WO2026007019A1 - 一种薁基支化聚(芳基-哌啶)阴离子交换膜及其制备方法和应用 - Google Patents

一种薁基支化聚(芳基-哌啶)阴离子交换膜及其制备方法和应用

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WO2026007019A1
WO2026007019A1 PCT/CN2024/103302 CN2024103302W WO2026007019A1 WO 2026007019 A1 WO2026007019 A1 WO 2026007019A1 CN 2024103302 W CN2024103302 W CN 2024103302W WO 2026007019 A1 WO2026007019 A1 WO 2026007019A1
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piperidine
azulene
aryl
anion exchange
branched poly
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English (en)
French (fr)
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庄小东
房梓榆
柯长春
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Shanghai Jiao Tong University
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Shanghai Jiao Tong University
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    • 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
    • C08G10/00—Condensation polymers of aldehydes or ketones with aromatic hydrocarbons or halogenated aromatic hydrocarbons only
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Definitions

  • This application relates to the field of membrane technology, and in particular to an azulene-branched poly(aryl-piperidine) anion exchange membrane, its preparation method, and its application.
  • Anion exchange membranes are a key component of anion exchange membrane fuel cells and alkaline electrolyzers. Preparing anion exchange membranes with high hydroxide conductivity and stable chemical properties is crucial for achieving high power density and long-term durability in these systems.
  • Anion exchange membranes consist of a polymer backbone, cationic groups, and migratable ions. The polymer backbone structure and the properties of the cationic groups directly determine the performance of the AEM.
  • Current research on AEMs faces the following technical bottlenecks: (1) Because the radius of OH- is larger than that of H + , the OH- conductivity in anion exchange membranes is only 20%–33% of the H + conductivity in proton exchange membranes under the same conditions.
  • IEC ion exchange capacity
  • this application provides an azulene-branched poly(aryl-piperidine).
  • Anion exchange membranes, their preparation methods, and applications are proposed to overcome the problems of low ion conductivity and poor alkali stability in existing technologies.
  • the first aspect of this application provides an azulene-branched poly(aryl-piperidine) anion exchange membrane, wherein the azulene-branched poly(aryl-piperidine) anion exchange membrane contains an azulene-branched poly(aryl-piperidine) polymer and has the following structure:
  • R is an aromatic group
  • A is an azuleyl branched group
  • a is any integer greater than or equal to
  • b is any integer greater than or equal to 1.
  • R is at least one of the following structures:
  • R1 and R2 are at least one of H atoms, aliphatic or aromatic long chains.
  • A is at least one of the following structures:
  • a second aspect of this application provides a method for preparing the azulene-branched poly(aryl-piperidine) anion exchange membrane described in the first aspect, the method comprising:
  • the aromatic monomer, azulene branched monomer and N-methyl-4-piperidinone are dissolved in a first organic solvent, trifluoroacetic acid and trifluoromethanesulfonic acid are added, and after reaction, the azulene branched poly(aryl-piperidine) precursor is collected;
  • the azulene branched poly(aryl-piperidine) precursor was dissolved in a second organic solvent, potassium carbonate and iodomethane were added, and after a light-protected reaction, ethyl acetate was added, and the mixture was purified to collect the cationic azulene branched poly(aryl-piperidine).
  • the cationic azulene-branched poly(aryl-piperidine) is dissolved in a third organic solvent, and the Cl - type membrane is collected.
  • the Cl - type membrane is then subjected to ion exchange to obtain an OH - type membrane.
  • the azulene-branched poly(aryl-piperidine) anion exchange membrane is collected.
  • the molar ratio of the aromatic monomer to the azulene branched monomer is 0-99:1;
  • the molar ratio of the sum of the amounts of the azulene branched monomer and the aromatic monomer to the amount of the N-methyl-4-piperidinone is 1:0.9-1.2.
  • the molar ratio of N-methyl-4-piperidinone to trifluoroacetic acid is 1:0.8-1.2;
  • the molar ratio of the N-methyl-4-piperidinone to the trifluoromethanesulfonic acid is 1:8-12.
  • the first organic solvent is one or more of chloroform, dichloromethane, carbon tetrachloride, dichloroethane, and 1,1,2,2-tetrachloroethane.
  • the second organic solvent is one or more of acetonitrile, tetrahydrofuran, N-methylpyrrolidone, dimethyl sulfoxide, N,N-dimethylacetamide, N,N-dimethylformamide, and sulfolane.
  • the third aspect of this application provides an azulene-branched poly(aryl-piperidine) anion exchange membrane as described in the first aspect, and the azulene-branched poly(aryl-piperidine) anion exchange membrane prepared by the method described in the second aspect for use in the preparation of alkaline fuel cells and alkaline electrolyzers.
  • the azulene-branched poly(aryl-piperidine) anion exchange membrane provided in this application is prepared as an alkaline anion exchange membrane through polymerization and quaternization.
  • the branched structure generates high mechanical strength, which greatly reduces the water absorption and swelling rate of the anion exchange membrane, thereby improving dimensional stability.
  • the highly stable cationic groups and nucleophilic azulene groups increase its alkaline stability. Its high OH- conductivity, alkaline stability and high mechanical strength indicate that the azulene-branched poly(aryl-piperidine) anion exchange membrane prepared in this application can be used as an anion exchange membrane material for alkaline fuel cells and alkaline electrolyzers.
  • the azulene-branched poly(aryl-piperidine) anion exchange membrane provided in this application has high OH- conductivity ( OH- conductivity >100mS cm -1 at 80°C), high mechanical strength (tensile strength >35MPa, elongation at break >10%), high dimensional stability, good processability, and excellent alkaline stability (>500h) in 1M KOH at 80°C.
  • nucleophilic azurite groups in its molecular structure makes the structure less susceptible to OH- attack, thus enhancing its basic stability; the formation of the branched structure causes the molecular chains to entangle with each other, enhancing its mechanical properties.
  • Figure 1 is a synthetic route diagram of the 6,6'-azulene-branched poly(p-terphenyl-piperidine) precursor polymer provided in this application;
  • Figure 2 is a synthetic route diagram of 6,6'-azulene-branched poly(p-terphenyl-piperidine) (h-PTP-BiAz-n) provided in this application;
  • Figure 3 is a comparison of the mechanical properties of the azulene-branched poly(p-terphenyl-piperidine) anion exchange membranes prepared in Examples 1 and 2 and the poly(p-terphenyl-piperidine) anion exchange membrane prepared in Comparative Example 1.
  • Figure 4 shows the swelling rate test results of the azulene-branched poly(p-terphenyl-piperidine) anion exchange membranes prepared in Examples 1 and 2;
  • Figure 5 shows the anion exchange membrane electrolysis test results of the azulene-branched poly(p-terphenyl-piperidine) anion exchange membranes prepared in Examples 1 and 2.
  • the term "at least one” means one or more, and “more than one” means two or more. "At least one of the following” or similar expressions refer to any combination of these items, including any combination of a single item or a plurality of items. For example, “at least one of a, b, or c", or “of a, b, and c”. "At least one” can be: a, b, c, ab (i.e., a and b), ac, bc, or abc, where a, b, and c can be a single or multiple.
  • Ion Exchange Capacity (IEC) Test Method Take an azulene-branched poly(aryl-piperidine) polymer Cl- or Br- type membrane, dry it in a vacuum oven at 75°C, and weigh it. Record the weight of the dry membrane. Immerse the dry membrane in 25 mL of 0.2 M NaNO3 solution for 6 h, repeating three times, and collect the NaNO3 solution after ion exchange. Add potassium chromate solution as an indicator to this solution, and titrate with 0.01 M AgNO3 standard solution. The titration is complete when a brick-red precipitate appears and does not disappear after shaking. Record the volume of AgNO3 solution consumed. Divide the product of the AgNO3 solution concentration and volume by the mass of the dry membrane to obtain the IEC.
  • the electrochemical workstation used was a CHI660E manufactured by Shanghai Chenhua Instrument Co., Ltd.
  • the conductivity of the branched membrane at different temperatures was tested using the electrochemical impedance spectroscopy (EIS).
  • EIS electrochemical impedance spectroscopy
  • the measured potential amplitude was 10 mV.
  • the in-plane resistance of the membrane sample was measured.
  • the membrane was cut into 40 mm ⁇ 10 mm pieces, placed in a fixture, and the fixture was placed in pure water.
  • the test temperature ranged from 30°C to 80°C.
  • the membrane resistance was tested every 10°C, and the membrane was kept warm for 1 hour before testing.
  • ⁇ l/(wdR), where l is the length of the membrane between electrodes (cm), w is the width of the membrane (cm), d is the thickness of the membrane ( ⁇ m), and R is the measured membrane resistance (m ⁇ ).
  • Alkaline fuel cell performance testing The instrument used was a Scribner Associates Co., Ltd., USA, model 850e multi-range fuel cell testing system, tested in current mode. The test conditions were complete humidification with H2 and O2 , test temperature 60°C, 80°C, and H2 and O2 flow rate 200mL/min.
  • Anion exchange membrane (MEA) water electrolysis performance testing The anode was a titanium felt loaded with IrO2 , the cathode was carbon paper loaded with Pt/C, the electrode area was 4 cm2, and the electrolyte was 1 M KOH.
  • An MEA electrolytic cell was assembled. A CHI660e was used for testing, and linear voltammetry was performed on the electrolytic cell.
  • Tensile strength test The dry film sample of 5 ⁇ 0.5cm was tested using an Instron M3300 electronic universal testing machine at a tensile rate of 5mm/min.
  • Alkali stability test The prepared anion exchange membrane was immersed in NaOH solutions of different temperatures and concentrations, and its conductivity was measured at the same time. The alkali stability was analyzed by the change in the conductivity of the electrolyte membrane.
  • embodiments of this application provide an azulene-branched poly(aryl-piperidine) anion exchange membrane, wherein the azulene-branched poly(aryl-piperidine) anion exchange membrane contains an azulene-branched poly(aryl-piperidine) polymer and has the following structure:
  • R is an aromatic group
  • A is an azuleyl branched group
  • a is any integer greater than or equal to
  • b is any integer greater than or equal to 1.
  • the azulene-branched poly(aryl-piperidine) anion exchange membrane provided in this application is an alkaline anion exchange membrane prepared by polymerization and quaternization.
  • the branched structure generates high mechanical strength, which greatly reduces the water absorption and swelling rate of the anion exchange membrane, thereby improving dimensional stability.
  • the highly stable cationic groups and nucleophilic azulene groups increase its alkaline stability. Its high OH- conductivity, alkaline stability and high mechanical strength indicate that the azulene-branched poly(aryl-piperidine) anion exchange membrane prepared in this application can be used as an anion exchange membrane material for alkaline fuel cells and alkaline electrolyzers.
  • R in this application is preferably one of the following structures:
  • R1 and R2 are preferably one of H atoms, aliphatic or aromatic long chains.
  • a of this application embodiment is preferably one of the following structures:
  • embodiments of this application provide a method for preparing the azulene-branched poly(aryl-piperidine) anion exchange membrane as described in the first aspect, the method comprising:
  • the aromatic monomer, azulene branched monomer and N-methyl-4-piperidinone are dissolved in a first organic solvent, trifluoroacetic acid and trifluoromethanesulfonic acid are added, and after reaction, the azulene branched poly(aryl-piperidine) precursor is collected;
  • the azulene branched poly(aryl-piperidine) precursor was dissolved in a second organic solvent, potassium carbonate and iodomethane were added, and after a light-protected reaction, ethyl acetate was added, and the mixture was purified to collect the cationic azulene branched poly(aryl-piperidine).
  • the cationic azulene-branched poly(aryl-piperidine) is dissolved in a third organic solvent, and the Cl - type membrane is collected.
  • the Cl - type membrane is then subjected to ion exchange to obtain an OH - type membrane.
  • the azulene-branched poly(aryl-piperidine) anion exchange membrane is collected.
  • the azulene-branched poly(aryl-piperidine) precursor in the embodiments of this application is prepared by the following method: firstly, aromatic monomers, azulene-branched monomers and N-methyl-4-piperidinone are dissolved in a first organic solvent in a certain proportion to obtain a mixture. The mixture is stirred and reacted at 0-4°C for 30 min. Then, a certain proportion of trifluoroacetic acid and trifluoromethanesulfonic acid are added. After reacting at 0-4°C for a certain time, the resulting viscous solution is placed in excess methanol to precipitate. The obtained polymer solid is collected, washed with potassium carbonate solution and dried to obtain the azulene-branched poly(aryl-piperidine) precursor.
  • azulene branched poly(aryl-piperidine) precursor in the embodiments of this application includes: washing with potassium carbonate solution overnight, then washing three times with deionized water, and vacuum drying.
  • drying temperature is preferably 80°C
  • drying time is preferably 24 hours.
  • N-methyl-4-piperidinone reacts with iodomethane to form a quaternary ammonium cation.
  • ethyl acetate in the embodiments of this application is a good solvent for iodomethane, which can dissolve unreacted monomers. At the same time, it is a poor solvent for polymers, causing the polymers to precipitate and thus purifying the polymers.
  • the molar ratio of the aromatic monomer to the azulene branched monomer in this application embodiment is preferably 0-99:1.
  • the azulene branched monomer has a weak effect on improving the performance of the anion exchange membrane.
  • the molar ratio of the sum of the amounts of azulene branched monomers and aromatic monomers to the amount of N-methyl-4-piperidinone added is preferably 1:0.9-1.2.
  • the molar ratio of N-methyl-4-piperidinone to trifluoroacetic acid is preferably 1:0.8-1.2.
  • the reaction rate will decrease; when the molar ratio of N-methyl-4-piperidinone to trifluoroacetic acid is greater than 1:0.8, the subsequent reaction (addition of trifluoromethanesulfonic acid) may produce severe fumes.
  • the preferred molar ratio of N-methyl-4-piperidinone to trifluoromethanesulfonic acid in this application is 1:8-12.
  • the first organic solvent in this application is preferably one of chloroform, dichloromethane, carbon tetrachloride, dichloroethane, and 1,1,2,2-tetrachloroethane.
  • the first organic solvents serve to dissolve the reactants.
  • the second organic solvent in this application is preferably one of acetonitrile, tetrahydrofuran, N-methylpyrrolidone, dimethyl sulfoxide, N,N-dimethylacetamide, N,N-dimethylformamide, and sulfolane.
  • embodiments of this application provide an azulene-branched poly(aryl-piperidine) anion exchange membrane as described in the first aspect, and the azulene-branched poly(aryl-piperidine) anion exchange membrane prepared by the method described in the second aspect for use in the preparation of alkaline fuel cells and alkaline electrolyzers.
  • the azulene-branched poly(p-terphenyl-piperidine) anion exchange membrane of this application preferably has an OH- conductivity of at least 150 mS/cm at 80°C.
  • Example 1 provides a method for preparing an azulene-branched poly(p-terphenyl-piperidine) anion exchange membrane, specifically a 6,6'-azulene-branched poly(p-terphenyl-piperidine) (h-PTP-BiAz-1) anion exchange membrane.
  • the specific steps are as follows:
  • n represents the molar content of BiAz monomer in percentage form.
  • this application provides a synthesis pathway diagram of the 6,6'-azulene-branched poly(p-terphenyl-piperidine) precursor polymer h-PTPE-BiAz-n, as shown in Figure 1.
  • Figure 1 is a synthesis pathway diagram of the 6,6'-azulene-branched poly(p-terphenyl-piperidine) precursor polymer provided in this application.
  • h-PTPE-BiAz-n polymer 1 g was dissolved in 30 mL of dimethyl sulfoxide (DMSO), followed by the addition of 0.39 g of K2CO3 and 1 mL of iodomethane. The mixture was stirred at room temperature in the dark for 24 h. Ethyl acetate was added to the resulting viscous solution. The pale yellow precipitate was filtered, washed three times with water, and dried under vacuum in an oven at 80 °C for 24 h to obtain h-PTP-BiAz-1.
  • DMSO dimethyl sulfoxide
  • h-PTPE-BiAz-1 (1 g) was dissolved in 30 mL of DMSO.
  • the polymer solution was filtered through a 0.45 ⁇ m polytetrafluoroethylene (PTFE) membrane and cast onto a clean glass plate.
  • the solution was then evaporated at 80 °C for 12 h, 120 °C for 12 h, and vacuum dried at 120 °C for 24 h to completely remove residual solvent.
  • An I-type membrane was obtained by peeling it off the glass plate. Ion exchange was performed in 1 M KCl solution at 80 °C for 12 h, followed by washing three times with deionized water to remove residual salt, yielding a Cl - type membrane.
  • Ion exchange was then performed in 1 M KOH solution at 80 °C for 12 h, followed by washing with deionized water under a nitrogen atmosphere. Washed three times with water, an OH - type membrane was obtained, namely azulene branched poly(aryl-piperidine)h-PTP-BiAz-1 anion exchange membrane.
  • Example 2 provides a method for preparing an azulene-branched poly(p-terphenyl-piperidine) anion exchange membrane, specifically a 6,6'-azulene-branched poly(p-terphenyl-piperidine) (h-PTP-BiAz-2) anion exchange membrane.
  • the specific steps are as follows:
  • h-PTP-BiAz-2 6,6'-azulene-branched poly(p-terphenyl-piperidine) (h-PTP-BiAz-2) anion exchange membrane was prepared according to the method of Example 1, except that the molar content of BiAz monomer in percentage form was 2.
  • Example 2 To verify the performance of the azulene-branched poly(aryl-piperidine) anion exchange membrane prepared in Example 1, the performance of the azulene-branched poly(aryl-piperidine) anion exchange membrane was tested, and the test results are shown in the figure.
  • h-PTP-BiAz-1 anion exchange membrane prepared in Examples 1-2 had an OH- conductivity of 154 mS/cm at 80°C, an ion exchange capacity of 2.4 mmol/g, a swelling ratio of 54%, a tensile strength of 55 MPa, an elongation at break of 10%, and maintained alkaline stability for 1000 h at 80°C in 1M KOH.
  • the h-PTP-BiAz-2 anion exchange membrane had an OH- conductivity of 168 mS/cm at 80°C, an ion exchange capacity of 2.4 mmol/g, a swelling ratio of 42%, a tensile strength of 72 MPa, an elongation at break of 13%, and maintained alkaline stability for 1000 h at 80°C in 1M KOH.
  • This indicates that the homogeneous anion exchange membranes prepared in these examples have low swelling, suitable ion conductivity and anion exchange capacity, and good mechanical properties.
  • the OH- conductivity increases, the swelling ratio decreases, and the mechanical properties are enhanced.
  • Comparative Example 1 provides a method for preparing a poly(p-terphenyl-piperidine) anion exchange membrane (PTP), the specific steps of which are as follows:
  • Poly(p-terphenyl-piperidine) anion exchange membranes were prepared according to the method of Example 1, except that 6,6'-azine monomer was not added.
  • the poly(p-terphenyl-piperidine) anion exchange membrane prepared in Comparative Example 1 had an OH- conductivity of 110 mS/cm at 80°C, an anion exchange capacity of 2.1 mmol/g, a swelling ratio of 55%, a tensile strength of 42 MPa, an elongation at break of 17%, and maintained alkaline stability for 728 h at 80°C in 1M KOH.
  • Figure 3 shows a comparison of the mechanical properties of the azulene-branched poly(p-terphenyl-piperidine) anion exchange membranes prepared in Examples 1 and 2 with those of the poly(p-terphenyl-piperidine) anion exchange membrane prepared in Comparative Example 1.
  • Figure 4 shows the swelling rate test results of the azulene-branched poly(p-terphenyl-piperidine) anion exchange membranes prepared in Examples 1 and 2.
  • Figure 5 shows the water electrolysis test results of the azulene-branched poly(p-terphenyl-piperidine) anion exchange membranes prepared in Examples 1 and 2.
  • the azulene-branched poly(p-terphenyl-piperidine) anion exchange membranes prepared in Examples 1 and 2 exhibit enhanced mechanical properties compared to the poly(p-terphenyl-piperidine) anion exchange membranes prepared in the comparative example.
  • the azulene-branched poly(p-terphenyl-piperidine) anion exchange membranes prepared in Examples 1 and 2 show relative...
  • the swelling ratio of the poly(p-terphenyl-piperidine) anion exchange membrane prepared in the comparative example was reduced.

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Abstract

一种薁基支化聚(芳基-哌啶)阴离子交换膜及其制备方法和应用，涉及膜技术领域，具体制备方法包括：制备薁基支化聚(芳基-哌啶)前驱体；制备阳离子化薁基支化聚(芳基-哌啶)；制备薁基支化聚(芳基-哌啶)阴离子交换膜。如此，通过聚合与季铵化后制备出一种碱性阴离子交换膜，其中，支化结构产生了高机械强度，大大降低了阴离子交换膜的吸水性和溶胀率，从而提高了尺寸稳定性；同时，高稳定性阳离子基团和亲核性薁基基团增加了其碱性稳定性，其高OH-导电率、碱性稳定性和高机械强度表明，该方法制备的薁基支化聚(芳基-哌啶)阴离子交换膜可作为碱性燃料电池和碱性电解池用阴离子交换膜材料。

Description

一种薁基支化聚(芳基-哌啶)阴离子交换膜及其制备方法和应用 技术领域
本申请涉及膜技术领域，尤其涉及一种薁基支化聚(芳基-哌啶)阴离子交换膜及其制备方法和应用。
背景技术
由于全球发展和人口增长，世界范围内的能源需求持续快速增长。发展清洁高效的氢能，符合“碳达峰”、“碳中和”的能源战略，有助于实现人类可持续发展。绿氢可由产能过剩“弃光-弃风废电”驱动的电解水技术制取，而燃料电池为氢能主要的应用方向。目前，在酸性条件下运行的质子交换膜燃料电池和酸性电解池需要使用贵金属催化剂及价格昂贵的质子交换膜，制取氢气和利用氢气的成本过高，工业化发展受到了较大的阻碍。阴离子交换膜燃料电池和碱性电解水技术可以使用低碱性电解液、非贵金属催化剂，使得运行成本大大降低，因此受到了广泛关注。
阴离子交换膜(AEM)是阴离子交换膜燃料电池和碱性电解池的关键组成部分，制备高氢氧根电导率和化学性质稳定的阴离子交换膜至关重要，从而实现阴离子交换膜燃料电池和碱性电解池的高功率密度和长期耐久性。AEM由聚合物骨架，阳离子基团以及可迁移离子构成。聚合物主链结构以及阳离子基团的性质直接决定AEM的性能。AEM的研究目前仍面临以下技术瓶颈：(1)由于OH-的半径比H+的半径大，AEM中OH-电导率仅为相同条件下质子交换膜中H+电导率的20％～33％，然而提高电导率最直接的方式就是提高离子交换容量(IEC)，IEC的提高意味着需要引入更多的亲水阳离子基团，这将导致膜吸水率增加，溶胀变大，从而导致膜的机械性能下降。因此解决膜的离子电导率与尺寸稳定性的“trade-off”效应对AEM的发展至关重要。(2)在热碱工作条件下，聚合物骨架以及阳离子基团易受亲核性OH-的进攻，导致主链结构和阳离子基团发生复杂的降解反应，从而使膜性能下降，甚至降低AEM的使用寿命。
因此，提高AEM的碱稳定性，延长膜使用寿命是急需解决的问题。
发明内容
为了解决现有技术存在的上述技术问题，本申请提供了一种薁基支化聚(芳基-哌啶) 阴离子交换膜及其制备方法和应用，以克服现有技术中AEM离子电导率低、碱稳定性差等问题。
为了实现上述目的，本申请实施例的技术方案是：
本申请的第一方面提供一种薁基支化聚(芳基-哌啶)阴离子交换膜，所述薁基支化聚(芳基-哌啶)阴离子交换膜中含有薁基支化聚(芳基-哌啶)聚合物，具有如下结构：
其中，R为芳香基团，A为薁基支化基团，a为大于等于0的任意整数，b为大于等于1的任意整数。
结合第一方面优选地，所述R为以下结构中的至少一种：
其中，R1和R2为H原子、脂肪族或芳香族长链中的至少一种。
结合第一方面优选地，所述A为以下结构中的至少一种：



本申请的第二方面提供一种第一方面所述的薁基支化聚(芳基-哌啶)阴离子交换膜的制备方法，该制备方法包括：
(1)制备薁基支化聚(芳基-哌啶)前驱体：
使芳香单体、薁基支化单体和N-甲基-4-哌啶酮溶于第一有机溶剂中，加入三氟乙酸和三氟甲烷磺酸，进行反应后，收集薁基支化聚(芳基-哌啶)前驱体；
(2)制备阳离子化薁基支化聚(芳基-哌啶)：
使所述薁基支化聚(芳基-哌啶)前驱体溶于第二有机溶剂中，加入碳酸钾和碘甲烷，进行避光反应后，加入乙酸乙酯，纯化处理，收集阳离子化薁基支化聚(芳基-哌啶)；
(3)制备薁基支化聚(芳基-哌啶)阴离子交换膜：
使所述阳离子化薁基支化聚(芳基-哌啶)溶于第三有机溶剂中，收集Cl-型薄膜，使所述Cl-型薄膜进行离子交换，得到OH-型膜，纯化处理后，收集薁基支化聚(芳基-哌啶)阴离子交换膜。
结合第二方面优选地，所述芳香单体与所述薁基支化单体的摩尔比为0-99：1；
和/或，所述薁基支化单体和所述芳香单体的添加量之和与所述N-甲基-4-哌啶酮的添加量的摩尔比为1：0.9-1.2。
结合第二方面优选地，所述N-甲基-4-哌啶酮与所述三氟乙酸的摩尔比为1：0.8-1.2；
和/或，所述N-甲基-4-哌啶酮与所述三氟甲烷磺酸的摩尔比为1：8-12。
结合第二方面优选地，所述第一有机溶剂为氯仿、二氯甲烷、四氯化碳、二氯乙烷和1,1,2,2-四氯乙烷中的一种或几种。
结合第二方面优选地，所述第二有机溶剂为乙腈、四氢呋喃、N-甲基吡咯烷酮、二甲基亚砜、N,N-二甲基乙酰胺、N,N-二甲基甲酰胺和环丁砜中的一种或几种。
本申请的第三方面提供一种第一方面所述的薁基支化聚(芳基-哌啶)阴离子交换膜，以及第二方面所述方法制备的薁基支化聚(芳基-哌啶)阴离子交换膜用于制备碱性燃料电池和碱性电解池中的应用。
与现有技术相比，本申请实施例的优点或有益效果至少包括：
本申请实施例提供的薁基支化聚(芳基-哌啶)阴离子交换膜，通过聚合与季铵化后制备出一种碱性阴离子交换膜，其中，支化结构产生了高机械强度，大大降低了阴离子交换膜的吸水性和溶胀率，从而提高了尺寸稳定性；同时，高稳定性阳离子基团和亲核性薁基基团增加了其碱性稳定性，其高OH-导电率、碱性稳定性和高机械强度表明，本申请制备的薁基支化聚(芳基-哌啶)阴离子交换膜可作为碱性燃料电池和碱性电解池用阴离子交换膜材料。
本申请提供的薁基支化聚(芳基-哌啶)阴离子交换膜具有高OH-导电率(80℃时，OH-导电率＞100mS cm-1)，高机械强度(抗拉强度>35MPa，断裂伸长率>10％)，高尺寸稳定性，良好的加工性能，和80℃下在1M KOH中优良的碱性稳定性(>500h)。
与其他类型支化聚(芳基-哌啶)阴离子交换膜相比，其分子结构中亲核性薁基基团的引入，使该结构不易受OH-攻击，增强了其碱性稳定性；支化结构的形成，使分子链间互相缠结，增强了其机械性能。
附图说明
图1为本申请提供的6，6’-连薁基支化聚(对三联苯-哌啶)前驱体聚合物的合成路径图；
图2为本申请提供的6，6’-连薁基支化聚(对三联苯-哌啶)(h-PTP-BiAz-n)的合成路径图；
图3是实施例1和2制备的薁基支化聚(对三联苯-哌啶)阴离子交换膜与对比例1制备的聚(对三联苯-哌啶)阴离子交换膜的机械性能对比图；
图4为实施例1和2制备的薁基支化聚(对三联苯-哌啶)阴离子交换膜的溶胀率测试结果；
图5为实施例1和2制备的薁基支化聚(对三联苯-哌啶)阴离子交换膜的阴离子交换膜电解水测试结果。
具体实施方式
为了使本申请的目的、技术方案和优点更加清楚，下面将结合附图对本申请作进一步地详细描述，所描述的实施例不应视为对本申请的限制，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其它实施例，都属于本申请保护的范围。
在以下的描述中，涉及到“一些实施例”，其描述了所有可能实施例的子集，但是可以理解，“一些实施例”可以是所有可能实施例的相同子集或不同子集，并且可以在不冲突的情况下相互结合。除非另有定义，本申请实施例所使用的所有的技术和科学术语与属于本申请实施例的技术领域的技术人员通常理解的含义相同。本申请实施例所使用的术语只是为了描述本申请实施例的目的，不是旨在限制本申请。
在本实施例以下描述中，术语“包括”、“包含”、“具有”和“含有”等均为开放性的用语，即意指包含但不限于。
需要说明的是，本申请实施例中的所有原料/试剂均可在市场上购买或按照本领域技术人员熟知的常规方法制备获得；本申请实施例中的术语“和/或”仅用于描述关联对象的关联关系，表示可以存在三种关系，例如，A和/或B表示单独存在A、单独存在B、同时存在A和B的三种情况，其中，A、B可以为单数或复数，字符“/”一般表示前后关联对象是一种“或”的关系。
在本实施例以下描述中，术语“至少一个”是指一个或者多个，“多个”是指两个或两个以上。“以下至少一项(个)”或其类似表达是指的这些项中的任意组合，包括单项(个)或复数项(个)的任意组合。例如，“a，b或c中的至少一项(个)”，或，“a，b和c中的 至少一项(个)”，均可以表示：a，b，c，a-b(即a和b)，a-c，b-c，或a-b-c，其中a，b，c分别可以是单个，也可以是多个。
本领域技术人员应当理解，在本申请实施例以下描述中，序号的先后并不意味着执行顺序的先后，部分或全部步骤可以并行执行或先后执行，各过程的执行顺序应以其功能和内在逻辑确定，而不应对本申请实施例的实施过程构成任何限定。
在本申请实施例中使用的术语是仅仅出于描述特定实施例的目的，而非旨在限制本申请。在本申请实施例和所附权利要求书中所使用的单数形式的“一种”和“该”也旨在包括多数形式，除非上下文清楚地表示其他含义。
本领域技术人员应当理解，在本申请实施例中的数值范围应理解为还具体公开该范围的上限和下限之间的每个中间值。在任何陈述值和陈述范围内的中间值以及其他任何陈述值或在所述范围内的中间值之间的每个较小的范围也包括在本申请内。这些较小范围的上限和下限可独立地包括或排除在范围内。
除非另有说明，否则本文使用的技术/科学术语具有本申请所述领域的常规技术人员通常理解的相同含义。虽然本申请仅描述优选的方法和材料，但在本申请的实施例或测试例中也可以使用与本文所述相似或等同的任何方法和材料。本说明书中提到的所有文献通常引用并入，用以公开和描述与所述文献相关的方法和/或材料。在与任何并入的文献冲突时，以本申请书的内容为准。
需要说明的是，本申请实施例中的的所有原料和/或试剂均是在市场上购买或按照本领域技术人员熟知的常规方法制备获得。
以下是实施例中所使用到的测试方法：
性能测试：
实施例所涉及的设备和测试方法：
离子交换容量(IEC)测试方法：取薁基支化聚(芳基-哌啶)聚合物的Cl-型或Br-型膜，真空烘箱75℃烘干并称取质量，记录干膜重量。将干膜浸泡在25mL的0.2M NaNO3溶液中6h，重复三次，收集离子交换后的NaNO3溶液。在该溶液中加入指示剂铬酸钾溶液，并用0.01M的AgNO3标准溶液进行滴定，当出现砖红色沉淀且摇晃后不消失即代表滴定完成。记录消耗的AgNO3溶液体积。将AgNO3溶液的浓度与体积的积除以干膜的质量，即为IEC。
电导率的测试：所用电化学工作站为上海辰华仪器公司出产，型号为CHI660E。采用交流阻抗法(EIS)测试支化膜不同温度下电导率。测量的电势振幅为10mV。为了减小接触电阻对测量结果造成的误差，测试的电阻为膜样品的横向(in-plane)电阻。实验中将膜裁成大小为40mm×10mm，置于夹具中，将夹具放于纯水中，测试温度从30℃到80℃， 每隔10℃测试膜电阻，测试前需保温1h。最后根据公式计算样品的离子电导率σ：σ＝l/(wdR)，式中，l为电极间膜的长度(cm)，w为膜的宽度(cm)，d为膜的厚度(μm)，R为测得的膜电阻(mΩ)。
碱性燃料电池性能测试：所用仪器为美国Scribner Associates co.公司生产，仪器型号为850e多量程范围燃料电池测试系统，电流模式下测试。测试条件为H2和O2完全增湿，测试温度60℃，80℃，H2和O2流速为200mL/min。
阴离子交换膜电解水性能测试：阳极为负载IrO2的钛毡，阴极为负载Pt/C的碳纸，电极面积为4cm2，电解液为1M KOH。组装MEA电解池。测试仪器为CHI660e，对电解池进行线性伏安扫描测试。
拉伸强度测试：采用InstronM3300电子万能试验机对干膜样品5×0.5cm进行测试，拉伸速率5mm/min。
碱性稳定性测试：将制得的阴离子膜分别不同温度不同浓度的NaOH溶液中浸泡，同时测量其电导率，通过电解质膜的电导率的变化分析其碱稳定性。
第一方面，本申请实施例提供一种薁基支化聚(芳基-哌啶)阴离子交换膜，所述薁基支化聚(芳基-哌啶)阴离子交换膜中含有薁基支化聚(芳基-哌啶)聚合物，具有如下结构：
其中，R为芳香基团，A为薁基支化基团，a为大于等于0的任意整数，b为大于等于1的任意整数。
本申请实施例提供的薁基支化聚(芳基-哌啶)阴离子交换膜，该材料通过聚合与季铵化后制备出一种碱性阴离子交换膜，其中，支化结构产生了高机械强度，大大降低了阴离子交换膜的吸水性和溶胀率，从而提高了尺寸稳定性；同时，高稳定性阳离子基团和亲核性薁基基团增加了其碱性稳定性，其高OH-导电率、碱性稳定性和高机械强度表明，本申请制备的薁基支化聚(芳基-哌啶)阴离子交换膜可作为碱性燃料电池和碱性电解池用阴离子交换膜材料。
具体实施例中，本申请实施例中的R优选为以下结构中的一种：

其中，R1和R2优选为H原子、脂肪族或芳香族长链中的一种。
具体实施例中，本申请实施例的A优选为以下结构中的一种：



第二方面，本申请实施例提供一种第一方面所述的薁基支化聚(芳基-哌啶)阴离子交换膜的制备方法，该制备方法包括：
(1)制备薁基支化聚(芳基-哌啶)前驱体：
使芳香单体、薁基支化单体和N-甲基-4-哌啶酮溶于第一有机溶剂中，加入三氟乙酸和三氟甲烷磺酸，进行反应后，收集薁基支化聚(芳基-哌啶)前驱体；
(2)制备阳离子化薁基支化聚(芳基-哌啶)：
使所述薁基支化聚(芳基-哌啶)前驱体溶于第二有机溶剂中，加入碳酸钾和碘甲烷，进行避光反应后，加入乙酸乙酯，纯化处理，收集阳离子化薁基支化聚(芳基-哌啶)；
(3)制备薁基支化聚(芳基-哌啶)阴离子交换膜：
使所述阳离子化薁基支化聚(芳基-哌啶)溶于第三有机溶剂中，收集Cl-型薄膜，使所述Cl-型薄膜进行离子交换，得到OH-型膜，纯化处理后，收集薁基支化聚(芳基-哌啶)阴离子交换膜。
需要说明的是，本申请实施例中的薁基支化聚(芳基-哌啶)前驱体是通过以下方式制备：先将芳香单体、薁基支化单体和N-甲基-4-哌啶酮按照一定比例溶解于第一有机溶剂中，得到混合液，将该混合液在0-4℃下搅拌反应30min，之后，加入一定比例的三氟乙酸和三氟甲烷磺酸，在0-4℃下反应一定时间后，将得到的粘性溶液置于过量甲醇中沉淀，收集所得聚合物固体，将该聚合物固体用碳酸钾溶液洗涤、干燥，得到薁基支化聚(芳基-哌啶)前驱体。
需要说明的是，本申请实施例中收集薁基支化聚(芳基-哌啶)前驱体包括：采用碳酸钾溶液洗涤过夜，再使用去离子水洗涤三次，真空干燥。
本申请中对干燥条件并没有特殊限定，能够得到恒重的产物即可。在本申请实施例中，所述干燥的温度优选为80℃，时间优选为24h。
需要说明的是，本申请实施例中是在室温下进行避光搅拌反应24h。
需要说明的是，本申请实施例中的N-甲基-4-哌啶酮与碘甲烷反应后形成季铵阳离子。
需要说明的是，本申请实施例中的乙酸乙酯作为碘甲烷的良溶剂，可以溶解未反应单体，同时作为聚合物的不良溶剂，使聚合物发生沉淀，从而纯化聚合物。
具体实施例中，本申请实施例中所述芳香单体与所述薁基支化单体的摩尔比优选为0-99：1。
其中，当芳香单体与所述薁基支化单体的摩尔比大于99：1时，即薁基支化单体含量过低时，薁基支化单体对阴离子交换膜性能的提升效果微弱。
具体实施例中，本申请实施例中薁基支化单体和芳香单体的添加量之和与N-甲基-4-哌啶酮的添加量的摩尔比优选为1：0.9-1.2。
具体实施例中，本申请实施例中N-甲基-4-哌啶酮与三氟乙酸的摩尔比优选为1：0.8-1.2。
其中，当N-甲基-4-哌啶酮与三氟乙酸的摩尔比小于1：1.2时，反应速率会降低；当N-甲基-4-哌啶酮与三氟乙酸的摩尔比大于1：0.8时，后续反应(加入三氟甲烷磺酸)时可能会发烟严重。
具体实施例中，本申请实施例中N-甲基-4-哌啶酮与三氟甲烷磺酸的摩尔比优选为1：8-12。
其中，当N-甲基-4-哌啶酮与三氟甲烷磺酸的摩尔比小于1：12时，会发生局部聚合速率过快，导致分子量分布过宽；当N-甲基-4-哌啶酮与三氟甲烷磺酸的摩尔比大于1：8时，反应产率和速率会降低。
具体实施例中，本申请实施例中的第一有机溶剂优选为氯仿、二氯甲烷、四氯化碳、二氯乙烷和1,1,2,2-四氯乙烷中的一种。
其中，该些第一有机溶剂起到溶解反应物的作用。
具体实施例中，本申请实施例中的第二有机溶剂优选为乙腈、四氢呋喃、N-甲基吡咯烷酮、二甲基亚砜、N,N-二甲基乙酰胺、N,N-二甲基甲酰胺和环丁砜中的一种。
其中，该些第二有机溶剂起到溶解反应物并使聚合物沉淀的作用。
第三方面，本申请实施例提供一种第一方面所述的薁基支化聚(芳基-哌啶)阴离子交换膜，以及第二方面所述方法制备的薁基支化聚(芳基-哌啶)阴离子交换膜用于制备碱性燃料电池和碱性电解池中的应用。
具体实施例中，本申请实施例的薁基支化聚(对三联苯-哌啶)阴离子交换膜在80℃下的OH-导电率优选为至少150mS/cm。
下面将结合具体实施例对本申请的技术方法作进一步地阐述。
实施例1
本实施例1提供一种薁基支化聚(对三联苯-哌啶)阴离子交换膜，即6,6’-连薁基支化聚(对三联苯-哌啶)(h-PTP-BiAz-1)阴离子交换膜的制备方法，具体步骤如下：
(1)制备薁基支化聚(芳基-哌啶)前驱体，即制备6，6’-连薁基支化聚(对三联苯-哌啶)前驱体聚合物(h-PTP-BiAz-n)：
将对三联苯TP(2.30g，10mmol)、6，6-连薁BiAz(0.025g，0.10mmol)、N-甲基-4-哌啶酮mPip(1.15g，10.15mmol)加入到二氯甲烷DCM(17mL)中形成溶液，将溶液在0℃下搅拌30min，将三氟乙酸TFA(0.82mL，10.1mmol)和三氟甲烷磺酸TFSA(8.97mL，101mmol)滴入溶液中，6h后，将得到的粘性溶液倒入过量的甲醇中沉淀，收集所得蓝色聚合物纤维；在50℃下，固体用1M K2CO3溶液洗涤过夜，再用去离子水洗涤三次，80℃真空干燥24h，得到h-PTPE-BiAz-1。其中，n为BiAz单体的百分比形式的摩尔含量。
为了便于理解上述6，6’-连薁基支化聚(对三联苯-哌啶)前驱体聚合物的合成过程，本申请提供一种6，6’-连薁基支化聚(对三联苯-哌啶)前驱体聚合物h-PTPE-BiAz-n的合成路径图，如图1所示，图1为本申请提供的6，6’-连薁基支化聚(对三联苯-哌啶)前驱体聚合物的合成路径图。
(2)制备阳离子化薁基支化聚(芳基-哌啶)，即6，6’-连薁基支化聚(对三联苯-哌啶)(h-PTP-BiAz-1)：
将1g h-PTPE-BiAz-n聚合物溶于30mL二甲基亚砜(DMSO)中，然后加入K2CO3(0.39g)和碘甲烷(1mL)，在暗处室温搅拌反应24h。在得到的粘性溶液中加入乙酸乙酯。将淡黄色沉淀物过滤后，用水洗涤三次，在80℃的烘箱中真空干燥24h，得到h-PTP-BiAz-1。
为了便于理解上述6，6’-连薁基支化聚(对三联苯-哌啶)(h-PTP-BiAz-n)的合成过程，本申请提供一种6，6’-连薁基支化聚(对三联苯-哌啶)(h-PTP-BiAz-n)的合成路径图，如图2所示，图2为本申请提供的6，6’-连薁基支化聚(对三联苯-哌啶)(h-PTP-BiAz-n)的合成路径图。
(3)制备薁基支化聚(芳基-哌啶)阴离子交换膜：
将h-PTPE-BiAz-1(1g)溶解于30mL DMSO中，聚合物溶液通过0.45μm聚四氟乙烯滤膜过滤，并浇铸在干净的玻璃板上。随后，将溶液在80℃下蒸发12h，120℃下蒸发12h，在120℃下真空干燥24h，完全去除残留溶剂。从玻璃板上剥离得到I-型膜。在1M KCl溶液中，在80℃条件下，离子交换12h，然后用去离子水洗涤3次，去除残留的盐，得到Cl-型的膜。在1M KOH溶液中，80℃放置12h进行离子交换，然后在氮气气氛下用去离 子水洗涤3次，得到OH-型膜，即薁基支化聚(芳基-哌啶)h-PTP-BiAz-1阴离子交换膜。
实施例2
本实施例2提供一种薁基支化聚(对三联苯-哌啶)阴离子交换膜，即6,6’-连薁基支化聚(对三联苯-哌啶)(h-PTP-BiAz-2)阴离子交换膜的制备方法，具体步骤如下：
按照实施例1的方法制备6,6’-连薁基支化聚(对三联苯-哌啶)(h-PTP-BiAz-2)阴离子交换膜，所不同的是BiAz单体的百分比形式的摩尔含量为2。
为了验证实施例1制备的薁基支化聚(芳基-哌啶)阴离子交换膜的性能，对薁基支化聚(芳基-哌啶)阴离子交换膜进行性能测试，测试结果如图所示。
经测试表明，本实施例1-2中制备的h-PTP-BiAz-1阴离子交换膜在80℃下OH-导电率为154mS/cm，其离子交换容量为2.4mmol/g，溶胀率为54％，拉伸强度为55MPa，断裂伸长率10％，在80℃、1M KOH中保持碱性稳定性1000h。同时，h-PTP-BiAz-2阴离子交换膜在80℃下OH-导电率为168mS/cm，其离子交换容量为2.4mmol/g，溶胀率为42％，拉伸强度为72MPa，断裂伸长率13％，在80℃、1M KOH中保持碱性稳定性1000h，表明本实施例中所制备的均相阴离子交换膜溶胀较小，具有合适的离子传导率和阴离子交换容量，机械性能良好；且随着薁基单体添加量的提高，OH-电导率升高，溶胀率降低，机械性能得到增强。
对比例1
本对比例1提供一种聚(对三联苯-哌啶)阴离子交换膜(PTP)的制备方法，具体步骤如下：
按照实施例1的方法制备聚(对三联苯-哌啶)阴离子交换膜(PTP)，所不同的是不添加6，6’-连薁单体。
经测试表明，本对比例1中制备的聚(对三联苯-哌啶)阴离子交换膜在80℃下OH-导电率为110mS/cm，其阴离子交换容量为2.1mmol/g，溶胀率为55％，拉伸强度为42MPa，断裂伸长率17％，在80℃、1M KOH中保持碱性稳定性728h。
图3为实施例1和2制备的薁基支化聚(对三联苯-哌啶)阴离子交换膜与对比例1制备的聚(对三联苯-哌啶)阴离子交换膜的机械性能对比图。图4为实施例1和2制备的薁基支化聚(对三联苯-哌啶)阴离子交换膜的溶胀率测试结果。图5为实施例1和2制备的薁基支化聚(对三联苯-哌啶)阴离子交换膜的阴离子交换膜电解水测试结果。
根据图3可知，实施例1和2制备的薁基支化聚(对三联苯-哌啶)阴离子交换膜相对于对比例中所制备的聚(对三联苯-哌啶)阴离子交换膜机械性能得到增强。
根据图4可知，实施例1和2制备的薁基支化聚(对三联苯-哌啶)阴离子交换膜相对 于对比例中所制备的聚(对三联苯-哌啶)阴离子交换膜溶胀率降低。
根据图5可知，实施例1和2制备的薁基支化聚(对三联苯-哌啶)阴离子交换膜相对于对比例中所制备的聚(对三联苯-哌啶)阴离子交换膜在阴离子交换膜电解水中性能得到增强。
结果显示，本对比例中所制备的阴离子交换膜与实施例1和2中所制备的阴离子交换膜相比，性能有明显下降。
以上所述，仅为本申请的具体实施方式，但本申请的保护范围并不局限于此，任何熟悉本技术领域的技术人员在本申请揭露的技术范围内，可轻易想到变化或替换，都应涵盖在本申请的保护范围之内。因此，本申请的保护范围应以所述权利要求的保护范围为准。

Claims (10)

  1. 一种薁基支化聚(芳基-哌啶)阴离子交换膜，其特征在于，所述薁基支化聚(芳基-哌啶)阴离子交换膜中含有薁基支化聚(芳基-哌啶)聚合物，具有如下结构：
    其中，R为芳香基团，A为薁基支化基团，a为大于等于0的任意整数，b为大于等于1的任意整数。
  2. 根据权利要求1所述的薁基支化聚(芳基-哌啶)阴离子交换膜，其特征在于，所述R为以下结构中的至少一种：
    其中，R1、R2为H原子、脂肪族或芳香族长链中的一种或几种。
  3. 根据权利要求1所述的薁基支化聚(芳基-哌啶)阴离子交换膜，其特征在于，所述A为以下结构中的至少一种：




  4. 一种权利要求1-3任一所述的薁基支化聚(芳基-哌啶)阴离子交换膜的制备方法，其特征在于，包括：
    (1)制备薁基支化聚(芳基-哌啶)前驱体：
    使芳香单体、薁基支化单体和N-甲基-4-哌啶酮溶于第一有机溶剂中，加入三氟乙酸和三氟甲烷磺酸，进行反应后，收集薁基支化聚(芳基-哌啶)前驱体；
    (2)制备阳离子化薁基支化聚(芳基-哌啶)：
    使所述薁基支化聚(芳基-哌啶)前驱体溶于第二有机溶剂中，加入碳酸钾和碘甲烷，进行避光反应后，加入乙酸乙酯，纯化处理，收集阳离子化薁基支化聚(芳基-哌啶)；
    (3)制备薁基支化聚(芳基-哌啶)阴离子交换膜：
    使所述阳离子化薁基支化聚(芳基-哌啶)溶于第三有机溶剂中，收集Cl-型薄膜，使所述Cl-型薄膜进行离子交换，得到OH-型膜，纯化处理后，收集薁基支化聚(芳基-哌啶)阴离子交换膜。
  5. 根据权利要求4所述的薁基支化聚(芳基-哌啶)阴离子交换膜的制备方法，其特征在于，所述芳香单体与所述薁基支化单体的摩尔比为0-99：1；
    和/或，所述薁基支化单体和所述芳香单体的添加量之和与所述N-甲基-4-哌啶酮的添加量的摩尔比为1：0.9-1.2。
  6. 根据权利要求4所述的薁基支化聚(芳基-哌啶)阴离子交换膜的制备方法，其特征在于，所述N-甲基-4-哌啶酮与所述三氟乙酸的摩尔比为1：0.8-1.2；
    和/或，所述N-甲基-4-哌啶酮与所述三氟甲烷磺酸的摩尔比为1：8-12。
  7. 根据权利要求4所述的薁基支化聚(芳基-哌啶)阴离子交换膜的制备方法，其特征在于，所述第一有机溶剂为氯仿、二氯甲烷、四氯化碳、二氯乙烷和1,1,2,2-四氯乙烷中的一种或几种。
  8. 根据权利要求4所述的薁基支化聚(芳基-哌啶)阴离子交换膜的制备方法，其特征 在于，所述第二有机溶剂为乙腈、四氢呋喃、N-甲基吡咯烷酮、二甲基亚砜、N,N-二甲基乙酰胺、N,N-二甲基甲酰胺和环丁砜中的一种或几种。
  9. 一种根据权利要求1-3任一所述的薁基支化聚(芳基-哌啶)阴离子交换膜，以及根据权利要求4-7任一所述方法制备的薁基支化聚(芳基-哌啶)阴离子交换膜在制备碱性燃料电池和碱性电解池中的应用。
  10. 根据权利要求9所述的应用，其特征在于，所述薁基支化聚(对三联苯-哌啶)阴离子交换膜在80℃下的OH-导电率为至少150mS/cm。
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