the casting solution on a clean glass flat plate respectively by using a scraper, evaporating the solvent to dryness and carefully peeling the film to obtain a corresponding high-performance ion exchange membrane material, performing functionalization treatment on the ion exchange membrane, respectively immersing the ion exchange membrane into 1M potassium hydroxide solution, immersing the ion exchange membrane for 48 hours, taking out the membrane, washing the membrane with deionized water until the aqueous solution is neutral, and drying the membrane at 100 ℃ for 48 hours to obtain the hydroxyl type alkaline fuel cell anion exchange membrane corresponding to the polymer A, the polymer B, the polymer C, the polymer D and the polymer E: film A, film B, film C, film D, film E.
And then performing relevant tests on the film A, the film B, the film C, the film D and the film E and testing the single cell performance of the corresponding films:
(1) Solubility test: 0.5g of each of the A film, the B film, the C film, the D film and the E film was dissolved in 15g of a solvent, and the dissolution was observed by heating and stirring at 80.0 ℃.
Intrinsic viscosity test: the film A, the film B, the film C, the film D and the film E are respectively dissolved in dimethyl sulfoxide to prepare clear solution with the concentration of 10g/L, and the clear solution is measured by a black-bone viscometer at the temperature of 23.0 ℃.
TABLE 1 viscosity and dissolution of film materials
Note that: ++ means soluble at room temperature, ++ -means swollen at room temperature, -means insoluble under heating.
Table 1 shows the viscosities and solubilities of films A, B, C, D and E. From the above data, it can be seen that the solubility of the A, B, C, D, E films in dimethyl sulfoxide and N-methylpyrrolidone is best, and that these two solvents can be selected as the film coating solvents. Wherein the viscosity of the film is moderate, and the requirement of the film coating is met.
(2) Water absorption and swelling ratio: cutting the film into a plurality of small sample strips with the diameter of 10mm and the diameter of 50mm by using a cutting die, vacuum drying the small sample strips at 80 ℃ for 24 hours, rapidly measuring the dry weight of the small sample strips, respectively soaking the small sample strips in constant-temperature water bath at 40 ℃ and 80 ℃ for 24 hours, wiping the surface of the dry film by using filter paper, and weighing the water absorption weight of the dry film. The film was then placed on a glass plate, and the length of the film was measured with a vernier caliper, and the water absorption (water up) and the volume swelling ratio (swollening ratio) of the film were calculated. The water absorption and swelling ratio were calculated as follows: water absorption = m a -m b /m a X 100%, swelling ratio=l a -l b /l b X 100%, where m a 、I a Respectively the quality and the length of the membrane after being soaked in water bath for 24 hours at a specific temperature; m is m b 、I b The mass and length of the film at the vacuum dry thickness, respectively.
Ion Exchange Capacity (IEC): the dry film with the mass of M is soaked in hydrochloric acid standard solution with the mass of 0.1mol/L for 48 hours, so that the neutralization reaction is completed at room temperature. The remaining hydrochloric acid solution was subjected to back titration with a 0.1mol/L sodium hydroxide standard solution. The calculation formula is as follows: iec=c 2 C 2 -C 1 C 1 W, where C 1 、C 2 (mol/L) is the concentration of hydrochloric acid and sodium hydroxide solution respectively; v (V) 1 、V 2 The volumes of hydrochloric acid and sodium hydroxide solution consumed, respectively.
TABLE 2 IEC values and Water absorption of Membrane materials
FIG. 1 shows the relationship between swelling degree and temperature of the materials of the films A, B, C, D and E, and Table 2 shows the IEC value and water absorption of the materials. When the high-performance alkaline anion exchange membrane absorbs water, the size of the membrane can be changed, the swelling phenomenon of the ion membrane occurs, and only then can the ion exchange membrane conduct ions more efficiently. However, too high swelling degree and water absorption rate can cause too large changes of mechanical properties and morphology of the membrane, so that the catalyst falls off and the like, and based on the water absorption rate, the swelling degree and IEC parameters, the membrane A, the membrane B, the membrane C, the membrane D and the membrane E can meet the basic use requirements of the alkaline fuel cell membrane.
(3) Mechanical properties: the test was carried out according to GB13022-91, the tensile test being carried out under ambient conditions (23.0 ℃ C., 20% relative humidity) on a universal tensile tester (SANS CMT 8102) at a tensile speed of 1cm/min.
Figure 2 shows the mechanical properties of the membrane material. The tensile strength of the film material decreases with increasing IEC, which causes an increase in the water content and swelling ratio of the film, an increase in the polymer chain spacing, and a decrease in the inter-chain interactions, resulting in a decrease in tensile strength. As can be seen from the figure, the tensile strength of the membrane materials is good, and the membrane materials A, B, C, D and E can meet the use requirements of the alkaline fuel cell membrane in a comprehensive way.
(4) Ion conductivity: ion conductivity was measured by AC impedance method, in-plane conductivity of ion membrane was measured by electrochemical workstation (CHI 660C, shanghai Chen Hua instruments Co., shanghai) at a test frequency of 1-10 5 Hz. Wherein during the test, the ionic membrane is clamped in a tetrafluoroethylene mold with two platinum electrodes and is fed in a constant current modeAnd testing the AC impedance. Ionic conductivity = two electrode spacing/membrane cross-sectional area in the electric field/membrane resistance.
FIG. 3 is a graph showing the relationship between ionic conductivity and temperature of a membrane material. As IEC increases, the number of ions in the ionic membrane increases, as does the ionic conductivity of the membrane material. As the temperature increases, the ionic conductivity of the membrane material increases. From the comprehensive data, the conductivities of the A film, the B film, the C film, the D film and the E film can meet the use requirement of the alkaline fuel cell film.
(5) Alkali stability: the membrane material is soaked in 1M potassium hydroxide solution at 60.0 ℃, a sample is taken out every 120h, the membrane material is washed with deionized water until the aqueous solution is neutral, then the ionic conductivity of the membrane material is tested, and the alkali stability of the membrane is judged by the change of the ionic conductivity.
FIG. 4 shows the stability of the membrane material immersed in 1M potassium hydroxide solution at 60.0deg.C. From the data in FIG. 4, it can be seen that the A film, the B film, the C film and the D film are kept in alkali liquor for 800 hours, and the conductivity is kept above 70%, wherein the D film has slightly lower alkali resistance due to the existence of ether bond, but comprehensively considered, the basic use requirements of the alkaline fuel cell film can be met. While the conductivity of E film in alkaline environment for 480h has been reduced to about 70%, probably due to poor structural stability of the polymer E backbone.
(6) Single cell performance test: firstly preparing a membrane electrode assembly by using a CCS method, namely spraying catalyst ink on carbon paper, then contacting the carbon paper with a membrane material through hot pressing treatment, weighing Pt/C and iridium dioxide catalyst according to a weight ratio of 20:1, mixing the catalyst, isopropanol and a polymer dimethyl sulfoxide solution (5.0% by mass fraction), and dispersing the catalyst and the iridium dioxide catalyst uniformly by using ultrasound. And uniformly spraying the mixed solution on carbon paper to prepare the gas diffusion electrode. The membrane is sandwiched between two electrodes, and the electrodes and the membrane are pressed into a membrane electrode assembly with an external force at room temperature.
In order to evaluate the practical application effect of the highly stable ion exchange membrane in the present invention, the membrane a having the highest conductivity was assembled into a membrane electrode assembly by CCS method. The performance was tested using a fuel cell workstation (TX) under the following conditions: at 60.0deg.C, the hydrogen flow rate was 150mL/min, the oxygen flow rate was 150mL/min, and the gas relative humidity was 100%.
Fig. 5 is a performance test of the hydrogen-oxygen type single cell. As can be seen from the test data, the open circuit voltage of the single cell was 0.99V, which is close to the theoretical value (1.25V), indicating excellent performance of the ion exchange membrane. At a current density of 300-450 mA/cm 2 When the power density of the single cell is 108-112 mW/cm 2 . The oxyhydrogen type single cell prepared by the membrane A has higher power density, and fully illustrates that the high-performance ion exchange membrane obtained by the invention can be used as a membrane material of a fuel cell.
The related test data and the single cell performance test show that the membrane A, the membrane B, the membrane C and the membrane D can well meet the use requirement of the ion exchange membrane of the alkaline fuel cell, wherein the membrane electrode assembly prepared by the membrane A also proves that the membrane electrode assembly with high performance can be used as a membrane electrode material of the fuel cell. Compared with the E film disclosed and reported for many times, the comprehensive properties of the A film, the B film, the C film and the D film are more outstanding, and although the related data of the E film also meet the basic use requirements of the fuel cell, the alkali resistance of the E film is obviously lower than that of the A film, the B film, the C film and the D film, and in the application of the alkaline fuel cell, the film material can be gradually decomposed, so that the service life of a film electrode can be greatly shortened. When the high-performance membrane material is used for a membrane electrode in an alkaline fuel cell, the high-performance membrane material not only has good ionic conductivity and moderate swelling rate, but also has excellent alkali resistance, so that the high-performance membrane material has great potential in the application of an anion membrane of the alkaline fuel cell.
The technical features of the above-described embodiments may be arbitrarily combined, and in order to simplify the description, all possible combinations of the technical features in the above-described embodiments are not exhaustive, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit or scope of the invention as defined in the appended claims.

Claims (5)

1. A high performance film material characterized in that the film material comprises a polymer having a structural formula selected from any one of the following structural formulas:
。
2. a method for preparing a high performance film material according to claim 1, wherein the method comprises:
s1, synthesis of polymer
Dissolving a monomer in a solvent, adding a catalyst and a ligand under the protection of inert gas, heating and preserving heat for polymerization reaction, pouring a reaction system into a precipitator after the reaction is finished, and filtering, cleaning and drying to obtain the polymer;
the monomer is selected from any one of the following structures:
；
s2, functionalization treatment
And (2) dissolving the polymer obtained in the step (S1) into a solvent, then adding iodobutane, sealing, keeping the temperature, stirring, finally pouring the reaction solution into a precipitator, and filtering, washing and drying to obtain the membrane material.
3. The method for preparing a high-performance membrane material according to claim 2, wherein the solvent is one or a combination of several of N-methylpyrrolidone, N-dimethylformamide, dimethyl sulfoxide and N, N-dimethylacetamide;
the precipitant is one or a combination of more of purified water, phosphoric acid, hydrobromic acid, hydrofluoric acid, dilute sulfuric acid, hydroiodic acid, industrial hydrochloric acid, cyanic acid and trifluoromethanesulfonic acid;
the catalyst is any one of trans-1, 5, 9-cyclododecatriene nickel (0), nickel chloride and nickel chloride glycol dimethyl ether complex, and the ligand is 2,2' -bipyridine.
4. The method for preparing a high-performance film material according to claim 2, wherein in the step S1, the dissolution temperature of the monomer in the solvent is 30.0 ℃ to 50.0 ℃, the heat-preserving reaction temperature is 130.0 ℃ to 135.0 ℃ and the heat-preserving reaction time is 10h to 20h;
in the step S2, the heating temperature is 75-85 ℃, and the airtight stirring time is 12-24 hours;
in the step S1 and the step S2, the filtering and washing temperature is 20.0-30.0 ℃; the drying temperature is 90.0-120.0 ℃, and the drying time is more than 24 hours.
5. Use of a high performance membrane material according to claim 1, wherein the membrane material is applied to an ion exchange membrane of a fuel cell.
CN202311330778.4A 2023-10-16 2023-10-16 High-performance membrane material and preparation method and application thereof Active CN117069921B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202311330778.4A CN117069921B (en) 2023-10-16 2023-10-16 High-performance membrane material and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202311330778.4A CN117069921B (en) 2023-10-16 2023-10-16 High-performance membrane material and preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN117069921A CN117069921A (en) 2023-11-17
CN117069921B true CN117069921B (en) 2024-02-06

Family

ID=88706419

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202311330778.4A Active CN117069921B (en) 2023-10-16 2023-10-16 High-performance membrane material and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN117069921B (en)

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109863227A (en) * 2016-08-04 2019-06-07 西蒙弗雷泽大学 The crosslinking of hydroxide stable polybenzimidazoles and polyimidazole film and ionomer
CN115109235A (en) * 2022-07-18 2022-09-27 烟台九目化学股份有限公司 Imidazole type group functionalized polymer and preparation method and application thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109863227A (en) * 2016-08-04 2019-06-07 西蒙弗雷泽大学 The crosslinking of hydroxide stable polybenzimidazoles and polyimidazole film and ionomer
CN115109235A (en) * 2022-07-18 2022-09-27 烟台九目化学股份有限公司 Imidazole type group functionalized polymer and preparation method and application thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Hydroxide-Stable Ionenes;Andrew G. Wright et al;《ACS Macro Lett.》;第3卷;第444-447页 *

Also Published As

Publication number Publication date
CN117069921A (en) 2023-11-17

Similar Documents

Publication Publication Date Title
Choudhury et al. High performance and eco-friendly chitosan hydrogel membrane electrolytes for direct borohydride fuel cells
CN111269550B (en) Crosslinked anion exchange membrane based on polyphenyl ether/polyvinyl alcohol and preparation method
CN109390617B (en) Cross-linked polybenzimidazole basic anion exchange membrane and preparation and application thereof
Xia et al. Polybenzimidazoles with pendant quaternary ammonium groups as potential anion exchange membranes for fuel cells
CN107556247B (en) Functional cross-linking agent, preparation method and high-phosphoric-acid-doped cross-linked polybenzimidazole film prepared from functional cross-linking agent
US9263757B2 (en) Highly basic ionomers and membranes and anion/hydroxide exchange fuel cells comprising the ionomers and membranes
WO2016095237A1 (en) N1-substituted imidazole compound, and alkaline anion exchange membrane and preparation
CN113912789B (en) Proton exchange membrane and preparation method and application thereof
Hao et al. Fabrication of N1-butyl substituted 4, 5-dimethyl-imidazole based crosslinked anion exchange membranes for fuel cells
Pan et al. Benzimidazolium functionalized polysulfone-based anion exchange membranes with improved alkaline stability
CN108649257A (en) A kind of high temperature proton exchange film and preparation method thereof
CN109888348B (en) Preparation method of fuel cell proton membrane material solid super acid/aza-epoxidized graphene/2, 5-polybenzimidazole
Song et al. Imidazolium-functionalized anion exchange polymer containing fluorine group for fuel cell application
CN115109235B (en) Imidazole group functionalized polymer and preparation method and application thereof
JP5032175B2 (en) Membrane-electrode structure for polymer electrolyte fuel cell
CN117069921B (en) High-performance membrane material and preparation method and application thereof
JP2007294213A (en) Membrane-electrode assembly for polymer electrolyte fuel cell
Ding et al. Quaternized poly (2, 6‐dimethyl‐1, 4‐phenylene oxide) crosslinked by tertiary amine and siloxane for anion exchange membranes
CN114695933B (en) Semi-interpenetrating anion exchange membrane and preparation method and application thereof
CN103996865A (en) High methanol resistant polymer electrolyte membrane and preparation method thereof
CN117402326B (en) Naphthol bisimidazole type membrane material and preparation method and application thereof
CN107887626B (en) Cross-linked composite high-temperature proton exchange membrane and preparation method thereof
CN103724648A (en) Strong alkaline polyarylether ionomer anion-exchange membrane as well as preparation and application thereof
CN111193054B (en) Preparation method of proton exchange membrane
CN115181250B (en) Side chain imidazole functionalized polymer and preparation method and application thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant