WO2022267392A1 - Method for preparing polytetrafluoroethylene/perfluorosulfonic acid/coupled phosphotungstic acid lignin ion exchange membrane - Google Patents

Method for preparing polytetrafluoroethylene/perfluorosulfonic acid/coupled phosphotungstic acid lignin ion exchange membrane Download PDF

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WO2022267392A1
WO2022267392A1 PCT/CN2021/139302 CN2021139302W WO2022267392A1 WO 2022267392 A1 WO2022267392 A1 WO 2022267392A1 CN 2021139302 W CN2021139302 W CN 2021139302W WO 2022267392 A1 WO2022267392 A1 WO 2022267392A1
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lignin
coupled
acid
polytetrafluoroethylene
phosphotungstic acid
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PCT/CN2021/139302
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French (fr)
Chinese (zh)
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叶家业
郑春花
李慧云
欧阳惠颖
孙天夫
刘艳琳
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中国科学院深圳先进技术研究院
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/1041—Polymer electrolyte composites, mixtures or blends
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/1041—Polymer electrolyte composites, mixtures or blends
    • H01M8/1046—Mixtures of at least one polymer and at least one additive
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
    • H01M8/1072—Polymeric electrolyte materials characterised by the manufacturing processes by chemical reactions, e.g. insitu polymerisation or insitu crosslinking
    • 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

  • the invention relates to the technical field of ion exchange membranes, in particular to a preparation method of a polytetrafluoroethylene/perfluorosulfonic acid/coupled phosphotungstic acid lignin ion exchange membrane.
  • H 2 -O 2 proton exchange membrane fuel cell has the advantages of rapid response, high energy conversion efficiency, high power density and zero pollutant emission, and is considered to be one of the most promising alternative power sources for stationary power and automotive power.
  • Ion exchange membranes need to have high proton conductivity, good stability and low fuel permeability.
  • the perfluorosulfonic acid ion exchange resin (PFSA) membrane commonly used in H 2 -O 2 proton exchange membrane fuel cells has the advantages of high proton conductivity, good chemical stability and thermal stability.
  • PFSA membranes are prone to dehydration under high temperature conditions, which affects the stability of batteries. That is, the proton conductivity of the PFSA membrane decreases under the condition of high temperature and low humidity, which causes the ohmic resistance of the H 2 -O 2 proton exchange membrane fuel cell to increase, resulting in rapid degradation of cell performance.
  • the application provides a preparation method of polytetrafluoroethylene/perfluorosulfonic acid/coupled phosphotungstic acid lignin ion exchange membranes.
  • the present application provides a polytetrafluoroethylene/perfluorosulfonic acid/coupled phosphotungstic acid lignin coating solution, the preparation raw materials of which include coupled phosphotungstic acid lignin, perfluorosulfonic acid resin and solvent;
  • the mass ratio of coupled phosphotungstic acid lignin and perfluorosulfonic acid resin is (0.1-15):100.
  • Coupled phosphotungstic acid lignin has the advantages of good dispersion, good hydrophilicity, and high proton conductivity. It is easy to regulate the proton transfer channel from the molecular scale, which can realize rapid proton transfer and improve the water retention rate of the membrane under high temperature and low humidity conditions. .
  • the surface of coupled phosphotungstic acid lignin is rich in conductive proton carriers such as phosphotungstic acid and hydroxyl groups. It has good hydrophilicity and can provide more transmission channels for proton transmission, thereby reducing the resistance of the diaphragm and promoting the proton exchange membrane fuel cell industry development of culture.
  • the mass ratio of the coupled phosphotungstic acid lignin and perfluorosulfonic acid resin is (1 ⁇ 15):100; more preferably, the mass ratio of the coupled phosphotungstic acid lignin and perfluorosulfonic acid resin Is (1 ⁇ 10):100; More preferably, the mass ratio of described coupled phosphotungstic acid lignin and perfluorosulfonic acid resin is (1 ⁇ 5):100; Most preferably, described coupled phosphotungstic acid The mass ratio of lignin and perfluorosulfonic acid resin is 1:20.
  • This application controls the mass ratio of coupled phosphotungstic acid lignin and perfluorosulfonic acid resin to be 1:20, and the prepared polytetrafluoroethylene/perfluorosulfonic acid/coupled phosphotungstic acid lignin ion exchange membrane is uniform and compact in texture, free of Dissolution phenomenon of polytetrafluoroethylene and coupled phosphotungstic acid lignin. And the surface water contact angle is smaller, and the water absorption, tensile strength and proton conductivity are all high.
  • the polytetrafluoroethylene/perfluorosulfonic acid/coupled phosphotungstic acid lignin ion exchange membrane meets the application requirements of proton exchange membrane fuel cells and can promote the industrial development of proton exchange membrane fuel cells.
  • the raw materials for the preparation of the coupled phosphotungstic acid lignin include coupling agent modified lignin and phosphotungstic acid aqueous solution; the ratio of the mass of the coupling agent modified lignin to the volume of the phosphotungstic acid aqueous solution is 1 /100 ⁇ 1/20 (g/mL); more preferably, the ratio of the mass of the lignin modified by the coupling agent to the volume of the phosphotungstic acid aqueous solution is 1/50 g/mL.
  • the preparation method of the coupling agent-modified lignin is as follows: add the lignin and the coupling agent to the mixed solution of deionized water and ethanol, stir and react at 20-80°C for 1-24 hours, centrifuge, After washing and drying, the lignin modified by the coupling agent is obtained; the mass ratio of the lignin to the coupling agent is 1:(0.1-10).
  • the reaction temperature of the lignin and the coupling agent is 20-50°C, and the reaction time is 10-16h; more preferably, the reaction temperature The temperature is 30°C, and the reaction time is 12h.
  • the mass ratio of the lignin to the coupling agent is 1:(0.5-1.5); more preferably, the mass ratio of the lignin to the coupling agent is 1:1.
  • Coupling agent modified lignin can maintain the advantages of lignin rich in hydroxyl groups and strong hydrophilicity, and can further improve its chemical stability, maintain water retention, and is not easy to reduce PTFE/perfluorosulfonic acid/coupled phosphorus Proton conductivity of lignin tungstate ion exchange membranes.
  • the volume ratio of deionized water and ethanol is 1:9.
  • the mass volume ratio of the lignin and the coupling agent in the mixed solution of deionized water and ethanol is 1/100 ⁇ 1/20 (g/mL); more preferably, the lignin and the coupling agent
  • the mass volume ratio of the coupling agent in the mixed solution of deionized water and ethanol is 1/50g/mL.
  • the mass-to-volume ratio refers to the ratio between the total mass of lignin and coupling agent and the total volume of the mixed solution of deionized water and ethanol.
  • the coupling agent is selected from 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane and N-(2-aminoethyl)-3-aminopropyltrimethoxysilane one or more of.
  • the concentration of the phosphotungstic acid aqueous solution is 1-20wt%; more preferably, the concentration of the phosphotungstic acid aqueous solution is 5-15wt%; most preferably, the concentration of the phosphotungstic acid aqueous solution is 10wt% .
  • the preparation method of the coupled phosphotungstic acid lignin is: mixing the lignin modified by the coupling agent and phosphotungstic acid aqueous solution, stirring for reaction, centrifuging, washing, and drying to obtain the coupled phosphotungstic acid lignin.
  • Coupling lignin phosphotungstic acid effectively reduces the density of ion exchange groups in the membrane when lignin is directly incorporated into the PFSA matrix, and improves the performance of the ion exchange membrane of polytetrafluoroethylene/perfluorosulfonic acid/coupling lignin phosphotungstic acid. proton conductivity.
  • Coupling phosphotungstic acid lignin uses a coupling agent to anchor phosphotungstic acid on the surface of lignin, which can play a fixed role, ensure the stability of proton transport in the membrane, and effectively reduce the dissolution of phosphotungstic acid with the operation of the fuel cell , thereby improving the stability of the battery.
  • the stirring reaction temperature is 25° C.
  • the stirring speed is 800-1200 r/min
  • the stirring time is 8-16 hours.
  • the present application provides a preparation method of polytetrafluoroethylene/perfluorosulfonic acid/coupled phosphotungstic acid lignin ion exchange membrane, comprising the following steps:
  • step S2 Add coupled phosphotungstic acid lignin to the PFSA solution prepared in step S1, and stir evenly to obtain a polytetrafluoroethylene/perfluorosulfonic acid/coupled phosphotungstic acid lignin coating liquid.
  • the reaction temperature of the S1 step is 200° C., and the reaction time is 6 h.
  • the mass ratio of the perfluorosulfonic acid resin to the solvent is (4-10):100; more preferably, the mass ratio of the perfluorosulfonic acid resin to the solvent is 1: 20.
  • the solvent is a mixed solution of propanol and deionized water, the volume ratio of the propanol and deionized water is 1:1; the propanol is n-propanol and/or isopropanol.
  • the stirring speed is 100-1000r/min, and the stirring time is 30-60min; preferably, the The stirring speed is 1000r/min, and the stirring time is 30min.
  • the present application provides a polytetrafluoroethylene/perfluorosulfonic acid/coupled phosphotungstic acid lignin ion exchange membrane, which contains the above-mentioned polytetrafluoroethylene/perfluorosulfonic acid/coupled phosphotungstic acid lignin coating film liquid coating.
  • the polytetrafluoroethylene/perfluorosulfonic acid/coupled phosphotungstic acid lignin ion exchange membrane includes a first PFSA/PWA@lignin coating, a porous polytetrafluoroethylene film and a second PFSA/PWA@lignin coating; both the first PFSA/PWA@lignin coating and the second PFSA/PWA@lignin coating are coated with polytetrafluoroethylene/perfluorosulfonic acid/coupled phosphotungstic acid lignin Membrane solution is obtained.
  • PTFE/perfluorosulfonic acid/coupled phosphotungstic acid lignin ion exchange membrane effectively improves the mechanics, high temperature water retention and thermal stability of the separator, thereby improving the stability and life of the separator during battery operation.
  • the porous polytetrafluoroethylene film is used as the middle layer of the composite membrane, which not only does not hinder proton transport, but also greatly improves the stability and mechanical properties of the membrane.
  • This application uses the synergistic effect of PFSA/PWA@lignin coating and porous polytetrafluoroethylene layer to improve the water retention, proton conductivity, thermal stability and mechanical stability of the membrane.
  • the present application provides a preparation method of polytetrafluoroethylene/perfluorosulfonic acid/coupled phosphotungstic acid lignin ion exchange membrane, comprising the following steps:
  • the polytetrafluoroethylene/perfluorosulfonic acid/coupled phosphotungstic acid lignin ion exchange membrane prepared by this application uses perfluorosulfonic acid as the main body, and the coupled phosphotungstic acid lignin is dispersed in the PFSA solution, and the porous polytetrafluoroethylene
  • the film is the middle layer, and the solution casting method is used to prepare the polytetrafluoroethylene/perfluorosulfonic acid/coupled phosphotungstic acid lignin ion exchange membrane, and the synergistic effect of the coupled phosphotungstic acid lignin and the porous polytetrafluoroethylene layer,
  • the water retention, proton conductivity, good thermal and mechanical stability and battery performance of polytetrafluoroethylene/perfluorosulfonic acid/coupled phosphotungstic acid lignin ion exchange membrane are improved.
  • the equipment used in the entire preparation process of this application has the characteristics of low price, low raw material cost, convenient operation and environmental protection, etc., which is helpful to promote the development of commercial diaphragm materials for proton exchange membrane fuel cells and the commercialization of proton exchange membrane fuel cells Production.
  • the PTFE/perfluorosulfonic acid/coupled phosphotungstic acid lignin coating solution needs to be subjected to ultrasonic dispersion treatment before coating to obtain uniformly dispersed PTFE/perfluorosulfonic acid/coupled Phosphotungstic acid lignin coating solution.
  • the power of the ultrasonic dispersion is 200-350W, and the time of the ultrasonic dispersion is 20-50min; preferably, the power of the ultrasonic dispersion is 300W, and the time of the ultrasonic dispersion is 30min.
  • the substrate is polyimide.
  • the drying includes two-step drying treatment; the drying temperature of the first step is 80-100°C, and the drying time of the first step is 10-60min; the drying temperature of the second step is 140-180°C, and the drying time of the second step is 1-3 hours; more preferably, the drying temperature of the first step is 100° C., and the drying time of the first step is 30 minutes; the drying temperature of the second step is 160° C., and the drying time of the second step is 2 hours.
  • the porous polytetrafluoroethylene film Preferably, before the recoating of polytetrafluoroethylene/perfluorosulfonic acid/coupled phosphotungstic acid lignin coating solution, it is necessary to wait for the porous polytetrafluoroethylene film to soak for 1 to 30 minutes; more preferably, the recoating It is necessary to wait for the porous PTFE film to soak for 10 minutes before applying the PTFE/perfluorosulfonic acid/coupled phosphotungstic acid lignin coating solution.
  • the porous polytetrafluoroethylene film has a pore size of 100-1000 nm and a thickness of 5-10 ⁇ m.
  • the thickness of the polytetrafluoroethylene/perfluorosulfonic acid/coupled phosphotungstic acid lignin ion exchange membrane is 10-40 ⁇ m; comprehensively considering factors such as diaphragm cost, stability, and battery performance, the polytetrafluoroethylene
  • the thickness of the ethylene/perfluorosulfonic acid/coupled phosphotungstic acid lignin ion exchange membrane is more preferably 12-30 ⁇ m.
  • the content of coupled phosphotungstic acid lignin is 0.1-15wt%; preferably, coupled phosphotungstic acid lignin The content of element is 0.5-10wt%.
  • This application uses the synergistic effect of PFSA/PWA@lignin coating and porous polytetrafluoroethylene layer to improve the water retention and proton conduction of polytetrafluoroethylene/perfluorosulfonic acid/coupled phosphotungstic acid lignin ion exchange membrane The efficiency, thermal stability and mechanical stability are good, which improves the stability and life of the membrane during battery operation.
  • This application uses coupled phosphotungstic acid lignin, which has the advantages of good dispersibility, good hydrophilicity, and high proton conductivity. It is easy to regulate the proton transfer channel from the molecular scale, which can realize rapid proton transmission, and at the same time improve the membrane in Water retention under high temperature and low humidity conditions.
  • the polytetrafluoroethylene/perfluorosulfonic acid/coupled phosphotungstic acid lignin ion exchange membrane prepared by this application uses active groups such as phosphotungstic acid and hydroxyl on the surface of the coupled phosphotungstic acid lignin as conductive proton carriers.
  • Coupled phosphotungstic acid lignin has good hydrophilicity, which can provide more transmission channels for proton transport, thereby reducing the resistance of the diaphragm, greatly improving the energy efficiency of the battery, and promoting the industrialization of proton exchange membrane fuel cells.
  • the polytetrafluoroethylene/perfluorosulfonic acid/coupled phosphotungstic acid lignin ion exchange membrane is prepared by the solution casting method.
  • the equipment used in the whole preparation process has the advantages of low price, low raw material cost, convenient operation and environmental protection, etc.
  • the characteristics of industrial practicability are helpful to promote the development of commercial diaphragm materials for proton exchange membrane fuel cells and the commercial production of proton exchange membrane fuel cells.
  • Figure 1 is a picture of the polytetrafluoroethylene/perfluorosulfonic acid/coupled phosphotungstic acid lignin ion exchange membrane prepared in Example 1.
  • Figure 2 is a schematic diagram of the water contact angle of the polytetrafluoroethylene/perfluorosulfonic acid/coupled phosphotungstic acid lignin ion exchange membrane prepared in Example 1.
  • Comparative Example 1 is a schematic diagram of the water contact angle of Comparative Example 1 (the commercial PFSA membrane of Gore 740).
  • Lignin is a natural and environmentally friendly polymer with good chemical stability, rich in hydroxyl and strong hydrophilicity. It is abundant in nature and is a by-product of the paper industry and fuel fermentation industry.
  • direct incorporation of lignin into the PFSA matrix reduces the density of ion-exchange groups in the separator.
  • lignin has a certain water retention effect, it reduces the proton conductivity of the membrane.
  • Phosphotungstic acid is the most acidic heteropolyacid, which can enhance the proton conductivity in the polymer matrix.
  • phosphotungstic acid has a certain water solubility and will dissolve with the operation of the fuel cell, affecting the stability of the battery. This application is researched on this basis.
  • Embodiment 1 provides a preparation method of polytetrafluoroethylene/perfluorosulfonic acid/coupled phosphotungstic acid lignin ion exchange membrane, the specific steps are as follows:
  • Preparation of coupling agent modified lignin adding lignin and 3-aminopropyltriethoxysilane with a mass ratio of 1:1 to a mixed solution of deionized water and ethanol with a volume ratio of 1:9 (wood The mass volume ratio of the element and the coupling agent in the mixed solution of deionized water and ethanol is 1/50g/mL), reacted at 30°C and 1000r/min stirring speed for 12h, after the reaction, washed with deionized water The reaction product was repeatedly centrifuged and washed, put in an oven at 60°C, and dried for 24 hours to obtain coupling agent-modified lignin;
  • the coupling agent modified lignin prepared above is added to 10wt% phosphotungstic acid aqueous solution (the quality of coupling agent modified lignin and the volume of 10wt% phosphotungstic acid aqueous solution The ratio is 1/50g/mL), reacted for 12 hours at 25°C with a stirring speed of 1000r/min, centrifuged, and washed the reaction product repeatedly with deionized water to obtain coupled phosphotungstic acid lignin;
  • Preparation of polytetrafluoroethylene/perfluorosulfonic acid/coupling phosphotungstic acid lignin coating solution add perfluorosulfonic acid resin to a mixture of n-propanol and deionized solution with a volume ratio of 1:1 (perfluorosulfonic acid resin The mass ratio of the mixed liquid to the mixed solution is 1:20), mixed evenly, transferred to the autoclave, reacted at 200 ° C for 6 hours, cooled to room temperature, and obtained the PFSA solution; the coupled phosphotungstic acid lignin prepared above was added to the PFSA solution (The mass ratio of coupled phosphotungstic acid lignin and perfluorosulfonic acid resin is 1:20), and reacted for 30 minutes at 25°C with a stirring speed of 1000r/min to obtain PTFE/perfluorosulfonic acid/coupled phosphorus Tungstate lignin coating solution.
  • the PTFE/perfluorosulfonic acid/coupled phosphotungstic acid lignin coating solution prepared above was ultrasonically dispersed for 30 minutes under 300W ultrasonic power to obtain uniformly dispersed PTFE/perfluorosulfonic acid/coupled phosphotungstic acid Lignin coating solution;
  • the porous polytetrafluoroethylene film On the upper surface of the porous polytetrafluoroethylene film, coat polytetrafluoroethylene/perfluorosulfonic acid/coupled phosphotungstic acid lignin coating solution and form the second PFSA/PWA@lignin coating (the second PFSA/PWA@ lignin coating is the same thickness as the first PFSA/PWA@lignin coating);
  • the polytetrafluoroethylene/perfluorosulfonic acid/coupled phosphotungstic acid lignin ion-exchange membrane prepared in Example 1 has a thickness of 17 ⁇ m. As can be seen from Figure 1, the ion-exchange membrane prepared in Example 1 has a uniform and dense texture. There is no porous PTFE film, coupled phosphotungstic acid lignin dissolution phenomenon, and has good flexibility and mechanical properties.
  • Example 1 For the polytetrafluoroethylene/perfluorosulfonic acid/coupled phosphotungstic acid lignin ion exchange membrane (ie PTFE/PFSA/PWA@lignin composite diaphragm) prepared in Example 1, the surface water contact angle was tested at 25°C, and the test results are shown in Figure 2; Water absorption, tensile strength and proton conductivity tests were performed, and the test data are shown in Table 1.
  • Example 2 a preparation method of polytetrafluoroethylene/perfluorosulfonic acid/coupled phosphotungstic acid lignin ion exchange membrane, the only difference from Example 1 is: coupling phosphotungstic acid lignin and perfluorosulfonic acid The mass ratio of resin is 1:100.
  • the polytetrafluoroethylene/perfluorosulfonic acid/coupled phosphotungstic acid lignin ion exchange membrane prepared in Example 2 has a thickness of 11 ⁇ m, which is too thin to easily cause fuel permeation, which is worse than the membrane prepared in Example 1, which is not conducive to the battery long run. Compared with the ion exchange membrane prepared in Example 1, the ion exchange membrane prepared in Example 2 is not conducive to the commercial application of proton exchange membrane fuel cells.
  • the ion-exchange membrane prepared in Example 2 has a uniform and dense texture, no porous polytetrafluoroethylene film, and no dissolution phenomenon of coupled phosphotungstic acid lignin, and has good flexibility and mechanical properties.
  • Example 3 a preparation method of polytetrafluoroethylene/perfluorosulfonic acid/coupled phosphotungstic acid lignin ion exchange membrane, the only difference from Example 1 is: coupling phosphotungstic acid lignin and perfluorosulfonic acid The mass ratio of resin is 1:10.
  • the polytetrafluoroethylene/perfluorosulfonic acid/coupled phosphotungstic acid lignin ion-exchange membrane prepared in Example 3 has a thickness of 23 ⁇ m, and the ion-exchange membrane prepared in Example 3 has a uniform texture, but it is different from that prepared in Example 1. Compared with the ion-exchange membrane, the ion-exchange membrane prepared in Example 3 has the phenomenon of coupled phosphotungstic acid lignin agglomeration, and is not suitable for application in proton exchange fuel cells.
  • Comparative Example 1 provides a commercial PFSA membrane (i.e. the original PFSA membrane) that is Gore 740.
  • the surface water contact angle of the polytetrafluoroethylene/perfluorosulfonic acid/coupled phosphotungstic acid lignin ion exchange membrane prepared in Comparative Example 1 was tested at 25°C, and the test results are shown in Figure 3.
  • the water contact angle of polytetrafluoroethylene/perfluorosulfonic acid/coupled phosphotungstic acid lignin ion exchange membrane in Example 1 is less than that of the commercialized PFSA membrane of Gore 740 in Comparative Example 1
  • the water contact angle shows that the hydrophilicity of polytetrafluoroethylene/perfluorosulfonic acid/coupled phosphotungstic acid lignin ion exchange membrane is better than that of the commercial PFSA membrane of model Gore 740.

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Abstract

Disclosed is a method for preparing a polytetrafluoroethylene/perfluorosulfonic acid/coupled phosphotungstic acid lignin ion exchange membrane. The raw materials for preparing a polytetrafluoroethylene/perfluorosulfonic acid/coupled phosphotungstic acid lignin coating solution comprise coupled phosphotungstic acid lignin, a perfluorosulfonic acid resin, and a solvent. The mass ratio of the coupled phosphotungstic acid lignin to the perfluorosulfonic acid resin is (0.1-15):100. The coupled phosphotungstic acid lignin has the advantages of good dispersibility, good hydrophilicity, high proton conductivity and the like, can easily regulate and control the proton transfer channel at the molecular scale, can realize rapid proton transmission, and improves the water retention rate of the perfluorosulfonic acid exchange membrane under high-temperature and low-humidity conditions, thereby promoting the development of proton exchange membrane fuel cell industrialization.

Description

一种聚四氟乙烯/全氟磺酸/耦合磷钨酸木质素离子交换膜的制备方法A preparation method of polytetrafluoroethylene/perfluorosulfonic acid/coupled phosphotungstic acid lignin ion exchange membrane 技术领域technical field
本发明涉及离子交换膜技术领域，尤其是涉及一种聚四氟乙烯/全氟磺酸/耦合磷钨酸木质素离子交换膜的制备方法。The invention relates to the technical field of ion exchange membranes, in particular to a preparation method of a polytetrafluoroethylene/perfluorosulfonic acid/coupled phosphotungstic acid lignin ion exchange membrane.
背景技术Background technique
H 2-O 2质子交换膜燃料电池，具有响应迅速、高能量转换效率、高功率密度和零污染物排放等优点，被认为是最具发展前景的固定电源和汽车电源的替代电源之一。 H 2 -O 2 proton exchange membrane fuel cell has the advantages of rapid response, high energy conversion efficiency, high power density and zero pollutant emission, and is considered to be one of the most promising alternative power sources for stationary power and automotive power.
离子交换膜需要具有高质子传导率，良好的稳定性和低燃料渗透率等特性。H 2-O 2质子交换膜燃料电池常用的全氟磺酸离子交换树脂(PFSA)膜具有质子传导性高、化学稳定性和热稳定性好等优点。但目前商业化PFSA膜的质子传导率在很大程度上取决于含水量，而PFSA膜在高温条件下容易脱水，影响电池的稳定性。即，在高温低湿度条件下PFSA膜的质子电导率下降，引起H 2-O 2质子交换膜燃料电池的欧姆电阻增加，从而导致电池性能迅速衰减。使用外部加湿设备是解决商业化PFSA膜在高温低湿度条件下质子电导率下降的常用办法，但增大了H 2-O 2质子交换膜燃料电池系统的整体尺寸和重量，同时也加剧了能量损耗。 Ion exchange membranes need to have high proton conductivity, good stability and low fuel permeability. The perfluorosulfonic acid ion exchange resin (PFSA) membrane commonly used in H 2 -O 2 proton exchange membrane fuel cells has the advantages of high proton conductivity, good chemical stability and thermal stability. However, the proton conductivity of commercial PFSA membranes depends largely on the water content, and PFSA membranes are prone to dehydration under high temperature conditions, which affects the stability of batteries. That is, the proton conductivity of the PFSA membrane decreases under the condition of high temperature and low humidity, which causes the ohmic resistance of the H 2 -O 2 proton exchange membrane fuel cell to increase, resulting in rapid degradation of cell performance. The use of external humidification equipment is a common way to solve the proton conductivity drop of commercial PFSA membranes under high temperature and low humidity conditions, but it increases the overall size and weight of the H 2 -O 2 proton exchange membrane fuel cell system, and also increases the energy consumption. loss.
因此，亟需研发一种在高温低湿条件下的保水能力高的质子交换膜。Therefore, there is an urgent need to develop a proton exchange membrane with high water retention capacity under high temperature and low humidity conditions.
发明内容Contents of the invention
为了提升质子交换膜在高温低湿条件下的保水能力，本申请提供一种聚四氟乙烯/全氟磺酸/耦合磷钨酸木质素离子交换膜的制备方法。In order to improve the water retention capacity of proton exchange membranes under high temperature and low humidity conditions, the application provides a preparation method of polytetrafluoroethylene/perfluorosulfonic acid/coupled phosphotungstic acid lignin ion exchange membranes.
第一方面，本申请提供一种聚四氟乙烯/全氟磺酸/耦合磷钨酸木质素涂膜液，其制备原料包括耦合磷钨酸木质素、全氟磺酸树脂和溶剂；所述耦合磷钨酸木质素和全氟磺酸树脂的质量比为(0.1～15):100。In the first aspect, the present application provides a polytetrafluoroethylene/perfluorosulfonic acid/coupled phosphotungstic acid lignin coating solution, the preparation raw materials of which include coupled phosphotungstic acid lignin, perfluorosulfonic acid resin and solvent; The mass ratio of coupled phosphotungstic acid lignin and perfluorosulfonic acid resin is (0.1-15):100.
耦合磷钨酸木质素具有分散性好、亲水性好以及质子传导性高等优点，容易从分子尺度对质子传递通道进行调控，能实现质子快速传输，同时提高膜在高温低湿条件下的保水率。耦合磷钨酸木质素表面富含磷钨酸、羟基等传导质子载体，具有良好的亲水性，可以为质子传输提供更多的传输通道，进而降低隔膜的电阻，促进质子交换膜燃料电池产业化的发展。Coupled phosphotungstic acid lignin has the advantages of good dispersion, good hydrophilicity, and high proton conductivity. It is easy to regulate the proton transfer channel from the molecular scale, which can realize rapid proton transfer and improve the water retention rate of the membrane under high temperature and low humidity conditions. . The surface of coupled phosphotungstic acid lignin is rich in conductive proton carriers such as phosphotungstic acid and hydroxyl groups. It has good hydrophilicity and can provide more transmission channels for proton transmission, thereby reducing the resistance of the diaphragm and promoting the proton exchange membrane fuel cell industry development of culture.
优选的，所述耦合磷钨酸木质素和全氟磺酸树脂的质量比为(1～15):100；更优选的，所述耦合磷钨酸木质素和全氟磺酸树脂的质量比为(1～10):100；更进一步优选的，所述耦合磷钨酸木质素和全氟磺酸树脂的质量比为(1～5):100；最优选的，所述耦合磷钨酸木质素和全氟磺酸树脂的质量比为1:20。Preferably, the mass ratio of the coupled phosphotungstic acid lignin and perfluorosulfonic acid resin is (1～15):100; more preferably, the mass ratio of the coupled phosphotungstic acid lignin and perfluorosulfonic acid resin Is (1～10):100; More preferably, the mass ratio of described coupled phosphotungstic acid lignin and perfluorosulfonic acid resin is (1～5):100; Most preferably, described coupled phosphotungstic acid The mass ratio of lignin and perfluorosulfonic acid resin is 1:20.
本申请控制耦合磷钨酸木质素和全氟磺酸树脂的质量比为1：20，制备的聚四氟乙烯/全氟磺酸/耦合磷钨酸木质素离子交换膜质地均匀、致密，无聚四氟乙烯、耦合磷钨酸木质素溶出现象。且表面水接触角更小，吸水率、拉伸强度和质子传导率均较高。该聚四氟乙烯/全氟磺酸/耦合磷钨酸木质素离子交换膜适应在质子交换膜燃料电池的应用要求，可以促进质子交换膜燃料电池的工业化发展。This application controls the mass ratio of coupled phosphotungstic acid lignin and perfluorosulfonic acid resin to be 1:20, and the prepared polytetrafluoroethylene/perfluorosulfonic acid/coupled phosphotungstic acid lignin ion exchange membrane is uniform and compact in texture, free of Dissolution phenomenon of polytetrafluoroethylene and coupled phosphotungstic acid lignin. And the surface water contact angle is smaller, and the water absorption, tensile strength and proton conductivity are all high. The polytetrafluoroethylene/perfluorosulfonic acid/coupled phosphotungstic acid lignin ion exchange membrane meets the application requirements of proton exchange membrane fuel cells and can promote the industrial development of proton exchange membrane fuel cells.
优选的，所述耦合磷钨酸木质素的制备原料包括偶联剂改性木质素和磷钨酸水溶液；所述偶联剂改性木质素的质量与磷钨酸水溶液的体积的比值为1/100～1/20(g/mL)；更优选的，所述偶联剂改性木质素的质量与磷钨 酸水溶液的体积的比值为1/50g/mL。Preferably, the raw materials for the preparation of the coupled phosphotungstic acid lignin include coupling agent modified lignin and phosphotungstic acid aqueous solution; the ratio of the mass of the coupling agent modified lignin to the volume of the phosphotungstic acid aqueous solution is 1 /100～1/20 (g/mL); more preferably, the ratio of the mass of the lignin modified by the coupling agent to the volume of the phosphotungstic acid aqueous solution is 1/50 g/mL.
优选的，所述偶联剂改性木质素的制备方法为：将木质素、偶联剂加至去离子水和乙醇的混合溶液中，在20～80℃、搅拌反应1～24h，离心、洗涤、干燥后得偶联剂改性木质素；所述木质素和偶联剂的质量比为1:(0.1～10)。Preferably, the preparation method of the coupling agent-modified lignin is as follows: add the lignin and the coupling agent to the mixed solution of deionized water and ethanol, stir and react at 20-80°C for 1-24 hours, centrifuge, After washing and drying, the lignin modified by the coupling agent is obtained; the mass ratio of the lignin to the coupling agent is 1:(0.1-10).
进一步优选的，所述偶联剂改性木质素的制备方法中，所述木质素和偶联剂的反应温度为20～50℃，反应时间为10～16h；更优选的，所述反应温度为30℃，反应时间为12h。Further preferably, in the preparation method of the coupling agent modified lignin, the reaction temperature of the lignin and the coupling agent is 20-50°C, and the reaction time is 10-16h; more preferably, the reaction temperature The temperature is 30°C, and the reaction time is 12h.
进一步优选的，所述木质素和偶联剂的质量比为1:(0.5～1.5)；更优选的，所述木质素和偶联剂的质量比为1:1。Further preferably, the mass ratio of the lignin to the coupling agent is 1:(0.5-1.5); more preferably, the mass ratio of the lignin to the coupling agent is 1:1.
偶联剂改性木质素可以保持木质素富含羟基、亲水性强的优点，还能进一步提高其化学稳定性，保持保水作用，且不易降低聚四氟乙烯/全氟磺酸/耦合磷钨酸木质素离子交换膜的质子传导率。Coupling agent modified lignin can maintain the advantages of lignin rich in hydroxyl groups and strong hydrophilicity, and can further improve its chemical stability, maintain water retention, and is not easy to reduce PTFE/perfluorosulfonic acid/coupled phosphorus Proton conductivity of lignin tungstate ion exchange membranes.
本申请中，所述去离子水和乙醇的混合溶液中，去离子水和乙醇体积比为1:9。In the present application, in the mixed solution of deionized water and ethanol, the volume ratio of deionized water and ethanol is 1:9.
本申请中，所述木质素和偶联剂在去离子水和乙醇的混合溶液中的质量体积比为1/100～1/20(g/mL)；更优选的，所述木质素和偶联剂在去离子水和乙醇的混合溶液中的质量体积比为1/50g/mL。In the present application, the mass volume ratio of the lignin and the coupling agent in the mixed solution of deionized water and ethanol is 1/100～1/20 (g/mL); more preferably, the lignin and the coupling agent The mass volume ratio of the coupling agent in the mixed solution of deionized water and ethanol is 1/50g/mL.
本申请中，所述质量体积比是指木质素和偶联剂的总质量与去离子水和乙醇的混合溶液的总体积之间的比值。In the present application, the mass-to-volume ratio refers to the ratio between the total mass of lignin and coupling agent and the total volume of the mixed solution of deionized water and ethanol.
优选的，所述偶联剂选自3-氨基丙基三乙氧基硅烷、3-氨基丙基三甲氧基硅烷和N-(2-氨基乙基)-3-氨基丙基三甲氧基硅烷中的一种或多种。Preferably, the coupling agent is selected from 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane and N-(2-aminoethyl)-3-aminopropyltrimethoxysilane one or more of.
优选的，所述磷钨酸水溶液的浓度为1～20wt％；更优选的，所述磷钨酸水溶液的浓度为5～15wt％；最优选的，所述磷钨酸水溶液的浓度为10wt％。Preferably, the concentration of the phosphotungstic acid aqueous solution is 1-20wt%; more preferably, the concentration of the phosphotungstic acid aqueous solution is 5-15wt%; most preferably, the concentration of the phosphotungstic acid aqueous solution is 10wt% .
优选的，所述耦合磷钨酸木质素的制备方法为：将偶联剂改性木质素和磷钨酸水溶液混合，搅拌反应，离心，洗涤，干燥后得耦合磷钨酸木质素。Preferably, the preparation method of the coupled phosphotungstic acid lignin is: mixing the lignin modified by the coupling agent and phosphotungstic acid aqueous solution, stirring for reaction, centrifuging, washing, and drying to obtain the coupled phosphotungstic acid lignin.
耦合磷钨酸木质素有效减少了木质素直接掺入到PFSA基体中会降低隔膜中离子交换基团的密度，提高了聚四氟乙烯/全氟磺酸/耦合磷钨酸木质素离子交换膜的质子传导率。耦合磷钨酸木质素通过偶联剂将磷钨酸锚定在木质素的表面，可以起到固定作用，确保膜的质子传输稳定性，有效减少了磷钨酸随着燃料电池的运行而溶解，从而提高了电池的稳定性。Coupling lignin phosphotungstic acid effectively reduces the density of ion exchange groups in the membrane when lignin is directly incorporated into the PFSA matrix, and improves the performance of the ion exchange membrane of polytetrafluoroethylene/perfluorosulfonic acid/coupling lignin phosphotungstic acid. proton conductivity. Coupling phosphotungstic acid lignin uses a coupling agent to anchor phosphotungstic acid on the surface of lignin, which can play a fixed role, ensure the stability of proton transport in the membrane, and effectively reduce the dissolution of phosphotungstic acid with the operation of the fuel cell , thereby improving the stability of the battery.
本申请中，所述耦合磷钨酸木质素的制备方法中，所述搅拌反应的温度为25℃，搅拌速度为800～1200r/min，搅拌时间为8～16h。In the present application, in the preparation method of coupled phosphotungstic acid lignin, the stirring reaction temperature is 25° C., the stirring speed is 800-1200 r/min, and the stirring time is 8-16 hours.
第二方面，本申请提供一种聚四氟乙烯/全氟磺酸/耦合磷钨酸木质素离子交换膜的制备方法，包括如下步骤：In the second aspect, the present application provides a preparation method of polytetrafluoroethylene/perfluorosulfonic acid/coupled phosphotungstic acid lignin ion exchange membrane, comprising the following steps:
S1、将全氟磺酸树脂加入和溶剂混合，混匀均匀后转移到反应釜内，在180～240℃反应2～8h，冷却，得PFSA溶液；所述全氟磺酸树脂和溶剂的质量比为(1～20):100；S1. Add the perfluorosulfonic acid resin and mix it with the solvent, transfer it to the reaction kettle after mixing evenly, react at 180-240°C for 2-8 hours, and cool to obtain the PFSA solution; the mass of the perfluorosulfonic acid resin and solvent The ratio is (1～20):100;
S2、将耦合磷钨酸木质素加入S1步骤制得的PFSA溶液中，搅拌均匀，得聚四氟乙烯/全氟磺酸/耦合磷钨酸木质素涂膜液。S2. Add coupled phosphotungstic acid lignin to the PFSA solution prepared in step S1, and stir evenly to obtain a polytetrafluoroethylene/perfluorosulfonic acid/coupled phosphotungstic acid lignin coating liquid.
本申请中，所述S1步骤的反应温度为200℃，反应时间为6h。In the present application, the reaction temperature of the S1 step is 200° C., and the reaction time is 6 h.
本申请中，所述S1步骤中，所述全氟磺酸树脂和溶剂的质量比为 (4～10):100；更优选的，所述全氟磺酸树脂和溶剂的质量比为1:20。In the present application, in the S1 step, the mass ratio of the perfluorosulfonic acid resin to the solvent is (4-10):100; more preferably, the mass ratio of the perfluorosulfonic acid resin to the solvent is 1: 20.
本申请中，所述溶剂为丙醇和去离子水的混合溶液中，所述丙醇和去离子水的体积比为1:1；所述丙醇为正丙醇和/或异丙醇。In the present application, the solvent is a mixed solution of propanol and deionized water, the volume ratio of the propanol and deionized water is 1:1; the propanol is n-propanol and/or isopropanol.
本申请中，所述S2步骤中，所述耦合磷钨酸木质素和PFSA溶液搅拌操中，所述搅拌的速度为100～1000r/min，搅拌的时间为30～60min；优选的，所述搅拌的速度为1000r/min，搅拌的时间为30min。In the present application, in the S2 step, in the stirring operation of coupling lignin phosphotungstate and PFSA solution, the stirring speed is 100-1000r/min, and the stirring time is 30-60min; preferably, the The stirring speed is 1000r/min, and the stirring time is 30min.
第三方面，本申请提供一种聚四氟乙烯/全氟磺酸/耦合磷钨酸木质素离子交换膜，含有由上述聚四氟乙烯/全氟磺酸/耦合磷钨酸木质素涂膜液制得的涂层。In the third aspect, the present application provides a polytetrafluoroethylene/perfluorosulfonic acid/coupled phosphotungstic acid lignin ion exchange membrane, which contains the above-mentioned polytetrafluoroethylene/perfluorosulfonic acid/coupled phosphotungstic acid lignin coating film liquid coating.
本申请中，从下往上，所述聚四氟乙烯/全氟磺酸/耦合磷钨酸木质素离子交换膜包括第一PFSA/PWA@lignin涂层、多孔聚四氟乙烯薄膜和第二PFSA/PWA@lignin涂层；所述第一PFSA/PWA@lignin涂层和第二PFSA/PWA@lignin涂层均由涂布聚四氟乙烯/全氟磺酸/耦合磷钨酸木质素涂膜液得到。In this application, from bottom to top, the polytetrafluoroethylene/perfluorosulfonic acid/coupled phosphotungstic acid lignin ion exchange membrane includes a first PFSA/PWA@lignin coating, a porous polytetrafluoroethylene film and a second PFSA/PWA@lignin coating; both the first PFSA/PWA@lignin coating and the second PFSA/PWA@lignin coating are coated with polytetrafluoroethylene/perfluorosulfonic acid/coupled phosphotungstic acid lignin Membrane solution is obtained.
聚四氟乙烯/全氟磺酸/耦合磷钨酸木质素离子交换膜有效提高了隔膜的力学、高温保水率和热稳定性，进而提升隔膜在电池运行过程中的稳定性和寿命。多孔聚四氟乙烯薄膜作为复合膜中间层，不但不会阻碍质子传输，还可以大幅提高膜的稳定性和机械性能。本申请利用PFSA/PWA@lignin涂层与多孔聚四氟乙烯层的协同作用，提高了膜的保水性、质子传导率、热学稳定性和力学稳定性好。PTFE/perfluorosulfonic acid/coupled phosphotungstic acid lignin ion exchange membrane effectively improves the mechanics, high temperature water retention and thermal stability of the separator, thereby improving the stability and life of the separator during battery operation. The porous polytetrafluoroethylene film is used as the middle layer of the composite membrane, which not only does not hinder proton transport, but also greatly improves the stability and mechanical properties of the membrane. This application uses the synergistic effect of PFSA/PWA@lignin coating and porous polytetrafluoroethylene layer to improve the water retention, proton conductivity, thermal stability and mechanical stability of the membrane.
第四方面，本申请提供一种聚四氟乙烯/全氟磺酸/耦合磷钨酸木质素离子交换膜的制备方法，包括以下步骤：In the fourth aspect, the present application provides a preparation method of polytetrafluoroethylene/perfluorosulfonic acid/coupled phosphotungstic acid lignin ion exchange membrane, comprising the following steps:
将聚四氟乙烯/全氟磺酸/耦合磷钨酸木质素涂膜液涂布到基材的上表面并形成第一PFSA/PWA@lignin涂层；Coating polytetrafluoroethylene/perfluorosulfonic acid/coupled phosphotungstic acid lignin coating solution to the upper surface of the substrate and forming the first PFSA/PWA@lignin coating;
将多孔聚四氟乙烯薄膜覆盖到第一PFSA/PWA@lignin涂层上；Overlay the porous PTFE film onto the first PFSA/PWA@lignin coating;
在多孔聚四氟乙烯薄膜的上表面再涂布聚四氟乙烯/全氟磺酸/耦合磷钨酸木质素涂膜液并形成第二PFSA/PWA@lignin涂层；Coat the upper surface of the porous PTFE film with PTFE/perfluorosulfonic acid/coupled phosphotungstic acid lignin coating solution and form the second PFSA/PWA@lignin coating;
干燥，冷却至室温，剥离基材，得聚四氟乙烯/全氟磺酸/耦合磷钨酸木质素离子交换膜。Dry, cool to room temperature, and peel off the substrate to obtain a polytetrafluoroethylene/perfluorosulfonic acid/coupled phosphotungstic acid lignin ion exchange membrane.
本申请制备的聚四氟乙烯/全氟磺酸/耦合磷钨酸木质素离子交换膜以全氟磺酸为主体，将耦合磷钨酸木质素分散至PFSA溶液中，以多孔聚四氟乙烯薄膜为中间层，采用溶液铸膜法制备聚四氟乙烯/全氟磺酸/耦合磷钨酸木质素离子交换膜，利用耦合磷钨酸的木质素与多孔聚四氟乙烯层的协同作用，提高了聚四氟乙烯/全氟磺酸/耦合磷钨酸木质素离子交换膜的保水性、质子传导率、热和力学稳定性好以及电池性能。本申请整个制备过程所用设备具有价格低廉、原料成本低、操作便捷及环保等工业实用化特点，有助于推进质子交换膜燃料电池商业化隔膜材料的发展以及推进质子交换膜燃料电池的商业化生产。The polytetrafluoroethylene/perfluorosulfonic acid/coupled phosphotungstic acid lignin ion exchange membrane prepared by this application uses perfluorosulfonic acid as the main body, and the coupled phosphotungstic acid lignin is dispersed in the PFSA solution, and the porous polytetrafluoroethylene The film is the middle layer, and the solution casting method is used to prepare the polytetrafluoroethylene/perfluorosulfonic acid/coupled phosphotungstic acid lignin ion exchange membrane, and the synergistic effect of the coupled phosphotungstic acid lignin and the porous polytetrafluoroethylene layer, The water retention, proton conductivity, good thermal and mechanical stability and battery performance of polytetrafluoroethylene/perfluorosulfonic acid/coupled phosphotungstic acid lignin ion exchange membrane are improved. The equipment used in the entire preparation process of this application has the characteristics of low price, low raw material cost, convenient operation and environmental protection, etc., which is helpful to promote the development of commercial diaphragm materials for proton exchange membrane fuel cells and the commercialization of proton exchange membrane fuel cells Production.
本申请中，所述聚四氟乙烯/全氟磺酸/耦合磷钨酸木质素涂膜液涂布前还需要进行超声分散处理，得分散均匀的聚四氟乙烯/全氟磺酸/耦合磷钨酸木质素涂膜液。所述超声分散的功率为200～350W，所述超声分散的时间为20～50min；优选的，所述超声分散的功率为300W，所述超声分散的时间为30min。In this application, the PTFE/perfluorosulfonic acid/coupled phosphotungstic acid lignin coating solution needs to be subjected to ultrasonic dispersion treatment before coating to obtain uniformly dispersed PTFE/perfluorosulfonic acid/coupled Phosphotungstic acid lignin coating solution. The power of the ultrasonic dispersion is 200-350W, and the time of the ultrasonic dispersion is 20-50min; preferably, the power of the ultrasonic dispersion is 300W, and the time of the ultrasonic dispersion is 30min.
本申请中，所述基材为聚酰亚胺。In the present application, the substrate is polyimide.
优选的，所述干燥包括两步干燥处理；第一步干燥温度为80～100℃，第一步干燥时间为10～60min；第二步干燥温度为140～180℃，第二步干燥时间为1～3h；更优选的，第一步干燥温度为100℃，第一步干燥时间为30min；第二步干燥温度为160℃，第二步干燥时间为2h。Preferably, the drying includes two-step drying treatment; the drying temperature of the first step is 80-100°C, and the drying time of the first step is 10-60min; the drying temperature of the second step is 140-180°C, and the drying time of the second step is 1-3 hours; more preferably, the drying temperature of the first step is 100° C., and the drying time of the first step is 30 minutes; the drying temperature of the second step is 160° C., and the drying time of the second step is 2 hours.
优选的，所述再涂布聚四氟乙烯/全氟磺酸/耦合磷钨酸木质素涂膜液操作之前需要等待多孔聚四氟乙烯薄膜浸润1～30min；更优选的，所述再涂布聚四氟乙烯/全氟磺酸/耦合磷钨酸木质素涂膜液操作之前需要等待多孔聚四氟乙烯薄膜浸润10min。Preferably, before the recoating of polytetrafluoroethylene/perfluorosulfonic acid/coupled phosphotungstic acid lignin coating solution, it is necessary to wait for the porous polytetrafluoroethylene film to soak for 1 to 30 minutes; more preferably, the recoating It is necessary to wait for the porous PTFE film to soak for 10 minutes before applying the PTFE/perfluorosulfonic acid/coupled phosphotungstic acid lignin coating solution.
优选的，所述多孔聚四氟乙烯薄膜的孔隙大小为100～1000nm，厚度为5～10μm。Preferably, the porous polytetrafluoroethylene film has a pore size of 100-1000 nm and a thickness of 5-10 μm.
优选的，所述聚四氟乙烯/全氟磺酸/耦合磷钨酸木质素离子交换膜的厚度为10～40μm；综合考虑隔膜成本、稳定性、以及电池性能等因素，所述聚四氟乙烯/全氟磺酸/耦合磷钨酸木质素离子交换膜的厚度更优选为12～30μm。Preferably, the thickness of the polytetrafluoroethylene/perfluorosulfonic acid/coupled phosphotungstic acid lignin ion exchange membrane is 10-40 μm; comprehensively considering factors such as diaphragm cost, stability, and battery performance, the polytetrafluoroethylene The thickness of the ethylene/perfluorosulfonic acid/coupled phosphotungstic acid lignin ion exchange membrane is more preferably 12-30 μm.
本申请中，聚四氟乙烯/全氟磺酸/耦合磷钨酸木质素离子交换膜的原料组成中，耦合磷钨酸木质素的含量为0.1～15wt％；优选的，耦合磷钨酸木质素的含量为0.5～10wt％。In this application, in the raw material composition of polytetrafluoroethylene/perfluorosulfonic acid/coupled phosphotungstic acid lignin ion exchange membrane, the content of coupled phosphotungstic acid lignin is 0.1-15wt%; preferably, coupled phosphotungstic acid lignin The content of element is 0.5-10wt%.
综上所述，本申请具有以下有益效果：In summary, the application has the following beneficial effects:
1、本申请利用PFSA/PWA@lignin涂层与多孔聚四氟乙烯层的协同作用，提高了聚四氟乙烯/全氟磺酸/耦合磷钨酸木质素离子交换膜的保水性、质子传导率、热学稳定性和力学稳定性好，提高了膜在电池运行过程中的稳定性和寿命。1. This application uses the synergistic effect of PFSA/PWA@lignin coating and porous polytetrafluoroethylene layer to improve the water retention and proton conduction of polytetrafluoroethylene/perfluorosulfonic acid/coupled phosphotungstic acid lignin ion exchange membrane The efficiency, thermal stability and mechanical stability are good, which improves the stability and life of the membrane during battery operation.
2、本申请采用耦合磷钨酸木质素，其具有分散性好、亲水性好以及质子传导性高等优点，容易从分子尺度对质子传递通道进行调控，能实现质子快速传输，同时提高膜在高温低湿条件下的保水率。2. This application uses coupled phosphotungstic acid lignin, which has the advantages of good dispersibility, good hydrophilicity, and high proton conductivity. It is easy to regulate the proton transfer channel from the molecular scale, which can realize rapid proton transmission, and at the same time improve the membrane in Water retention under high temperature and low humidity conditions.
3、本申请制备的聚四氟乙烯/全氟磺酸/耦合磷钨酸木质素离子交换膜，利用耦合磷钨酸木质素表面富含磷钨酸、羟基等活性基团作为传导质子载体，耦合磷钨酸木质素具有良好的亲水性，可以为质子传输提供更多的传输通道，进而降低隔膜的电阻，大幅提高电池能量效率，促进质子交换膜燃料电池产业化的发展。3. The polytetrafluoroethylene/perfluorosulfonic acid/coupled phosphotungstic acid lignin ion exchange membrane prepared by this application uses active groups such as phosphotungstic acid and hydroxyl on the surface of the coupled phosphotungstic acid lignin as conductive proton carriers. Coupled phosphotungstic acid lignin has good hydrophilicity, which can provide more transmission channels for proton transport, thereby reducing the resistance of the diaphragm, greatly improving the energy efficiency of the battery, and promoting the industrialization of proton exchange membrane fuel cells.
4、本申请用溶液铸膜法制备的聚四氟乙烯/全氟磺酸/耦合磷钨酸木质素离子交换膜，整个制备过程中所用设备具有价格低廉、原料成本低、操作便捷及环保等工业实用化特点，有助于推进质子交换膜燃料电池商业化隔膜材料的发展以及推进质子交换膜燃料电池的商业化生产。4. In this application, the polytetrafluoroethylene/perfluorosulfonic acid/coupled phosphotungstic acid lignin ion exchange membrane is prepared by the solution casting method. The equipment used in the whole preparation process has the advantages of low price, low raw material cost, convenient operation and environmental protection, etc. The characteristics of industrial practicability are helpful to promote the development of commercial diaphragm materials for proton exchange membrane fuel cells and the commercial production of proton exchange membrane fuel cells.
附图说明Description of drawings
图1是实施例1制备的聚四氟乙烯/全氟磺酸/耦合磷钨酸木质素离子交换膜的图片。Figure 1 is a picture of the polytetrafluoroethylene/perfluorosulfonic acid/coupled phosphotungstic acid lignin ion exchange membrane prepared in Example 1.
图2是实施例1制备聚四氟乙烯/全氟磺酸/耦合磷钨酸木质素离子交换膜的水接触角示意图。Figure 2 is a schematic diagram of the water contact angle of the polytetrafluoroethylene/perfluorosulfonic acid/coupled phosphotungstic acid lignin ion exchange membrane prepared in Example 1.
图3是对比例1(型号为Gore 740的商业化PFSA膜)的水接触角示意图。3 is a schematic diagram of the water contact angle of Comparative Example 1 (the commercial PFSA membrane of Gore 740).
具体实施方式detailed description
木质素是一种化学稳定性良好、富含羟基亲水性强的天然环保性聚合物，其在自然界中产量丰富是造纸工业和燃料发酵工业的副产物。但是将 木质素直接掺入到PFSA基体中会降低隔膜中离子交换基团的密度。虽然木质素有一定的保水作用，但降低了膜的质子传导率。磷钨酸是酸性最强的杂多酸，其在聚合物基体中可以增强质子传导率。但是磷钨酸有一定的水溶性，会随着燃料电池的运行而溶解，影响电池的稳定性。本申请就是在此基础上进行研究的。Lignin is a natural and environmentally friendly polymer with good chemical stability, rich in hydroxyl and strong hydrophilicity. It is abundant in nature and is a by-product of the paper industry and fuel fermentation industry. However, direct incorporation of lignin into the PFSA matrix reduces the density of ion-exchange groups in the separator. Although lignin has a certain water retention effect, it reduces the proton conductivity of the membrane. Phosphotungstic acid is the most acidic heteropolyacid, which can enhance the proton conductivity in the polymer matrix. However, phosphotungstic acid has a certain water solubility and will dissolve with the operation of the fuel cell, affecting the stability of the battery. This application is researched on this basis.
以下结合实施例和附图对本申请作进一步详细说明。The present application will be described in further detail below in conjunction with the embodiments and accompanying drawings.
实施例Example
实施例1，提供了一种聚四氟乙烯/全氟磺酸/耦合磷钨酸木质素离子交换膜的制备方法，其具体步骤如下： Embodiment 1 provides a preparation method of polytetrafluoroethylene/perfluorosulfonic acid/coupled phosphotungstic acid lignin ion exchange membrane, the specific steps are as follows:
偶联剂改性木质素的制备：将质量比为1:1的木质素和3-氨基丙基三乙氧基硅烷加至体积比为1:9的去离子水和乙醇的混合溶液(木质素和偶联剂在去离子水和乙醇的混合溶液中的质量体积比为1/50g/mL)中，在30℃、1000r/min搅拌速度条件下反应12h，反应结束后，用去离子水反复离心洗涤反应产物，放入烘箱60℃，干燥24h，得偶联剂改性木质素；Preparation of coupling agent modified lignin: adding lignin and 3-aminopropyltriethoxysilane with a mass ratio of 1:1 to a mixed solution of deionized water and ethanol with a volume ratio of 1:9 (wood The mass volume ratio of the element and the coupling agent in the mixed solution of deionized water and ethanol is 1/50g/mL), reacted at 30°C and 1000r/min stirring speed for 12h, after the reaction, washed with deionized water The reaction product was repeatedly centrifuged and washed, put in an oven at 60°C, and dried for 24 hours to obtain coupling agent-modified lignin;
耦合磷钨酸木质素的制备：将上述制得的偶联剂改性木质素加入到10wt％磷钨酸水溶液中(偶联剂改性木质素的质量与10wt％磷钨酸水溶液的体积的比值为1/50g/mL)，在25℃下以1000r/min搅拌速度条件下反应12h后离心、用去离子水反复离心洗涤反应产物，得耦合磷钨酸木质素；Preparation of coupled phosphotungstic acid lignin: the coupling agent modified lignin prepared above is added to 10wt% phosphotungstic acid aqueous solution (the quality of coupling agent modified lignin and the volume of 10wt% phosphotungstic acid aqueous solution The ratio is 1/50g/mL), reacted for 12 hours at 25°C with a stirring speed of 1000r/min, centrifuged, and washed the reaction product repeatedly with deionized water to obtain coupled phosphotungstic acid lignin;
聚四氟乙烯/全氟磺酸/耦合磷钨酸木质素涂膜液的制备：将全氟磺酸树脂加入体积比为1:1的正丙醇和去离子的混合液(全氟磺酸树脂和混合液的质量比为1:20)，混合均匀后转移到高压反应釜内，在200℃反应6h，冷却至室温，得PFSA溶液；将上述制备的耦合磷钨酸木质素加入PFSA 溶液中(耦合磷钨酸木质素和全氟磺酸树脂的质量比为1:20)，在25℃下以1000r/min搅拌速度条件下反应30min，得聚四氟乙烯/全氟磺酸/耦合磷钨酸木质素涂膜液。Preparation of polytetrafluoroethylene/perfluorosulfonic acid/coupling phosphotungstic acid lignin coating solution: add perfluorosulfonic acid resin to a mixture of n-propanol and deionized solution with a volume ratio of 1:1 (perfluorosulfonic acid resin The mass ratio of the mixed liquid to the mixed solution is 1:20), mixed evenly, transferred to the autoclave, reacted at 200 ° C for 6 hours, cooled to room temperature, and obtained the PFSA solution; the coupled phosphotungstic acid lignin prepared above was added to the PFSA solution (The mass ratio of coupled phosphotungstic acid lignin and perfluorosulfonic acid resin is 1:20), and reacted for 30 minutes at 25°C with a stirring speed of 1000r/min to obtain PTFE/perfluorosulfonic acid/coupled phosphorus Tungstate lignin coating solution.
将上述制备的聚四氟乙烯/全氟磺酸/耦合磷钨酸木质素涂膜液在300W超声功率下超声分散30min，得分散均匀的聚四氟乙烯/全氟磺酸/耦合磷钨酸木质素涂膜液；The PTFE/perfluorosulfonic acid/coupled phosphotungstic acid lignin coating solution prepared above was ultrasonically dispersed for 30 minutes under 300W ultrasonic power to obtain uniformly dispersed PTFE/perfluorosulfonic acid/coupled phosphotungstic acid Lignin coating solution;
将分散均匀的聚四氟乙烯/全氟磺酸/耦合磷钨酸木质素涂膜液用刮刀涂覆在洁净的平整的聚酰亚胺薄膜的上表面并形成第一PFSA/PWA@lignin涂层；Coat the uniformly dispersed polytetrafluoroethylene/perfluorosulfonic acid/coupled phosphotungstic acid lignin coating solution on the upper surface of a clean and flat polyimide film to form the first PFSA/PWA@lignin coating Floor;
紧接着用厚度5μm的多孔聚四氟乙烯薄膜覆盖在第一PFSA/PWA@lignin涂层上；Then cover the first PFSA/PWA@lignin coating with a porous polytetrafluoroethylene film with a thickness of 5 μm;
让聚四氟乙烯/全氟磺酸/耦合磷钨酸木质素涂膜液在多孔聚四氟乙烯薄膜浸润10min；Let the polytetrafluoroethylene/perfluorosulfonic acid/coupled phosphotungstic acid lignin coating solution soak in the porous polytetrafluoroethylene film for 10 minutes;
在多孔聚四氟乙烯薄膜的上表面再涂布聚四氟乙烯/全氟磺酸/耦合磷钨酸木质素涂膜液并形成第二PFSA/PWA@lignin涂层(第二PFSA/PWA@lignin涂层与第一PFSA/PWA@lignin涂层的厚度相同)；On the upper surface of the porous polytetrafluoroethylene film, coat polytetrafluoroethylene/perfluorosulfonic acid/coupled phosphotungstic acid lignin coating solution and form the second PFSA/PWA@lignin coating (the second PFSA/PWA@ lignin coating is the same thickness as the first PFSA/PWA@lignin coating);
在100℃条件下干燥30min后，在160℃干燥2h，得聚四氟乙烯/全氟磺酸/耦合磷钨酸木质素离子交换膜。After drying at 100°C for 30 minutes, dry at 160°C for 2 hours to obtain a polytetrafluoroethylene/perfluorosulfonic acid/coupled phosphotungstic acid lignin ion exchange membrane.
实施例1制得的聚四氟乙烯/全氟磺酸/耦合磷钨酸木质素离子交换膜，厚度为17μm，由图1可知，实施例1制得的离子交换膜的质地均匀、致密，无多孔聚四氟乙烯薄膜、耦合磷钨酸木质素溶出现象，同时具有较好的柔韧性和机械性能。The polytetrafluoroethylene/perfluorosulfonic acid/coupled phosphotungstic acid lignin ion-exchange membrane prepared in Example 1 has a thickness of 17 μm. As can be seen from Figure 1, the ion-exchange membrane prepared in Example 1 has a uniform and dense texture. There is no porous PTFE film, coupled phosphotungstic acid lignin dissolution phenomenon, and has good flexibility and mechanical properties.
对实施例1制备的聚四氟乙烯/全氟磺酸/耦合磷钨酸木质素离子交换膜(即PTFE/PFSA/PWA@lignin复合隔膜)在25℃进行表面水接触角测试，测试效果见图2；进行吸水率、拉伸强度和质子传导率测试，测试数据见表1。For the polytetrafluoroethylene/perfluorosulfonic acid/coupled phosphotungstic acid lignin ion exchange membrane (ie PTFE/PFSA/PWA@lignin composite diaphragm) prepared in Example 1, the surface water contact angle was tested at 25°C, and the test results are shown in Figure 2; Water absorption, tensile strength and proton conductivity tests were performed, and the test data are shown in Table 1.
实施例2，一种聚四氟乙烯/全氟磺酸/耦合磷钨酸木质素离子交换膜的制备方法，与实施例1不同之处仅在于：耦合磷钨酸木质素和全氟磺酸树脂的质量比为1:100。Example 2, a preparation method of polytetrafluoroethylene/perfluorosulfonic acid/coupled phosphotungstic acid lignin ion exchange membrane, the only difference from Example 1 is: coupling phosphotungstic acid lignin and perfluorosulfonic acid The mass ratio of resin is 1:100.
实施例2制得的聚四氟乙烯/全氟磺酸/耦合磷钨酸木质素离子交换膜，厚度为11μm，厚度过薄，容易造成燃料渗透，比实施例1制备隔膜差，不利于电池长期运行。与实施例1制备的离子交换膜相比，实施例2制备的离子交换膜不利于质子交换膜燃料电池商业化应用。实施例2制得的离子交换膜的质地均匀、致密，无多孔聚四氟乙烯薄膜、耦合磷钨酸木质素溶出现象，同时具有较好的柔韧性和机械性能。The polytetrafluoroethylene/perfluorosulfonic acid/coupled phosphotungstic acid lignin ion exchange membrane prepared in Example 2 has a thickness of 11 μm, which is too thin to easily cause fuel permeation, which is worse than the membrane prepared in Example 1, which is not conducive to the battery long run. Compared with the ion exchange membrane prepared in Example 1, the ion exchange membrane prepared in Example 2 is not conducive to the commercial application of proton exchange membrane fuel cells. The ion-exchange membrane prepared in Example 2 has a uniform and dense texture, no porous polytetrafluoroethylene film, and no dissolution phenomenon of coupled phosphotungstic acid lignin, and has good flexibility and mechanical properties.
对实施例2制备的聚四氟乙烯/全氟磺酸/耦合磷钨酸木质素离子交换膜进行吸水率、拉伸强度和质子传导率测试，测试数据见表1。The water absorption, tensile strength and proton conductivity of the polytetrafluoroethylene/perfluorosulfonic acid/coupled phosphotungstic acid lignin ion exchange membrane prepared in Example 2 were tested, and the test data are shown in Table 1.
实施例3，一种聚四氟乙烯/全氟磺酸/耦合磷钨酸木质素离子交换膜的制备方法，与实施例1不同之处仅在于：耦合磷钨酸木质素和全氟磺酸树脂的质量比为1:10。Example 3, a preparation method of polytetrafluoroethylene/perfluorosulfonic acid/coupled phosphotungstic acid lignin ion exchange membrane, the only difference from Example 1 is: coupling phosphotungstic acid lignin and perfluorosulfonic acid The mass ratio of resin is 1:10.
实施例3制得的聚四氟乙烯/全氟磺酸/耦合磷钨酸木质素离子交换膜，厚度为23μm，实施例3制得的离子交换膜的质地均匀，但与实施例1制备的离子交换膜相比，实施例3制得的离子交换膜有耦合磷钨酸木质素团聚现象，，不适合在质子交换燃料电池中应用。The polytetrafluoroethylene/perfluorosulfonic acid/coupled phosphotungstic acid lignin ion-exchange membrane prepared in Example 3 has a thickness of 23 μm, and the ion-exchange membrane prepared in Example 3 has a uniform texture, but it is different from that prepared in Example 1. Compared with the ion-exchange membrane, the ion-exchange membrane prepared in Example 3 has the phenomenon of coupled phosphotungstic acid lignin agglomeration, and is not suitable for application in proton exchange fuel cells.
对实施例3制备的聚四氟乙烯/全氟磺酸/耦合磷钨酸木质素离子交换膜进行吸水率、拉伸强度和质子传导率测试，测试数据见表1。The water absorption, tensile strength and proton conductivity of the polytetrafluoroethylene/perfluorosulfonic acid/coupled phosphotungstic acid lignin ion exchange membrane prepared in Example 3 were tested, and the test data are shown in Table 1.
对比例comparative example
对比例1，提供了一种型号为Gore 740的商业化PFSA膜(即原始PFSA膜)。Comparative Example 1 provides a commercial PFSA membrane (i.e. the original PFSA membrane) that is Gore 740.
测试对比例1制备的聚四氟乙烯/全氟磺酸/耦合磷钨酸木质素离子交换膜在25℃的表面水接触角，测试效果见图3。从图2和图3可知，实施例1中聚四氟乙烯/全氟磺酸/耦合磷钨酸木质素离子交换膜的水接触角小于对比例1中型号为Gore 740的商业化PFSA膜的水接触角，说明聚四氟乙烯/全氟磺酸/耦合磷钨酸木质素离子交换膜的亲水性比型号为Gore 740的商业化PFSA膜好。测试对比例1制备的聚四氟乙烯/全氟磺酸/耦合磷钨酸木质素离子交换膜的吸水率、拉伸强度和质子传导率测试，测试数据见表1。The surface water contact angle of the polytetrafluoroethylene/perfluorosulfonic acid/coupled phosphotungstic acid lignin ion exchange membrane prepared in Comparative Example 1 was tested at 25°C, and the test results are shown in Figure 3. As can be seen from Figure 2 and Figure 3, the water contact angle of polytetrafluoroethylene/perfluorosulfonic acid/coupled phosphotungstic acid lignin ion exchange membrane in Example 1 is less than that of the commercialized PFSA membrane of Gore 740 in Comparative Example 1 The water contact angle shows that the hydrophilicity of polytetrafluoroethylene/perfluorosulfonic acid/coupled phosphotungstic acid lignin ion exchange membrane is better than that of the commercial PFSA membrane of model Gore 740. Test the water absorption, tensile strength and proton conductivity of the polytetrafluoroethylene/perfluorosulfonic acid/coupled phosphotungstic acid lignin ion exchange membrane prepared in Comparative Example 1. The test data are shown in Table 1.
表1Table 1
Figure PCTCN2021139302-appb-000001
Figure PCTCN2021139302-appb-000001
由表1可知，实施例制备的聚四氟乙烯/全氟磺酸/耦合磷钨酸木质素离子交换膜的吸水率高于型号为Gore 740的商业化PFSA膜的吸水率。且实施例1-2的拉伸强度和质子传导率均优于型号为Gore 740的商业化PFSA膜，已经适应在质子交换膜燃料电池的应用要求，可以促进质子交换膜燃料电池的工业化发展。It can be seen from Table 1 that the water absorption of the polytetrafluoroethylene/perfluorosulfonic acid/coupled phosphotungstic acid lignin ion exchange membrane prepared in the embodiment is higher than that of the commercial PFSA membrane of Gore 740. Moreover, the tensile strength and proton conductivity of Examples 1-2 are better than the commercial PFSA membrane of Gore 740, which has been adapted to the application requirements of proton exchange membrane fuel cells and can promote the industrial development of proton exchange membrane fuel cells.
本具体实施例仅仅是对本申请的解释，其并不是对本申请的限制，本领域技术人员在阅读完本说明书后可以根据需要对本实施例做出没有创造性贡献的修改，但只要在本申请的权利要求范围内都受到专利法的保护。This specific embodiment is only an explanation of this application, and it is not a limitation of this application. Those skilled in the art can make modifications to this embodiment without creative contribution according to needs after reading this specification, but as long as the rights of this application All claims are protected by patent law.

Claims (14)

  1. 一种聚四氟乙烯/全氟磺酸/耦合磷钨酸木质素涂膜液，其特征在于，其制备原料包括耦合磷钨酸木质素、全氟磺酸树脂和溶剂；所述耦合磷钨酸木质素和全氟磺酸树脂的质量比为(0.1～15):100。A polytetrafluoroethylene/perfluorosulfonic acid/coupled phosphotungstic acid lignin coating solution is characterized in that its preparation raw materials include coupled phosphotungstic acid lignin, perfluorosulfonic acid resin and solvent; the coupled phosphotungstic acid The mass ratio of acid lignin and perfluorosulfonic acid resin is (0.1-15):100.
  2. 根据权利要求1所述的聚四氟乙烯/全氟磺酸/耦合磷钨酸木质素涂膜液，其特征在于，所述耦合磷钨酸木质素的制备原料包括偶联剂改性木质素和磷钨酸水溶液；所述偶联剂改性木质素和磷钨酸水溶液的质量比为1:(10～100)。The polytetrafluoroethylene/perfluorosulfonic acid/coupled phosphotungstic acid lignin coating liquid according to claim 1, characterized in that, the raw materials for the preparation of the coupled phosphotungstic acid lignin include coupling agent modified lignin and phosphotungstic acid aqueous solution; the mass ratio of the coupling agent modified lignin and phosphotungstic acid aqueous solution is 1:(10～100).
  3. 根据权利要求2所述的聚四氟乙烯/全氟磺酸/耦合磷钨酸木质素涂膜液，其特征在于，所述偶联剂改性木质素的制备方法为：将木质素、偶联剂加至去离子水和乙醇的混合溶液中，在20～80℃、搅拌反应1～24h，离心、洗涤、干燥后得偶联剂改性木质素。The polytetrafluoroethylene/perfluorosulfonic acid/coupling phosphotungstic acid lignin coating solution according to claim 2, wherein the preparation method of the coupling agent modified lignin is as follows: lignin, coupling The coupling agent is added to the mixed solution of deionized water and ethanol, stirred and reacted at 20-80° C. for 1-24 hours, centrifuged, washed and dried to obtain the coupling agent-modified lignin.
  4. 根据权利要求3所述的聚四氟乙烯/全氟磺酸/耦合磷钨酸木质素涂膜液，其特征在于，所述木质素和偶联剂的质量比为1:(0.1～10)。The polytetrafluoroethylene/perfluorosulfonic acid/coupled phosphotungstic acid lignin coating solution according to claim 3, wherein the mass ratio of the lignin to the coupling agent is 1:(0.1～10) .
  5. 根据权利要求3所述的聚四氟乙烯/全氟磺酸/耦合磷钨酸木质素涂膜液，其特征在于，所述偶联剂选自3-氨基丙基三乙氧基硅烷、3-氨基丙基三甲氧基硅烷和N-(2-氨基乙基)-3-氨基丙基三甲氧基硅烷中的一种或多种。The polytetrafluoroethylene/perfluorosulfonic acid/coupled phosphotungstic acid lignin coating liquid according to claim 3, wherein the coupling agent is selected from 3-aminopropyl triethoxysilane, 3 - one or more of aminopropyltrimethoxysilane and N-(2-aminoethyl)-3-aminopropyltrimethoxysilane.
  6. 根据权利要求2所述的聚四氟乙烯/全氟磺酸/耦合磷钨酸木质素涂膜液，其特征在于，所述磷钨酸水溶液的浓度为1～20wt％。The polytetrafluoroethylene/perfluorosulfonic acid/coupled phosphotungstic acid lignin coating solution according to claim 2, characterized in that the concentration of the phosphotungstic acid aqueous solution is 1-20 wt%.
  7. 根据权利要求2所述的聚四氟乙烯/全氟磺酸/耦合磷钨酸木质素涂膜液，其特征在于，所述耦合磷钨酸木质素的制备方法为：将偶联剂改性木质素和磷钨酸水溶液混合，搅拌反应，离心，洗涤，干燥后得耦合磷钨酸 木质素。The polytetrafluoroethylene/perfluorosulfonic acid/coupled phosphotungstic acid lignin coating liquid according to claim 2, characterized in that, the preparation method of the coupled phosphotungstic acid lignin is: modifying the coupling agent Lignin and phosphotungstic acid aqueous solution are mixed, stirred for reaction, centrifuged, washed, and dried to obtain coupled phosphotungstic acid lignin.
  8. 权利要求1-7中任一项所述的聚四氟乙烯/全氟磺酸/耦合磷钨酸木质素涂膜液的制备方法，其特征在于，包括如下步骤：The preparation method of the polytetrafluoroethylene/perfluorosulfonic acid/coupled phosphotungstic acid lignin coating liquid described in any one of claims 1-7, is characterized in that, comprises the following steps:
    S1、将全氟磺酸树脂加入和溶剂混合，混合均匀后转移到反应釜内，在180～240℃反应2～8h，冷却，得PFSA溶液；所述全氟磺酸树脂和溶剂的质量比为(1～20):100；S1. Add the perfluorosulfonic acid resin and mix it with the solvent, transfer it to the reaction kettle after mixing evenly, react at 180-240°C for 2-8 hours, and cool to obtain the PFSA solution; the mass ratio of the perfluorosulfonic acid resin to the solvent For (1～20):100;
    S2、将耦合磷钨酸木质素加入S1步骤制得的PFSA溶液中，搅拌均匀，得聚四氟乙烯/全氟磺酸/耦合磷钨酸木质素涂膜液。S2. Add coupled phosphotungstic acid lignin to the PFSA solution prepared in step S1, and stir evenly to obtain a polytetrafluoroethylene/perfluorosulfonic acid/coupled phosphotungstic acid lignin coating liquid.
  9. 一种聚四氟乙烯/全氟磺酸/耦合磷钨酸木质素离子交换膜，其特征在于，含有由权利要求1-7中任一项所述的一种聚四氟乙烯/全氟磺酸/耦合磷钨酸木质素涂膜液制得的涂层。A polytetrafluoroethylene/perfluorosulfonic acid/coupled phosphotungstic acid lignin ion exchange membrane, characterized in that it contains a polytetrafluoroethylene/perfluorosulfonic acid described in any one of claims 1-7 Coating made of acid/coupling phosphotungstic acid lignin coating solution.
  10. 一种权利要求9所述的聚四氟乙烯/全氟磺酸/耦合磷钨酸木质素离子交换膜的制备方法，其特征在于，包括以下步骤：A preparation method of polytetrafluoroethylene/perfluorosulfonic acid/coupled phosphotungstic acid lignin ion exchange membrane according to claim 9, characterized in that it comprises the following steps:
    将聚四氟乙烯/全氟磺酸/耦合磷钨酸木质素涂膜液涂布到基材的上表面并形成第一PFSA/PWA@lignin涂层；Coating polytetrafluoroethylene/perfluorosulfonic acid/coupled phosphotungstic acid lignin coating solution to the upper surface of the substrate and forming the first PFSA/PWA@lignin coating;
    将多孔聚四氟乙烯薄膜覆盖到第一PFSA/PWA@lignin涂层上；Overlay the porous PTFE film onto the first PFSA/PWA@lignin coating;
    在多孔聚四氟乙烯薄膜的上表面再涂布聚四氟乙烯/全氟磺酸/耦合磷钨酸木质素涂膜液并形成第二PFSA/PWA@lignin涂层；Coat the upper surface of the porous PTFE film with PTFE/perfluorosulfonic acid/coupled phosphotungstic acid lignin coating solution and form the second PFSA/PWA@lignin coating;
    干燥，冷却至室温，剥离基材，得聚四氟乙烯/全氟磺酸/耦合磷钨酸木质素离子交换膜。Dry, cool to room temperature, and peel off the substrate to obtain a polytetrafluoroethylene/perfluorosulfonic acid/coupled phosphotungstic acid lignin ion exchange membrane.
  11. 根据权利要求10所述的聚四氟乙烯/全氟磺酸/耦合磷钨酸木质素离子交换膜的制备方法，其特征在于，所述干燥包括两步干燥处理；第一步 干燥温度为80～100℃，第一步干燥时间为10～60min；第二步干燥温度为140～180℃，第二步干燥时间为1～3h。The preparation method of polytetrafluoroethylene/perfluorosulfonic acid/coupling phosphotungstic acid lignin ion exchange membrane according to claim 10, is characterized in that, described drying comprises two-step drying treatment; The first step drying temperature is 80 ~100°C, the drying time of the first step is 10~60min; the drying temperature of the second step is 140~180°C, and the drying time of the second step is 1~3h.
  12. 根据权利要求10所述的聚四氟乙烯/全氟磺酸/耦合磷钨酸木质素离子交换膜的制备方法，其特征在于，所述再涂布聚四氟乙烯/全氟磺酸/耦合磷钨酸木质素涂膜液操作之前需要等待多孔聚四氟乙烯薄膜浸润1～30min。The preparation method of polytetrafluoroethylene/perfluorosulfonic acid/coupled phosphotungstic acid lignin ion exchange membrane according to claim 10, characterized in that, the recoated polytetrafluoroethylene/perfluorosulfonic acid/coupled Before operating the phosphotungstic acid lignin coating solution, it is necessary to wait for the porous polytetrafluoroethylene film to soak for 1 to 30 minutes.
  13. 根据权利要求10所述的聚四氟乙烯/全氟磺酸/耦合磷钨酸木质素离子交换膜的制备方法，其特征在于，所述多孔聚四氟乙烯薄膜的孔隙大小为100～1000nm，厚度为5～10μm。The preparation method of polytetrafluoroethylene/perfluorosulfonic acid/coupled phosphotungstic acid lignin ion exchange membrane according to claim 10, characterized in that the pore size of the porous polytetrafluoroethylene film is 100-1000nm, The thickness is 5-10 μm.
  14. 根据权利要求10所述的聚四氟乙烯/全氟磺酸/耦合磷钨酸木质素离子交换膜的制备方法，其特征在于，所述聚四氟乙烯/全氟磺酸/耦合磷钨酸木质素离子交换膜的厚度为10～40μm。The preparation method of polytetrafluoroethylene/perfluorosulfonic acid/coupled phosphotungstic acid lignin ion exchange membrane according to claim 10, characterized in that, the polytetrafluoroethylene/perfluorosulfonic acid/coupled phosphotungstic acid The thickness of the lignin ion exchange membrane is 10-40 μm.
PCT/CN2021/139302 2021-06-26 2021-12-17 Method for preparing polytetrafluoroethylene/perfluorosulfonic acid/coupled phosphotungstic acid lignin ion exchange membrane WO2022267392A1 (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101173107A (en) * 2007-10-23 2008-05-07 福州大学 Raw material prescription for xylogen-inorganic nano composite material producing process thereof
CN101777659A (en) * 2009-12-07 2010-07-14 山东东岳神舟新材料有限公司 Perfluorosulfonic composite proton exchange membrane for fuel cell
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