WO2016205973A1 - 一种偏氟聚芳芴醚噁二唑两性离子交换膜及其制备方法 - Google Patents

一种偏氟聚芳芴醚噁二唑两性离子交换膜及其制备方法 Download PDF

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WO2016205973A1
WO2016205973A1 PCT/CN2015/000448 CN2015000448W WO2016205973A1 WO 2016205973 A1 WO2016205973 A1 WO 2016205973A1 CN 2015000448 W CN2015000448 W CN 2015000448W WO 2016205973 A1 WO2016205973 A1 WO 2016205973A1
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oxadiazole
exchange membrane
ion exchange
amphoteric ion
polyarylene ether
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谢晓峰
费哲君
王树博
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Tsinghua 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
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/08—Polyhydrazides; Polytriazoles; Polyaminotriazoles; Polyoxadiazoles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/20—Manufacture of shaped structures of ion-exchange resins
    • C08J5/22—Films, membranes or diaphragms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/06—Polyhydrazides; Polytriazoles; Polyamino-triazoles; Polyoxadiazoles
    • 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
    • H01M8/02—Details
    • 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
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    • Y02E60/50—Fuel cells

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  • the invention belongs to the technical field of fuel cell materials, and particularly relates to a fluorine-containing polyarylene ether oxadiazole amphoteric ion exchange membrane and a preparation method thereof.
  • Ion exchange membrane is one of the most important components, and its properties directly affect the performance of the battery.
  • the film is already excellent in performance, it has the disadvantage of high vanadium ion permeability and high cost. Therefore, the researchers tried to find an alternative A novel ion exchange membrane for membranes.
  • cation exchange membranes and anion exchange membranes are the main research objects, while studies on amphoteric ion exchange membranes are rare.
  • the cation exchange membrane is proton-excited because of its high ion conductivity, but vanadium resistance is often poor.
  • the anion exchange membrane has a relatively low ionic conductivity, but its vanadium resistance is stronger due to the Donnan effect.
  • the original intention of the zwitterionic exchange membrane design is to combine the advantages of the cation exchange membrane and the anion exchange membrane.
  • the polymer structure of the zwitterionic exchange membrane there are both acidic functional groups to ensure the transport of ions and basic functional groups to block the passage of larger cations such as vanadium ions.
  • the main methods for preparing an amphoteric ion exchange membrane include a copolymerization method and a radiation grafting method. Radiation grafting is the process of radiation grafting a polymer into a polymer solution with functional groups.
  • the EFTE-based amphoteric ion exchange membrane prepared by radiation grafting has an ion conductivity of 39 mS ⁇ cm -1 and a vanadium ion permeability coefficient of 5.21 ⁇ 10 -9 cm 2 ⁇ min -1 .
  • the coefficient of the 117 film is two orders of magnitude smaller.
  • the amphoteric ion exchange membrane prepared by the radiation grafting method using PVDF as the base film has an ion conductivity of 45 mS ⁇ cm -1 when the degree of grafting is 25%, and the vanadium ion permeability coefficient is greatly reduced.
  • the copolymerization rule is to copolymerize a monomer having a heterophilic charge functional group.
  • the sulfonate is introduced on the difluorobenzophenone
  • the quaternary ammonium group is introduced on the bisphenol oxime
  • the amphoteric ion exchange membrane is prepared by copolymerizing the two monomers.
  • the ion conductivity is 10.8 mS ⁇ cm -1 at room temperature, vanadium ion.
  • the permeability coefficient is 0.88 ⁇ 10 -7 cm 2 ⁇ min -1 .
  • the current method for preparing an amphoteric ion exchange membrane is cumbersome.
  • the radiation grafting method requires a radiation source
  • the copolymerization method requires a functional group that introduces an opposite charge on the monomer in advance.
  • the present invention provides a fluorinated polyarylene ether oxadiazole amphoteric ion exchange membrane and a preparation method thereof, and the specific technical scheme is as follows:
  • a fluorinated polyarylene ether oxadiazole amphoteric ion exchange membrane wherein the fluorinated polyarylene ether oxadiazole amphoteric ion exchange membrane is obtained by copolymerization of a monomer to obtain a base polymer, and then reacted with a functionalizing agent. owned;
  • the fluorinated polyarylene ether oxadiazole amphoteric ion exchange membrane has a sulfonic acid group as a strong acidic functional group for increasing ionic conductivity; and an amino group as a weakly basic functional group for blocking passage of large volume cations;
  • the ion conductivity of the fluorine-containing polyarylene ether oxadiazole amphoteric ion exchange membrane at 70 ° C is 58 mS ⁇ cm -1 or more.
  • the monomer is decafluorobenzene oxadiazole and bisphenol oxime; and the functionalizing agent is aminophenol sulfonic acid and a derivative thereof.
  • aminophenolsulfonic acid and its derivative are 2-aminophenol-4-sulfonic acid.
  • the bulk cation is vanadium ion
  • the vanadium ion permeability coefficient of the fluorinated polyarylene ether oxadiazole amphoteric ion exchange membrane is 1.56 ⁇ 10 -8 cm 2 ⁇ min ⁇ 1 .
  • a preparation method of a fluorine-containing polyarylene ether oxadiazole amphoteric ion exchange membrane the specific steps are as follows:
  • the plate was placed in an oven at 70 ° C to volatilize the solvent, and after 12 hours, it was taken out to obtain a fluorine-containing polyarylene ether oxadiazole amphoteric ion exchange membrane; wherein the 2-aminophenol-4-sulfonic acid, base polymerization
  • the catalyst is potassium fluoride or potassium carbonate.
  • the solvent is N,N-dimethylformamide.
  • the zwitterionic proton membrane prepared by the invention has high ionic conductivity, the ion conductivity is 20.7 mS ⁇ cm -1 at 40 ° C, and the conductivity reaches 58.5 mS at 70 ° C. ⁇ cm -1 .
  • the prepared amphoteric film has superior vanadium resistance and its vanadium ion permeability coefficient is 1.56 ⁇ 10 -8 cm 2 ⁇ min -1 . 117 is two orders of magnitude smaller.
  • the invention adopts a novel one-step method for preparing an amphoteric ion exchange membrane, which has simple experimental steps and convenient and easy to obtain raw materials.
  • FIG. 1 is a schematic view showing a preparation process of a fluorinated polyarylene ether oxadiazole amphoteric ion exchange membrane
  • FIG. 2 is a graph showing the ionic conductivity of the fluorinated polyarylene ether oxadiazole amphoteric ion exchange membrane obtained in the present invention.
  • the present invention provides a fluorine-containing polyarylene ether oxadiazole amphoteric ion exchange membrane and a preparation method thereof, and the present invention will be further described below in conjunction with the accompanying drawings and specific embodiments.
  • the structure of the fluorinated polyarylene ether oxadiazole amphoteric ion exchange membrane was confirmed by 19 F spectrum.
  • the peak position of the 19 F spectrum of decafluorobenzene oxadiazole (FPOx) corresponds to the literature value, which proves the successful preparation of the monomer.
  • FPOx decafluorobenzene oxadiazole
  • the peak corresponding to the para-F atom disappeared, demonstrating that the para-F atom has been completely replaced by bisphenol quinone.
  • the peak area corresponding to the Ox ortho-F atom is reduced.
  • the ratio is 0.7:1, which is basically understood as per One of the four ortho-F atoms is replaced by an aromatic nucleophile.
  • the ionic conductivity of the fluorinated polyarylene ether oxadiazole amphiphilic ion exchange membrane increases with increasing temperature.
  • the conductivity is 20.7 mS ⁇ cm -1
  • the conductivity reaches 58.5 mS ⁇ cm -1 .
  • the tensile strength and Young's modulus of the fluorinated polyarylene ether oxadiazole amphoteric ion exchange membrane are both 117 film is large, and Young's modulus is Four times the 117 membrane.
  • Good mechanical properties are the structural basis for the long-term operation of ion exchange membranes in batteries.
  • the vanadium ion permeability coefficient of the fluorinated polyarylene ether oxadiazole amphoteric ion exchange membrane was 1.56 ⁇ 10 -8 cm 2 .min -1 by the vanadium ion permeability test. 117 is two orders of magnitude smaller. The lower vanadium ion permeability can effectively suppress the cross-contamination of the positive and negative electrolytes to improve the coulombic efficiency of the all-vanadium flow battery.

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Abstract

本发明公开了一种偏氟聚芳芴醚噁二唑两性离子交换膜及其制备方法。所述两性离子交换膜通过一步法制备得到，具体为：将十氟苯噁二唑和双酚芴共聚得到基础聚合物，再与功能化试剂混合反应，成膜，得到所述两性离子交换膜。其中与功能化试剂的反应主要是通过芳香亲核取代实现的。本发明得到的两性离子交换膜具有较高的离子传导率，在40℃时，其离子传导率为20.7mS·cm-1，而在70℃，其传导率达到58.5mS·cm-1。此外，本发明得到的两性离子交换膜拥有优越的阻钒性，其钒离子渗透系数为1.56×10-8cm2·min-1，比Nafion® 117小两个数量级。本发明采用了一种新颖的一步制备两性离子交换膜的方法，实验步骤简单，原料方便易得。

Description

一种偏氟聚芳芴醚噁二唑两性离子交换膜及其制备方法 技术领域
本发明属于燃料电池材料技术领域，具体涉及一种偏氟聚芳芴醚噁二唑两性离子交换膜及其制备方法。
背景技术
液流电池作为一种重要的储能装置，受到了越来越多人的关注。离子交换膜是其中非常重要的部件之一，其性质的好坏直接影响电池的性能。目前普遍使用的
Figure PCTCN2015000448-appb-000001
膜虽然性能已经非常优异，但存在钒离子渗透率高以及成本高昂的缺点。因此，研究人员试图找出一种可以替代
Figure PCTCN2015000448-appb-000002
膜的新型离子交换膜。目前，阳离子交换膜和阴离子交换膜是主要的研究对象，而两性离子交换膜的研究较少。阳离子交换膜因其传输的是质子，一般而言，离子传导率较高，但阻钒性往往不好。相反，阴离子交换膜的离子传导率相对较低，但因为Donnan效应，其阻钒性较强。
两性离子交换膜设计的初衷便是将阳离子交换膜和阴离子交换膜的优点结合起来。在两性离子交换膜的聚合物结构上，既有酸性官能基团来保证离子的传输，又有碱性官能基团来阻挡较大阳离子如钒离子的通过。目前制备两性离子交换膜采用的主要方法有共聚法和辐射接枝法等。辐射接枝法是将聚合物置于带官能基团的聚合物溶液中进行辐射接枝。通过辐射接枝法制备的以EFTE为基底的两性离子交换膜，离子传导率为39mS·cm-1，钒离子渗透系数为5.21×10-9cm2·min-1，比
Figure PCTCN2015000448-appb-000003
117膜的系数小两个数量级。以PVDF为基膜通过辐射接枝法制备的两性离子交换膜，当接枝度为25％时，离子传导率达到45mS·cm-1，而钒离子渗透系数大大降低。共聚法则是将带有异性电荷官能基团的单体进行共聚。例如在二氟二苯酮上引入磺酸根，在双酚芴上引入季铵基团，再将两种单体进行共聚制备两性离子交换膜，室温下离子传导率为10.8mS·cm-1，钒离子渗透系数为0.88×10-7cm2·min-1。综上所述，目前制备两性离子交换膜的方法较为繁琐。辐射接枝法需要辐射源，共聚法则需要事先在单体上引入异性电荷的官能团。
发明内容
针对现有技术的不足，本发明提供了一种偏氟聚芳芴醚噁二唑两性离子交换膜及其制备方法，具体技术方案如下：
一种偏氟聚芳芴醚噁二唑两性离子交换膜，所述偏氟聚芳芴醚噁二唑两性离子交换膜是通过单体共聚得到基础聚合物，然后再与功能化试剂进行反应所得到的；
所述偏氟聚芳芴醚噁二唑两性离子交换膜以磺酸基作为强酸性官能团，用以提高离子传 导率；以氨基作为弱碱性官能团，用以阻挡大体积阳离子的通过；所述偏氟聚芳芴醚噁二唑两性离子交换膜在70℃时的离子传导率为58mS.cm-1以上。
进一步地，所述单体为十氟苯噁二唑和双酚芴；所述功能化试剂为氨基苯酚磺酸及其衍生物。
进一步地，所述氨基苯酚磺酸及其衍生物为2-氨基苯酚-4-磺酸。
进一步地，所述大体积阳离子为钒离子，所述偏氟聚芳芴醚噁二唑两性离子交换膜的钒离子渗透系数为1.56×10-8cm2·min-1。
一种偏氟聚芳芴醚噁二唑两性离子交换膜的制备方法，具体步骤如下：
(1)基础聚合物的制备：将十氟苯噁二唑和双酚芴混合溶于溶剂中，加入催化剂，然后在冰浴下反应3-4小时，至溶液明显变粘稠后停止反应；将反应溶液倾倒于甲醇与水的混合溶液中进行析出，洗涤、干燥，得到基础聚合物；其中所述十氟苯噁二唑、双酚芴和催化剂的摩尔比为十氟苯噁二唑∶双酚芴∶催化剂＝1∶1∶(1.5～4)；
(2)偏氟聚芳芴醚噁二唑两性离子交换膜的制备：将所述基础聚合物溶于溶剂中，再加入2-氨基苯酚-4-磺酸和催化剂，在60℃下反应3天；将反应溶液倾倒于乙酸乙酯中进行析出，洗涤、干燥，在1mol·L-1的硫酸中浸泡1天，用去离子水洗涤；将所得反应物溶于溶剂中，倾倒于光滑玻璃板上，并置于70℃烘箱中让溶剂挥发，12小时后取出，即得偏氟聚芳芴醚噁二唑两性离子交换膜；其中所述2-氨基苯酚-4-磺酸、基础聚合物中重复单元和催化剂的摩尔比为2-氨基苯酚-4-磺酸∶基础聚合物中重复单元∶催化剂＝2∶1∶6。
进一步地，所述催化剂为氟化钾或碳酸钾。
进一步地，所述溶剂为N，N-二甲基甲酰胺。
本发明的有益效果为：本发明制备得到的两性离子质子膜具有较高的离子传导率，在40℃时，离子传导率为20.7mS·cm-1，而在70℃，传导率达到58.5mS·cm-1。所制备的两性膜拥有优越的阻钒性，其钒离子渗透系数为1.56×10-8cm2·min-1，比
Figure PCTCN2015000448-appb-000004
117小两个数量级。本发明采用了一种新颖的一步制备两性离子交换膜的方法，实验步骤简单，原料方便易得。
附图说明
图1为偏氟聚芳芴醚噁二唑两性离子交换膜的制备流程示意图；
图2为本发明所得到的偏氟聚芳芴醚噁二唑两性离子交换膜的离子传导率曲线图。
具体实施方式
本发明提供了一种偏氟聚芳芴醚噁二唑两性离子交换膜及其制备方法，下面结合附图和具体实施方式对本发明做进一步说明。
实施例1
在烧瓶中加入1.2081g十氟苯噁二唑(FPOx)和1.5012g双酚芴后加入30mL二甲基甲酰胺(DMF)让其均匀溶解。再加入1.24g过量催化剂碳酸钾，让溶液在冰浴环境下搅拌3-4小时，至溶液明显变粘稠后停止反应。将反应溶液倾倒于甲醇与水的混合溶液中进行析出，反复洗涤与干燥后，得到基础聚合物FPFEO。
在烧瓶中加入1.5g FPFEO和30mL DMF让其充分溶解后加入1.2g 2-氨基苯酚-4磺酸与过量碳酸钾，让溶液在60℃搅拌反应3天。之后将反应溶液倾倒于乙酸乙酯中进行析出，并反复洗涤与干燥。再将产物在1mol·L-1的硫酸中浸泡1天，后用去离子水反复洗涤，得到带官能基团的聚合物FPFEO-SN。
将FPFEO-SN溶于适量的DMF中后将溶液倾倒于光滑玻璃板上，并置于70℃烘箱中让溶剂挥发，12小时后取出，即得两性离子交换膜。其制备流程如图1所示。
通过19F谱图对偏氟聚芳芴醚噁二唑两性离子交换膜的结构进行了确证。其中十氟苯噁二唑(FPOx)的19F谱出峰位置与文献值相应，证明了单体的成功制备。而在基础聚合物FPFEO的19F谱中，对位F原子对应的峰消失了，证明了对位F原子已经完全被双酚芴取代。在终产物FPFEO-SN的19F谱中，Ox邻位F原子所对应的峰面积有所减小，相较于对位F原子的峰面积，其比值为0.7∶1，基本可以理解为每4个邻位F原子中，有一个被芳香亲核试剂取代。
通过溶胀性和吸水性的测试，偏氟聚芳芴醚噁二唑两性离子交换膜的溶胀率和吸水率均较小，证明其在使用过程中，不会产生较大的形变。
通过离子传导性能的测试，偏氟聚芳芴醚噁二唑两性离子交换膜的离子传导率随着温度的上升而增大。当温度为40℃时，其传导率为20.7mS·cm-1，而当温度上升到70℃时，其传导率达到58.5mS·cm-1。
通过机械性能的测试，偏氟聚芳芴醚噁二唑两性离子交换膜的拉伸强度和杨氏模量都比
Figure PCTCN2015000448-appb-000005
117膜大，且杨氏模量是
Figure PCTCN2015000448-appb-000006
117膜的四倍。良好的机械性能是离子交换膜在电池中长期运行的结构基础。
通过钒离子渗透性的测试，偏氟聚芳芴醚噁二唑两性离子交换膜的钒离子渗透系数为1.56×10-8cm2.min-1，比
Figure PCTCN2015000448-appb-000007
117小两个数量级。较低的钒离子透过率能够有效遏制正负极电解液的交叉污染，以提高全钒液流电池的库伦效率。
以上所述，仅为本发明的具体可操作实施方式，本发明的保护范围以权利要求书为准。

Claims (7)

  1. 一种偏氟聚芳芴醚噁二唑两性离子交换膜，其特征在于，所述偏氟聚芳芴醚噁二唑两性离子交换膜是通过单体共聚得到基础聚合物，然后再与功能化试剂进行反应所得到的；
    所述偏氟聚芳芴醚噁二唑两性离子交换膜以磺酸基作为强酸性官能团，用以提高离子传导率；以氨基作为弱碱性官能团，用以阻挡大体积阳离子的通过；所述偏氟聚芳芴醚噁二唑两性离子交换膜在70℃时的离子传导率为58mS·cm-1以上。
  2. 根据权利要求1所述的一种偏氟聚芳芴醚噁二唑两性离子交换膜，其特征在于，所述单体为十氟苯噁二唑和双酚芴；所述功能化试剂为氨基苯酚磺酸及其衍生物。
  3. 根据权利要求2所述的一种偏氟聚芳芴醚噁二唑两性离子交换膜，其特征在于，所述氨基苯酚磺酸及其衍生物为2-氨基苯酚-4-磺酸。
  4. 根据权利要求1所述的一种偏氟聚芳芴醚噁二唑两性离子交换膜，其特征在于，所述大体积阳离子为钒离子，所述偏氟聚芳芴醚噁二唑两性离子交换膜的钒离子渗透系数为1.56×10-8cm2·min-1。
  5. 根据权利要求1-4任意一项权利要求所述的一种偏氟聚芳芴醚噁二唑两性离子交换膜的制备方法，其特征在于，具体步骤如下：
    (1)基础聚合物的制备：将十氟苯噁二唑和双酚芴混合溶于溶剂中，加入催化剂，然后在冰浴下反应3-4小时，至溶液明显变粘稠后停止反应；将反应溶液倾倒于甲醇与水的混合溶液中进行析出，洗涤、干燥，得到基础聚合物；其中所述十氟苯噁二唑、双酚芴和催化剂的摩尔比为十氟苯噁二唑∶双酚芴∶催化剂＝1∶1∶(1.5～4)；
    (2)偏氟聚芳芴醚噁二唑两性离子交换膜的制备：将所述基础聚合物溶于溶剂中，再加入2-氨基苯酚-4-磺酸和催化剂，在60℃下反应3天；将反应溶液倾倒于乙酸乙酯中进行析出，洗涤、干燥，在1mol·L-1的硫酸中浸泡1天，用去离子水洗涤；将所得反应物溶于溶剂中，倾倒于光滑玻璃板上，并置于70℃烘箱中让溶剂挥发，12小时后取出，即得偏氟聚芳芴醚噁二唑两性离子交换膜；其中所述2-氨基苯酚-4-磺酸、基础聚合物中重复单元和催化剂的摩尔比为2-氨基苯酚-4-磺酸∶基础聚合物中重复单元∶催化剂＝2∶1∶6。
  6. 根据权利要求5所述的一种偏氟聚芳芴醚噁二唑两性离子交换膜的制备方法，其特征在于，所述催化剂为氟化钾或碳酸钾。
  7. 根据权利要求5所述的一种偏氟聚芳芴醚噁二唑两性离子交换膜的制备方法，其特征在于，所述溶剂为N，N-二甲基甲酰胺。
PCT/CN2015/000448 2015-06-24 2015-06-24 一种偏氟聚芳芴醚噁二唑两性离子交换膜及其制备方法 Ceased WO2016205973A1 (zh)

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Publication number Priority date Publication date Assignee Title
WO2011151775A1 (en) * 2010-05-31 2011-12-08 Basf Se Mechanically stabilized polyazoles
CN103242552A (zh) * 2013-05-23 2013-08-14 北京大学 一种季铵化两性离子交换膜的制备方法
JP2014500567A (ja) * 2010-05-31 2014-01-09 ビーエーエスエフ ソシエタス・ヨーロピア 機械的に安定なポリアゾール
CN104250383A (zh) * 2014-08-27 2014-12-31 清华大学 两性离子交换膜及其制备方法

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011151775A1 (en) * 2010-05-31 2011-12-08 Basf Se Mechanically stabilized polyazoles
EP2576670A1 (en) * 2010-05-31 2013-04-10 Basf Se Mechanically stabilized polyazoles
JP2014500567A (ja) * 2010-05-31 2014-01-09 ビーエーエスエフ ソシエタス・ヨーロピア 機械的に安定なポリアゾール
CN103242552A (zh) * 2013-05-23 2013-08-14 北京大学 一种季铵化两性离子交换膜的制备方法
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